Citation
Thermal and photochemical studies of 9,10-BIS(trifluoroethenyl) phenanthrene and perfluoro-E,Z,E- and E,E,E-4,5-dimethyl-2,4,6-octatriene and thermal studies of terminally fluorinated 1,5-dienes

Material Information

Title:
Thermal and photochemical studies of 9,10-BIS(trifluoroethenyl) phenanthrene and perfluoro-E,Z,E- and E,E,E-4,5-dimethyl-2,4,6-octatriene and thermal studies of terminally fluorinated 1,5-dienes
Creator:
Palmer, Keith W., 1966-
Publication Date:
Language:
English
Physical Description:
ix, 197 leaves : ill. ; 29 cm.

Subjects

Subjects / Keywords:
Boats ( jstor )
Carbon ( jstor )
Ethers ( jstor )
Flames ( jstor )
Fluorine ( jstor )
Hydrocarbons ( jstor )
Mass spectra ( jstor )
Orbitals ( jstor )
Photolysis ( jstor )
Thermal decomposition ( jstor )
Chemistry thesis Ph. D ( lcsh )
Dissertations, Academic -- Chemistry -- UF ( lcsh )
Fluorine compounds ( lcsh )
Photochemistry ( lcsh )
Thermal analysis ( lcsh )
City of Gainesville ( local )
Genre:
bibliography ( marcgt )
non-fiction ( marcgt )

Notes

Thesis:
Thesis (Ph. D.)--University of Florida, 1993.
Bibliography:
Includes bibliographical references (leaves 189-196).
General Note:
Typescript.
General Note:
Vita.
Statement of Responsibility:
by Keith W. Palmer.

Record Information

Source Institution:
University of Florida
Holding Location:
University of Florida
Rights Management:
Copyright [name of dissertation author]. Permission granted to the University of Florida to digitize, archive and distribute this item for non-profit research and educational purposes. Any reuse of this item in excess of fair use or other copyright exemptions requires permission of the copyright holder.
Resource Identifier:
001938258 ( ALEPH )
30947327 ( OCLC )
AKB4394 ( NOTIS )

Downloads

This item has the following downloads:


Full Text









THERMAL AND PHOTOCHEMICAL STUDIES OF
9,10-BIS(TRIFLUOROETHENYL)PHENANTHRENE AND
PERFLUORO-E,Z,E- AND E,E,E-4,5-DIMETHYL-2,4,6-OCTATRIENE AND
THERMAL STUDIES OF TERMINALLY FLUORINATED 1,5-DIENES













By

KEITH W. PALMER


A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY


UNIVERSITY OF FLORIDA

1993
UNIVERSITY OF FLORIDA LIBRARIES




THERMAL AND PHOTOCHEMICAL STUDIES OF
9,10-BIS(TRIFLUOROETHENYL)PHENANTHRENE AND
PERFLUORO-E,Z,E- AND E.E.E-^-DIMETHYL^Ae-OCTATRIENE AND
THERMAL STUDIES OF TERMINALLY FLUORINATED 1,5-DIENES
By
KEITH W. PALMER
A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
1993
UNIVERSITY OF FLORIDA LIBRARIES


TO DAD, MOM, JACQUELINE, HELEN AND KARYN


ACKNOWLEDGEMENTS
A complete list of all of the friends I am indebted to for assisting me to this
point would require a dissertation in itself. Hopefully in this short space I can
give justice to a few, with the many not mentioned being assured that they will
always be in my thoughts.
I wish to express my gratitude for the excellent guidance and friendship
of my advisor, Professor William R. Dolbier, Jr. Besides attempting to attain a
fraction of his vast knowledge of chemistry, and perhaps more important, I leave
with an appreciation for his understanding, and his methods of motivating those
around him in a positive fashion. With Professor Dolbier, the chemistry is
always surmountable and one comes away with a positive feeling towards
oneself and the tasks ahead. Such an attitude is refreshing in times of stress
and leads to an enjoyable and rewarding experience.
The love and support of my parents and sisters was and will always be
essential. No matter where they live, it is always "home" when I make it away to
see them and the time spent together is cherished. The valuable lessons
learned at a younger age--from Dad's "Pick up the tools!" to Moms "Stop
procrastinating, and get to your homework!"--echo in my head from time to time
and raise my level of productivity.
The friends and colleagues I have met since at the University of Florida
Department of Chemistry are numerous. Greatly appreciated are the
exceptional faculty members I have had the opportunity to interact with and
whose courses helped to form the core of my chemical intuition. Due to my
extended stay in the Dolbier group, thanks are required to a number of


labmates: Sarah Weaver for her help in learning the ropes around the lab and
roller-blading companionship; Conrad Burkholder for numerous stimulating
discussions; Jeff Keaffaber, Laurent Wedlinger, Hania Wotowicz, Lech
Celewicz, Mohammed Alii Asghar, Hua Qi Zhang, He Qi Pan, Wen Juan Cao,
Xiao Xin Rong, and more recently Martin McClinton, Mike Bartberger and
Michelle Fletcher, all for providing valuable friendships. Last and certainly not
least, special thanks go to Dr. Henryk Koroniak. A true friend, Henryk is greatly
appreciated for teaching me a variety of technical skills and returning more than
once at just the right time to give me a fresh charge of enthusiasm.
Outside the Dolbier group, I will always remember my pistachio addicted
roommates and true friends Kevin Kinter and Brent Kleintop. The
companionship and good times we had together helped maintain proper
perspective and kept me from spending too much time in the lab.
IV


TABLE OF CONTENTS
ACKNOWLEDGEMENTS iii
ABSTRACT vii
CHAPTER
1 AN OVERVIEW OF FLUORINE SUBSTITUENT EFFECTS IN
ORGANIC SYSTEMS 1
Introduction 1
Fluoroalkanes 2
Fluoroalkenes 5
Fluorine Non-bonded Electron Interactions 8
Fluorine Steric Effects : 11
The Thermal Cyclobutene/1,3-Diene Electrocyclic Process 13
Conclusions 22
2 THERMAL AND PHOTOCHEMICAL REARRANGEMENTS OF
9,10-BIS(TRIFLUOROETHENYL)PHENANTHRENE AND
PERFLUORO-E,E,E-(AND E,Z,E-)4,5-DIMETHYL-2,4,6-OCTATRIENE 23
Introduction 23
Development of a Suitable 1,3(Z),5-Triene/1,3-Cyclohexadiene
System 27
Thermal Study of 9,10-Bis(trifluoroethenyl)phenanthrene 31
Thermal Study of Perfluoro-E,Z,E(E,E,E)-4,5-dimethyl-2,4,6-
octatriene 33
Photochemical Rearrangements of 9,10 Bis(trifluoroethenyl)phenan-
threne and Perfluoro-E,Z,E(E,E,E)-4,5-dimethyl-2,4,6-octatriene 40
Discussion 45
Conclusions 77
3 [3,3]-SIGMATROPIC REARRANGEMENTS OF TERMINALLY
FLUORINATED 1,5-DIENES 79
Introduction 79
The [3,3]-Sigmatropic Shift of 1,5-Dienes: The Cope Rearrangement 80
Fluorinated Cope Systems 82
Synthesis and Thermolysis of Terminally Fluorinated Cope Systems 86
1,1,6,6-Tetrafluoro-1,5-hexadiene 86
1-Difluoromethylidene-4-methylidenecyclohexane 89
v


1,4-D¡(d¡fluoromethyl¡dene)cyclohexane 91
meso- and c/,/-1-(2-Difluorcmethylidenecyclopentyl)-2-
difluoromethylidenecyclopentane 94
Discussion 95
Conclusions 109
4 EXPERIMENTAL 111
General Methods 111
Experimental Procedures 112
APPENDIX A: GAS PHASE THERMOLYSIS APPARATUS 160
APPENDIX B: SELECTED 19F NMR SPECTRA 163
REFERENCES 189
BIOGRAPHICAL SKETCH 197
VI


Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy
THERMAL AND PHOTOCHEMICAL STUDIES OF
9,10-BIS(TRIFLUOROETHENYL)PHENANTHRENE AND
PERFLUORO-E,Z,E- AND E,E,E-4,5-DIMETHYL-2,4,6-OCTATRIENE AND
THERMAL STUDIES OF TERMINALLY FLUORINATED 1,5-DIENES
By
Keith W. Palmer
August 1993
Chairman: William R. Dolbier, Jr.
Major Department: Chemistry
Thermolysis of 9,10-bis(trifluoroethenyl)phenanthrene was examined in
solution between 140C and 193C, and led to formation of 1,2,2,3,3,4-
hexafluoro-2,3-dihydrotriphenylene and 1,4,4,5,6,6-hexafluoro-2,3-(9,10-
phenanthro)bicyclo[3.1.0]hex-2-ene by irreversible, competitive first-order
processes. The competitive formation of 1,4,4,5,6,6-hexafluoro-2,3-(9,10-
phenanthro)bicyclo[3.1.0]hex-2-ene is virtually unprecedented in 1,3,5-triene
thermal chemistry with only one similar cyclization found in the hydrocarbon
literature. Thermolysis of 1,4,4,5,6,6-hexafluoro-2,3-(9,10-phenanthro)-
bicyclo[3.1.0]hex-2-ene led to further rearrangement and was examined in
solution between 180C and 193C. This material was found to rearrange to 4-
difluoromethylidene-3,3,5,5-tetrafluoro-1,2-(9,10-phenanthro)cyclopent-1 -ene
vii


and 1,2-(9,10-phenanthro)-3,5,5-trifluoro-4-trifluoromethyl-1,3-cyclopentadiene
through irreversible, competitive first-order processes.
Photolysis of 9,10-bis(trifluoroethenyl)phenanthrene in solution led to
1.4.4.5.6.6-hexafluoro-2,3-(9,10-phenanthro)bicyclo[3.1.0]hex-2-ene as the
major product with 1,2,2,3,3,4-hexafluoro-2,3-dihydrotriphenylene and [2n+2n]
cycloaddition products 1,4,5,5,6,6,-hexafluoro-2,3-(9,10-phenanthro)-
bicyclo[2.1,1]hex-2-ene and 1,4,5,5,6,6-hexafluoro-2,3-(9,10-phenanthro)-
bicyclo[2.2.0]hex-2-ene being observed in minor amounts.
Thermolysis of perfluoro-E,Z,E- and E,E,E-4,5-dimethyl-2,4,6-octatriene
was studied in solution between 154C and 202C and initially found to
undergo C4-C5 double bond isomerization. At higher temperatures, an
equilibrium between the perfluorooctatriene and perfluoro-c/'s- and frans-1,3,4-
trimethyl-4-(E-1-propenyl)cyclobutene is established requiring an 4rc electron,
conrotatory electrocyclic process.
Photolysis of perfluoro-E,Z,E- and E,E,E-4,5-dimethyl-2,4,6-octatriene in
solution leads to formation of perfluoro-frans-2,3,5,6-tetramethyl-1,3-
cyclohexadiene by a 6tt electron, conrotatory electrocyclic process. This
material was found to undergo further photo-cyclization to perfluoro-trans-
2.3.5.6-tetramethylbicyclo[2.2.0]hex-2-ene through a 47c electron, disrotatory
electrocyclic process.
Reluctance of these perfluorinated-1,3(Z),5-trienes to undergo the
thermal, 6n electron, disrotatory electrocyclization via the required boat
transition state was evident, as was the facility of the photoprocess to occur
through the photo-allowed 6n electron, conrotatory electrocyclization via a chair
transition state. This disparity was believed to arise from a detrimental
interaction between terminal cis fluorines as the 1,3(Z),5-triene approaches the
boat-like disrotatory transition state and required further study.
VIII


The system chosen to probe this effect was the thermal [3,3]-sigmatropic
rearrangement of terminally gem-difluorinated 1,5-dienes. Synthesis and gas
phase thermal study of 1,1,6,6-tetrafluoro-1,5-hexadiene, 1-difluoro-
methylidene-4-methylidenecyclohexane, 1,4-di(difluoromethylidene)cyclo-
hexane, and solution phase thermal study of meso- and af,/-1-(2*
difluoromethylidenecyclopentyl)-2-difluoromethylidenecyclopentane, were
carried out and the transformations found to occur by well-behaved, irreversible,
first-order processes to the respective [3,3]-shift products. Comparison of the
measured activation parameters for these processes and values for the
corresponding hydrocarbon and partially fluorinated 1,5-dienes from the
literature indicates that terminal gem-difluorination accelerates thermal
processes occurring through chair transition states while inhibiting processes
occurring through boat transition states.
IX


CHAPTER 1
AN OVERVIEW OF FLUORINE SUBSTITUENT EFFECTS
IN ORGANIC SYSTEMS
Introduction
The isolation of fluorine by Henri Moissan on June 26, 1886, created
considerable academic interest, and led to rapid advances in the field of
fluorine chemistry.1 In 1930, Midgely and Henne developed CF2CI2 as a cheap
and safe refrigerant to replace the toxic gas ammonia which elevated fluorine
chemistry out of it's status as an academic novelty and initiated the organo-
fluorine industry. Due to the Manhattan Project and nuclear energy applications
in the early 1940s, large scale production of elemental fluorine became
necessary. The post-World War Two era saw intense interest in organo-fluorine
chemistry develop in industrial and academic sectors. This interest was
primarily due to the fascinating properties exhibited by fluoroorganic materials
developed during the concentrated research directed towards production of the
atomic bomb. Fluorine exhibits remarkable effects when utilized as a
substituent in organic systems and a variety of factors intrinsic to the fluorine
atom are responsible. The purpose of this introduction is to address factors
which will be pertinent within this current study by reviewing fluorine effects in a
series of simple and well characterized organic systems.
The effects exhibited by fluorine as a substituent are due to three intrinsic
characteristics of the fluorine atom; extreme electronegativity, non-bonded
electron pairs, and small relative size. Fluorine is the most electronegative of all
1


2
elements with a Pauling scale value of 4.10 as compared with oxygen (3.50),
chlorine (2.83), bromine (2.74), carbon (2.50), and hydrogen (2.20).2 Strong
polarization of fluorinated molecules through the a bonding framework and
through space (field effects) are results of fluorine's large electronegativity. The
atom is mono-valent and accommodates three non-bonded electron pairs in
orbitals of similar dimension to hybridized orbitals on carbon.3 Because of
these two preceding factors, fluorine exhibits an interesting donor/acceptor
contradiction under certain circumstances in that the strong removal of electron
density from a bound atom can be offset due to back donation of density from
the non-bonded electrons. The van der Waals radius of fluorine is 1.47 .4
Compared with the other halogens, carbon, and hydrogen (van der Waals radii:
Cl, 1.73 ; Br, 1.84 ; I, 2.01 ; Caiipha,|C, 1.70 ; H, 1.20 ),4 fluorine should
exhibit minimal spatial requirements as a substituent, a fact which has allowed
for complete substitution of hydrogen by fluorine in many hydrocarbon systems.
This has enabled the completely synthetic field of perfluorocarbon chemistry to
be developed and exploited by industry and academics with substantial
financial and scholarly success.
The effects of fluorine as a substituent in organic systems have been the
subject of a number of reviews,1'5'6'7'8 those of Smart5 6 being most insightful.
This introduction will demonstrate the ways in which fluorine substitution
perturbs the structure and reactivity of simple hydrocarbons.
Fluoroalkanes
The series of fluorinated methanes show an interesting trend in C-F
bonding. Table 1-15 illustrates the strengthening and incremental shortening of
the C-F bond in this series. This trend of bond strengthening with increased


3
Table 1-1. C-F Bond Lengths and Dissociation Energies in Fluoromethanes.
Fluoromethane
r (C-F) iAl
D(C-F) (kcal/mol)
ch3f
1.385
109.0
ch2f2
1.358
122
chf3
1.332
128.0
cf4
1.317
129.7
Table 1-2. Bond Lengths and Dissociation Energies in Fluoroethanes.
Fluoroethane
r (C-C)jAl
D(C-C) (kcal/mol)
DfC-F) (kcal/mol)
ch3-ch3
1.532
90.4
-
ch3-ch2f
1.502
91.2
107.7
ch3-chf2
1.498
95.6
Unknown
ch3-cf3
1.494
101.2
124.8
fch2-cf3
1.501
94.6
109.4 (CH2F)
cf3-cf3
1.545
98.7
126.8
substitution is unique to fluorine among the halogens. The series of chlorinated
methanes exhibits a similar bond shortening but is accompanied by an
incremental weakening; 83.7 kcal/mol down to 72.9 kcal/mol per first C-CI bond
homolysis in the series from CH3CI to CCI4.5
Table 1-26 illustrates the effect of successive fluorination on the bond
lengths and strengths in the case of ethane. Geminal fluorination leads to
strengthening and shortening of the C-C bond in the series CH3-CH3 to CH3-
CF3. The C-C bond lengths increase upon vicinal fluorination from CH3-CF3 to
CF3-CF3 while the C-C bond strength decreases. The C-F bond strengths in the


4
series of ethanes follows a similar trend of strengthening with increased
geminal fluorination as observed in the series of methanes.
As of this time, the trends in C-C bond strengths and lengths with various
degrees of fluorination has not been fully explained. However, valence bond
arguments have been used to rationalize the observed trends in C-F bonding in
alkanes. As previously mentioned, fluorine contains three non-bonded electron
pairs in orbitals of dimension which can accommodate appreciable overlap with
orbitals of other period two elements. It is rationalized that for carbon
substituted with two or more fluorines, double-bond no-bond resonance
structures, or negative hyperconjugation, as shown in the classical sense by
Figure 1-1, lead to increased bond order between the carbon and fluorine.39'10
f F-
Figure 1-1. Fluorine Double-bond, No-bond Resonance.
As the degree of geminal fluorination increases, the number of valence bond
structures involving doubly bound fluorine increases and the C-F bonds are
increasingly shorter and stronger. Theoretical calculations at the ab initio level
have confirmed such a bonding scheme where it is found that the stabilizing
interaction arises from back-donation of a fluorine lone pair into an antibonding
o*c-f orbital.9'1011 This explanation based on fluorine non-bonded electron
interactions to rationalize the observed bonding and geometry characteristics in
fluoro-organics is complemented by other arguments which inherently do not
involve the non-bonding electrons on fluorine. One such argument suggests
that when carbon is bound to more electronegative elements, atomic p
character concentrates in orbitals directed towards the electronegative species


5
since p electrons are less tightly bound than s electrons.12'13 Carbon
rehybridization then assists in accounting for bonding and geometry trends in
fluoro-organics. Another argument arising from ab initio level theoretical study
attributes bond shortening to Coulombic interactions between oppositely
charged fluorine and carbon.14 In effect, an increase in C-F bond ionic
character is predicted as the degree of fluorination increases. Calculations
indicate the trend arises from negligible change in charge on fluorine but
considerable increase in positive charge on carbon as the degree of
fluorination increases. The variety of rationalizations for C-F bonding in such
simple systems illustrates the complexities in theoretically and certainly
qualitatively explaining bonding trends in fluoroorganic systems.
Fluoroalkenes
Fluorine substitution at a vinylic carbon leads to substantial changes in
alkene geometry and reactivity. The data in Table 1-456 reveal that
fluoroethylenes have shorter C=C bonds than ethylene and the C-F bond
lengths are shorter than similarly geminal or vicinal fluorinated alkanes. The
Table 1-4. Structural Aspects of Fluoroethylenes.
CH2=CH2
ch2=chf
ch2=cf2
CHF=CFo
CFo=CFo
r(C-C)
1.339
1.333
1.315
1.309
1.311
r(C-F)
-
1.348
1.323
1.32
1.319
H-C-H deg
117.8
120.4
121.8
-
-
H-C-F deg
-
115.4
-
116.2
-
F-C-F deg
-
-
109.3
112.2
112.5
Dn kcal/mol
59.1
Unknown
62.1
Unknown
52.3


6
geminally difluorinated olefins contain FCF bond angles which are much
smaller than ethylene and very close to the tetrahedral value of 109.47.
Theoretical ab initio level calculations show the C-F bond shortening can be
attributed to fluorine non-bonded electron delocalization into the 7t(c=c)
molecular orbital as depicted in a valence bond fashion by Figure 1-2.915'16 FCF
bond angle contraction in this case may be rationalized by attraction between
the charged and neutral fluorine atoms.16
Figure 1-2. Fluorine Non-bonded Electron Pair Delocalization in Alkenes.
Fluoroalkene Reactivities
Reactivities in fluoroalkene series lead in some cases to clear trends as
the degree of olefin fluorination is changed, but are often found to be specific to
the olefin and transformation in question. Generally, reactions involving
transformation of unsaturated, fluorine substituted carbon to a saturated state
are more exothermic than the process for a similar hydrocarbon. Table 1-56
illustrates the increasing exothermicity for hydrogenations in the series of
fluoroethylenes, CH2=CHF clearly deviating from the trend. Other reactions
involving saturation of CF2=CF2's double bond such as bromination,
chlorination, HX (X = Br, Cl, I) addition, and polymerization are all in excess of
10 kcal/mol more exothermic than the corresponding reaction with ethylene.6
Cyclobutene to butadiene isomerizations (Table 1-66) illustrate a reverse
in thermal stability between the hydrocarbon (1) and perfluorinated (2) case.
Perfluoro-1,3-butadiene (2) is found to be 11.7 kcal/mol less stable than
perfluorocyclobutene, a result which is in line with the increased exothermicity


7
Table 1-5. Fluoroalkene Heats of Hydrogenation.
Alkene
AHH (kcal/moO
ch2=ch2
-32.6
ch2=chf
-29.7
ch2=cf2
-38.8
chf=cf2
-45.7
Table 1-6. Fluorinated Cyclobutene/1,3-Diene Thermal Isomerizations.
c
A
B
£
D
AH0 (kcal/moh
Keg_(315C)
1
H
H
H
H
-9.7
9000
2
F
F
F
F
11.7
0.0056
3
H
H
F
F
-
77.5
4
ch3
H
F
F
-
0.50
5
ch2ch3
H
F
F
-
0.24
revealed
by AHh2 upon transcending the series of fluoroethylenes in Table 1-5.
Although
II
CM
X
o
o
CM
X
o
X
<
=CF2 is 6.2 kcal/mol more exothermic than ethylene,
isomerization in the case of 3,3,4,4-tetrafluorocyclobutene (3) favors the diene,
indicating the fluoroalkene is lower in energy. Simple alkyl substitution at C1 in
3,3,4,4-tetrafluorocyclobutene as seen with 4 and 5, dramatically shift the
equilibrium towards the cyclobutene, creating doubt as to the usefulness of this
system in demonstrating the thermodynamic influence of fluorine on an olefin.
Other systems as illustrated in Figure 1-3,17 indicate gem-difluoroolefins are


8
destabilized relative to the saturated species. Results pertaining to the stability
of monofluorinated alkenes are contradictory but it is generally accepted that
monofluorination stabilizes a double bond relative to the saturated state.56
f2c=chch3
A, l2
HCF2CH=CH2
AH = -2.5 kcal/mol
f^CF2
A
<^cf2
AH = -5.1 kcal/mol
Figure 1-3. Equilibria Involving Gem-difluoro Alkenes.
Since the enthalpy of reaction is a relative energy change between
reactant and product, it is not entirely established whether the favorable driving
force for transformation of a trifluoro- of gem-difluoroolefin to a saturated
fluoroalkane is due to n bond destabilization in the fluoroolefin or stability as a
result of rehybridization of the fluorinated carbon from sp2 in the fluoroolefin to
sp3 in the fluoroalkane. Arguments for both factors are offered and it appears
that both are important in these systems with n bond destabilization being the
major contributor.5 6
Fluorine Non-bonded Electron Interactions
As the stabilizing influence of fluorination upon alkanes has been
offered, a discussion on fluorine's non-bonded electron interactions with
adjacent occupied and non-occupied orbital systems is warranted in light of the
aforementioned question of fluoroolefin destabilization.
Destabilization of n systems has related precedent in the case of a-fluoro
carbanions. Such systems are found to be destabilized in situations where the
carbon bearing the negative charge and fluorine are planar.1 Figure 1-4


9
OH OH
F
10.59 10.49
pKa in 30% EtOH at 25.0C
D 1
F 0.125
Cl 400
Br 700
Figure 1-4. Destabilization in Planar a-Fluorocarbanions.
illustrates the decrease in acidity in 4-fluorophenol (6)18 relative to phenol and
rate inhibition in isotope exchange in 9-fluorofluorene relative to fluorene-9-d2
(7)19and other 9-halogenofluorenes. Conjugative destabilization is invoked in
these cases between the fluorine non-bonded electron pairs and the planar
carbanion.
A variety of experimentally observed situations occur with fluorine bound
to sp2 hybridized carbon for which perturbation of an adjacent neutral n system
is induced by interaction with fluorine non-bonded electrons. Fluorine is found
to be an ortho and para director and frequently a net activator in electrophillic
aromatic substitutions.7 Along the same line of thought, fluorine and oxygen are
found to strongly influence the distribution of n electron charge in aromatic


10
Table 1-3. 13C NMR Shifts (8jms) for Heteroatom Substituted Benzene.
X
Geminal
ortho
meta
para
F
163.8
114.4
129.6
124.3
OH
154.9
115.4
129.7
121.0
Cl
134.3
128.6
129.8
126.5
SH
130.7
129.2
128.9
125.4
13CNMR Shift for C6H6 21: 128.5
systems leading to the development of partial negative charge at the ortho and
para positions. This is revealed by the observed shielding of carbons at these
positions in the 13C NMR spectra of representative substituted benzenes as
illustrated in Table 1-3.20 The larger third period analogies, chlorine and sulfur
respectively, show a minimal effect as might be expected due to poorer overlap
of their non-bonded electrons with the aromatic n system.
Direct evidence for the stabilization of carbocations by geminally
substituted fluorine has been obtained by a gas phase, ion cyclotron resonance
technique. This study has revealed that the ascending order of stability in the
series of fluoromethyl carbocations is +CH3 < +CF3 < +CH2F < +CHF2.2223
Furthermore, the +CF3 cation has been generated by matrix photoionization of
trifluoromethyl halides and exhibits an infrared spectrum which is consistent
with extensive 7t(P.P) bonding.24 Generally, the degree to which carbocations are
stabilized by hydrogen, fluorine, and alkyl will be found to follow the order +CH
< +CF < +CR.5


11
a-Fluorine changes the geometry of methyl radical from planar to
pyramidal which is proposed to be due to repulsion between the radical and
fluorine non-bonded pairs.25'26 Stability of a and (3-fluoro radicals as
established5 from bond dissociation energies is relatively unchanged from
hydrocarbon analogs and thermal rearrangement of 8 to 10 occurs with
activation parameters which are almost identical when X = H or F.27 The overall
effect of fluorination on the stability of free radicals is believed to be minimal.5'6
Figure 1-5. Thermal Rearrangement of 6-Methylidenebicyclo[3.2.0]heptane (8).
Fluorine Steric Effects
It is often assumed that when considered alone, the small differences
between hydrogen and fluorine in size and bond length to carbon will lead to
minimal or no effect on the conformation and reactivity in a hydrocarbon upon
substitution of C-F for C-H. This is often the case and has allowed for synthesis
and study of many poly and perfluorinated hydrocarbons, a situation which is
not available for any other atom to the extent to which it is for fluorine. Although
this is true, there remain a number of situations in which substitution of fluorine
for hydrogen in a hydrocarbon leads to a profound effect on the conformation
and (or) reactivity in a system due solely to the relative size and charge density
of fluorine versus hydrogen.
The potential energy barrier for rotation of the C-C bond in CH3-CH3 is
2.8 kcal/mol whereas in CF3-CF3 it is increased to 3.9 kcal/mol.28 1,3-Repulsion


12
between fluorines in perfluoro-n-alkanes leads to a twisting in the carbon
backbone. Such an effect is said to be evidenced by polytetrafluoroethylene,
which below 19C contains a 360 twist in the carbon backbone per 26 CF2
units.29 This is in marked contrast to polyethylene, where the carbon backbone
maintains a zig-zag structure with all of the C-C bonds in the same plane and all
of the hydrogen atoms in straight rows.29 Examples of fluorine influencing
conformational processes are offered in Figure 1-6.30 In these systems,
conformational barriers develop upon substitution of fluorine for hydrogen
arising from electrostatic repulsion between fluorine and the group moving past.
Figure 1-7 shows a persistent radical (14) which was able to be formed up to
88% (weight) in solution and could be diluted in the open air and dissolved in
good hydrogen donor solvents like toluene, or heated to 100C without
11
Ring Flip kH/kp = 1011 at 25C
S
/(CH^
s
12
Ring Flip AG* = 23.5n=4, 15.3n=5, 10.5n=6 kcal/mol
Figure 1-6. Influence of Fluorine on Conformational Processes.
13
14
15
Figure 1-7. A Persistent Perfluoroalkyl Radical (14).


13
destroying the ESR signals.1 The stability of this species was attributed to the
sheltering of the radical center provided by the perfluoroethyl and
perfluoroisopropyl groups. From Taft Es values, the CF3 group is found to be
larger than CH(CFl3)2 and the CF(CF3)2 group is similar in size to C(CFI3)3.31
Steric effects attributed to fluorine are most occurrent and documented in
the case of perfluorinated systems. For fluorine to exhibit a steric effect in a
mono or partially fluorinated system, the molecule must exist with very small
spatial tolerance, whereby substitution of hydrogen by fluorine leads to
destabilization. This would be the result of attempted direct overlap of nuclei or,
more likely, electrostatic repulsion between a substituent and fluorine's high
negative charge density. As shown, steric effects due to fluorine are most
frequently documented for conformational processes occurring in rigid systems
or in the sheltering of a reaction site by a perfluoroalkyl group.
The Thermal Cvclobutene/1.3-Diene Electrocvclic Process
In the previous discussions, examples of the novelty of fluorine
substituent effects were offered and rationalized based on intrinsic
characteristics of the fluorine atom. With this basic groundwork in mind, the
effect of fluorine on the thermal cyclobutene to 1,3-diene electrocyclic
interconversion will be discussed. Understanding the studies of this system is
imperative since the results lead to a hypothesis which this author's initial
project (Chapter 2) was developed to further address.
An electrocyclic rearrangement is a subset of the pericyclic class of
reactions which involve bonding changes in a concerted fashion through a
closed cycle of atoms.32 The electrocyclic rearrangement involves the formation
of a a bond between the termini of a conjugated linear n system which results in
the formation of a ring containing one fewer n bond.33 The reaction is potentially


14
reversible, a fact which will depend on the relative thermodynamics of the
specific system in question.
Woodward and Hoffmann identified the thermal cyclobutene to butadiene
interconversion as occurring through a concerted, conrotatory pathway.34
Concertedness in a process, a situation where the energetics of bond breaking
assist bond making,33 is evidenced in these systems by low activation energies
relative to the energy of a corresponding homolytic or heterolytic process, low
activation entropies, and stereoselectivity in product formation. The
stereoselectivity in the product butadiene (or cyclobutene for the reverse
reaction) is a result of the conrotatory nature of this process. Woodward and
Hoffmann proposed that conservation of orbital symmetry from reactants to
products is the lowest energy path by which the process may occur.34 To
maintain symmetry for the thermal 4k process, C3 and C4 of cyclobutene (or
terminal carbons in butadiene) must rotate in a similar direction upon breaking
of the a bond; hereby defining a conrotatory process.34 Two equivalent,
stereodistinct, conrotatory processes are allowed by orbital symmetry for the 4k
thermal reaction. As shown in Figure 1-8, each leads to a different conjugated
diene. Theoretical studies show that a concerted transition structure does not
exist for the thermally forbidden disrotatory process and estimates the non-
concerted path involving the allylmethylene diradical to be 9-11 kcal/mol above
the concerted conrotatory transition state.35
Figure 1-8. Conrotatory 4k Electrocyclic Process.


15
Stereochemistry of butadiene products from early thermal studies of C3
and C4 alkylated cyclobutenes were rationalized based on a steric argument.
The C3 and C4 methylated cyclobutenes (Figure 1-9) yielded butadienes in
which the bulkier substituent had stereospecifically rotated outward to form the
References: 1636, 1737
Figure 1-9. Thermal Ring Opening of Methyl Substituted Cyclobutenes.
E-alkenes, away from the breaking C3-C4 a bond in the concerted transition
state. In 1980 Curry and Stevens reported a series of 3,3-disubstituted
cyclobutenes which yielded products contrary to those which would have been
predicted on steric grounds.38 Figure 1-10 illustrates their results in which ethyl,
n-propyl, and /-propyl favor inward rotation over methyl to predominately form Z-
butadienes and, surprisingly, f-butyl yields 32% of the product where this very
bulky group has rotated inward. More intriguing examples have followed as
illustrated in Figure 1-11. In each case, the reaction is 100% stereoselective
and occurs contrary to expectations based on steric interactions.
Thermal Study of the Fluorinated Cyclobutene/1.3-Diene Interconversion
The unquantified nature of the system and an interest in fluorine
substituent effects led Dolbier et al. to investigate the thermodynamics and


16
kinetics of the process for a series of fluorinated materials in the mid-1980s.42'43
Fairly rapidly, studies in the fluorocarbon systems showed drastic deviations
from the corresponding hydrocarbons. One of the major differences is that the
relative thermodynamics of the perfluorocarbon systems are reversed from the
hydrocarbons; at equilibrium, mainly perfluorocyclobutenes exist.4244 The
Z E
Ratio of Products
R Z E
Ethyl
68
32
n-Propyl
62
38
/-Propyl
66
34
f-Butyl
32
68
Figure 1-10. Thermal Ring Opening of 3,3-Dialkylcyclobutenes.
19
z
och3
C(CH3)3 A
20
A
COOH
References: 1839, 1940, 2041
Figure 1-11. Contrasteric Stereoselective Thermal Ring Openings in
Substituted Cyclobutenes.


17
hydrocarbon cyclobutene ring opening is found to occur with AH* = 32.0
kcal/mol,45 AS* = 0.1 cal/molxdeg,45 and is irreversible at reasonable
temperatures due to an exothermicity of 9.7 kcal/mol.46 The exothermicity of the
hydrocarbon process arises roughly from differences in release of cyclobutene
ring strain47 (34.0 kcal/mol) and overall bonding change of a 7t (=61 kcal/mol)33
for a a (=79 kcal/mol)33 bond. This exothermicity is offset in the case of the
perfluorinated species by the preference of fluorine to be bound to carbon
orbitals hybridized with maximal p character. This factor amounts to 2 5
kcal/mol upon conversion of a gem-difluoroalkene to alkane as discussed
earlier (Figure 1-3). Figure 1-12 shows some of the systems reported by
Dolbier et al. In all of the systems, fluorine kinetically prefers outward rotation
and in some cases, outward rotation of fluorine is favored even at the steric
expense of rotating the bulkier CF3 group inward. Formation of the Z-alkenes
(23, 26) from thermolysis of 22 and 25 occur with activation energies 12.9 and
27.1 kcal/mol respectively lower than the alternate processes leading to the E-
alkenes (21, 24). This corresponds to ratios of rates for Z and E-diene
formation (kz/kf) of 7219 and 4.3x106 respectively for these two systems at
200.0C. With only one possible butadiene available from both conrotatory
processes, 27 undergoes ring opening to stereospecifically yield 28 with
relative normal activation parameters. The partially fluorinated cyclobutenes
29, 31, and 34 were investigated to quantitatively determine the effect of a
single fluoro or trifluoromethyl substituent. 3-Fluorocyclobutene (29) was found
to open stereospecifically to 30 with an activation energy 16.9 kcal/mol lower
than that required for ring opening of 34, the large difference in activation
energies arising from inward rotation of a fluorine in 34 versus 29. To
demonstrate that thermodynamic factors were not contributing to the
stereospecificities in ring opening of 29 and 31, iodine catalyzed thermal


18
F
F
ApF3
"IF
*l'F
CF3
27
0
38.1(2.0)
32.7(-10.5)
CF3 F
28
5.7
28.1 (-3.5)
36.3(3.9)
F
/-F 45.0(8.1)
34
30
32
97.8% (at 200.0C)
CF,
33
2.2%
35
Format is, Ea in kcal/mol (AS*, cal/mobcdeg); Relative AH0 in kcal/mol is shown below
structures for 21-23, 24-26, 27-28. References: (21-28)42, (29-35)43
Figure 1-12. Thermal Fluorocyclobutene/Fluoro-1,3-Diene Interconversions
Studied by Dolbier et al.


19
equilibria of each butadiene system was examined. Z-1-Fluoro-1,3-butadiene
was found to be more stable than the E-diene 30 with K(z/p, of 1.77 at 60 C and
E-5,5,5-trifluoro-1,3-pentadiene (32) was more stable than Z-33 with AH0 = 2.5
kcal/mol for the E<-Z equilibrium. No significant thermodynamic difference
between the Z and E-alkenes was observed in any of the cases examined, as
evidenced by these small differences in AH0 values. Therefore in these
systems, the observed kinetic difference must derive from substituent effects on
the relative transition state stability for the two competing conrotatory processes.
Considering all of the data, it was determined that in thermal conrotatory
cyclobutene ring openings, inward rotation of fluorine raises the activation
energy for the process by 10 kcal/mol while outward rotation lowers it by 4
kcal/mol.43
Theoretical Study of the Thermal Cvclobutene/1.3-Diene Interconversion
From the variety of examples and the nature of substituents examined for
this 4k, thermal process, it was obvious that the stereoselectivities observed
were not steric in origin except in a minor number of cases. Rather, the
stereoselectivities originate from a strong electronic effect involving interaction
of cyclobutene C3 and C4 position substituents with molecular orbitals of the 4k
transition state. Substituents at the C3 and C4 positions able to act as k
electron donors such as F, Cl, OCH3, and OCOCH3, kinetically favored outward
rotation whereas k electron acceptors such as CHO and COOH favored inward
rotation.
Rondan and Houk developed a hypothesis around results obtained by
theoretical ab initio level calculations on the cyclobutene/1,3-diene thermal
conrotatory process.48 Figure 1-13 is a representation of their proposed HOMO
(Highest Occupied Molecular Orbital) and LUMO (Lowest Unoccupied


20
'Stabilization
a* (LUMO)
Destabilizatior
4-
a (HOMO)
Figure 1-13. Representation of Donor Orbital Interactions with the HOMO and
LUMO of the Cyclobutene Conrotatory Transition Structure.
Molecular Orbital) for the cyclobutene thermal electrocyclic, conrotatory ring
opening transition structure with the donor orbital system indicated for either
outward or inward rotation. Upon inward rotation, a donor orbital (rccH3 on CH3
or a lone pair of electrons on a heteroatom) destabilizes the transition state due
to a repulsive interaction with the occupied bonding o orbital, while minimal
interaction exists with a* as the donor orbital is directed at the nodal surface.
Outward rotation of a donor is slightly stabilizing due to overlap with the a* and
the fact that the donor orbital experiences less repulsion with a upon rotating
out. Interaction of acceptors containing a n bond is more complicated due to the
interactions of occupied n bonding and unoccupied n* antibonding orbitals with
the a and o* orbitals of the cyclobutene transition state. The maximal stabilizing
interaction in the case of acceptors containing a n bond is proposed to occur
upon inward rotation. The two electron interaction between the cyclobutene


21
C3-C4 a orbital and the n* orbital on the acceptor leads to a small preference
for inward rotation. Experimentally, acceptors show little preference for inward
or outward rotation, the reason being that the stabilizing n*-o interaction is
countered by a repulsive interaction between the occupied n orbital and C3-C4
a orbital of the cyclobutene transition structure. Rondan and Houk suggested a
powerful electron acceptor such as the empty p orbital on a BH2 group would
favor inward rotation due to the strong interaction with the occupied cyclobutene
a bonding orbital. Table 1-748 illustrates calculated AEa's for inward versus
outward rotation for BH2 and other donor and acceptor substituents which
further demonstrate strong rotational selectivities.
Table 1-7. Calculated AEa's for Inward versus Outward Rotation in Substituted
Cyclobutenes.
Substituents
Eaut. £>
trans-3,4-diboryl
+13
frans-3,4-dimethyl
-13
trans-3,4-dichloro
-22
trans -3,4-difluoro
-29
trans-3,4-dihydroxy
-31.6
The cleavage of the a bond in the cyclobutene system biased by the
electronic character of an attached substituent was dubbed "torquoselectivity"
by Houk.49 He argues that in this system, the torque about the stretching o bond
is controlled by interaction with geminal electron donor or acceptor substituents.
It is further stated that such electronic based selectivities should be observable
in a variety of other organic pericyclic processes.


22
Conclusion
The preceding discussions have introduced the variety and fashion in
which fluorine substitution can perturb hydrocarbon chemistry and aid in
mechanistic interpretation. The body of this thesis will address experimental
results obtained from the study of fluorine as a substituent in thermal and
photochemical 67: electrocyclic (Chapter 2) and thermal [3,3]-sigmatropic
rearrangements (Chapter 3).


CHAPTER 2
THERMAL AND PHOTOCHEMICAL REARRANGEMENTS OF
9,10-BIS(TRIFLUOROETHENYL)PHENANTHRENE AND
PERFLUORO-E,E,E- AND E,Z,E-4,5-DIMETHYL-2,4,6-OCTATRIENE
Introduction
The concept of torquoselectivity, developed by Rondan and Houk to
rationalize the strong electronic control of C3 and C4 substituents upon ring
opening of cyclobutenes, was suggested to be operating in a variety of
pericyclic processes. The potential was discussed for various processes such
as 67t electrocyclic reactions, cyclopropane isomerizations, and sigmatropic
shifts, to undergo a bond cleavage in a stereoselective fashion biased by
overlap with geminally bound acceptor or donor substituents.4849 Disrotatory
electrocyclic processes are expected to exhibit rotational preferences to a
smaller degree than those observed for conrotatory cases. This is due to a
smaller difference in overlap (Figure 2-1) between the breaking o bond and
geminal substituent in inward and outward rotational configurations for
disrotatory as compared to conrotatory processes.
Outward
Disrotatory
^ Conrotatory
Inward
Figure 2-1. Geminal Substituent Overlap With o Bond in Outward and Inward
Rotation for Disrotatory and Conrotatory Processes.
23


24
Surprisingly, probing of torquoelectronic effects through suitably
designed systems has received minimal attention outside of the thermal
cyclobutene ring opening examples discussed in Chapter 1. Torquoselectivity
in the electrocyclic conversion of benzocyclobutenes to o-xylylenes has been
studied through Diels-Alder trapping experiments.50 A few examples involving
cyclopropane ring cleavage, such as: solvolysis of cyclopropyl halides,51 1,3-
sigmatropic shifts of substituted methylenecyclopropanes,49 and retro-ene
reactions of methyl vinylcyclopropanes,49 have been rationalized assisted by
torquoelectronic arguments.
In light of the torquoelectronic effects observed in the thermal 4n
electrocyclic fluorinated cyclobutene/1,3-diene system and the relatively
unexplored question of applicability to other pericyclic processes, a study of the
thermal 6n electrocyclic fluorinated 1,3(Z),5-triene/1,3-cyclohexadiene
interconversion was proposed. Woodward and Hoffman described the thermal
671 1,3(Z),5-triene to 1,3-cyclohexadiene reaction as occurring through an
orbital symmetry allowed disrotatory pathway.34 Experimentally, it is found that
the cyclized products are formed in a stereospecific fashion in line with a
disrotatory closure involving rotation of terminal 1,3(Z),5-triene substituents in
an opposite sense as illustrated by the examples in Figure 2-2.52
Figure 2-2. Stereospecific Thermal Disrotatory 6tt Electrocyclizations.


25
For hydrocarbon 1,3(Z),5-trienes, a wide variety of substituted systems have
been investigated to establish the relationship between triene structure and
reactivity towards cyclization.53
Observing torqueoelectronics in thermal ring opening of this 67c system is
unlikely, as the thermodynamics for conversion of 1,3-cyclohexadiene (38) to Z-
1,3,5-hexatriene (37) are unfavorable. The enthalpy diagram in Figure 2-354
illustrates the conversion of 37 to 38 is 15 kcal/mol exothermic due to loss of
AH
(kcal/mol)
36 37 38
Figure 2-3. Enthalpy Diagram for E and Z-1,3,5-Hexatriene (36, 37) and
1,3-Cyclohexadiene (38).
the conjugated triene double bond and formation of a o bond in 1,3-
cyclohexadiene. 1,3(Z),5-Triene Z^E isomerization (37-36) does not
compete with 6tt cyclization at lower temperatures as such a process involves
homolytic cleavage of the central double bond, occurring with a transition state
16 kcal/mol higher in energy than that required for the electrocyclic process.
The large exothermicity observed for Z-1,3,5-hexatriene cyclization leads to an
estimated AH* = 44 kcal/mol for ring opening of 1,3-cyclohexadiene. This
magnitude of an energy barrier for ring opening also accommodates a variety of


26
sigmatropic shift processes. Retrocyclizations of substituted 1,3-
cyclohexadienes have been observed at higher temperatures but
stereochemical analysis of the formed 1,3(Z),5-trienes in search of
torquoelectronic effects is futile due to competing rearrangements. Ring
opening of 39 (Figure 2-4) at 560C led to complete equilibration of the labels
and was rationalized as occurring through retrocyclizations and [1,7]-H(D)
Figure 2-4. Thermal Ring Opening of a 1,3-Cyclohexadiene.
shifts.55 1,3,5-Triene Z<->E isomerizations will also be competitive at these
elevated temperatures and create another source of stereochemical
scrambling.56'57
It is obvious from the preceding discussion that productive ring opening
and observation of torquoelectronics in substituted 1,3-cyclohexadienes will
require an adjustment in the thermodynamics of this system. In effect, reduction
or reversal of the enthalpy difference between a 1,3(Z),5-triene and 1,3-
cyclohexadiene would allow retrocyclization to be observed. The achievement
of such a situation would allow for ring opening of a 1,3-cyclohexadiene system
to occur at a reasonable temperature and allow study of torquoelectronic effects


27
by observing the 1,3(Z),5-triene stereochemistry and activation parameters
required.
Development of a Suitable 1.3(Z).5-Triene/1.3-Cvclohexadiene System
In theory, the exothermicity of 1,3(Z),5-triene cyclization may be offset by
ground state stabilization of the 1,3(Z),5-triene, destabilization of the 1,3-
cyclohexadiene, or some combination of both.
A system in which the thermodynamics seem favorable for observing ring
opening of a 1,3-cyclohexadiene is one in which the 1,3(Z),5-triene/1,3-
cyclohexadiene system shares a n bond with an aromatic ring as illustrated for
a general case in Figure 2-5. Cyclization in this case is impeded by loss of the
aromatic ring n bond, in effect destroying the resonance energy for that ring in
the aromatic system. By selecting the appropriate aromatic system and
Figure 2-5. Aromatic Annulated 1,3(Z),5-Triene/1,3-Cyclohexadiene System.
placement, 1,3-cyclohexadiene ring opening can become a competitive
process with 1,3(Z),5-triene cyclization at lower temperatures. Building a
fluorinated 1,3(Z),5-triene system into an phenanthrene ring was believed to be
the best suited entry into thermal study of 1,3-cyclohexadiene ring opening.
As previously discussed, Z-1,3,5-hexatriene cyclization is exothermic by
15 kcal/mol and terminal gem-difluorination or trifluorination of an pendant
alkene will increase this value by 2-5 kcal/mol peralkene. In line with the C-C a
bond strengthening trend observed for the series of fluorinated ethanes
(Chapter 1, Table 1-2), the C5-C6 a bond in the cyclohexadiene product will be


28
stronger than the corresponding C5-C6 a bond in the hydrocarbon. Such an
effect is difficult to quantize due to the nonlinear energy changes in geminal
bond strengths upon successive fluorination. An increase in the exothermicity
of the cyclization process from formation of the tetrafluorinated C5-C6 a bond
can be estimated to have an upper limit of 8 kcal/mol obtained from the
difference in C-C a bond strength between CH3-CH3 and CF3-CF3 (Chapter
One, Table 1-2). This yields an potential enthalpy of reaction range of -19
kcal/mol to -33 kcal/mol for cyclization of the hypothetical 1,1,2,5,6,6-hexafluoro-
1,3(Z),5-hexatriene. Although conceptually straightforward, estimation of this
AHr using AHf of each species through Benson58 type group values cannot
be performed because of the missing groups; CD-(CD)(F), CD-(C)(F), and C-
(C)(CD)(F)(F).59 Likewise, theoretical computations at any level less than ab
initio lead to woefully incorrect energy parameters for fluorinated materials.60
The resonance energy for phenanthrene is observed to be 91 kcal/mol.61
Loss of phenanthrene's C9-C10 double bond is accompanied by an 20
kcal/mol increase in enthalpy, or the difference in resonance energy between
phenanthrene and biphenyl.6162
Considering the energetics of the 1,3(Z),5-fluorotriene cyclization and
disruption of phenanthrene resonance energy by C9-C10 k bond cleavage
Figure 2-6. Proposed Thermal Electrocyclic Interconversion between 9,10-
Bis(trifluoroethenyl)phenanthrene (40) and 1,2,2,3,3,4-Hexafluoro-2,3-dihydro-
triphenylene (41).


29
together in a single system such as 9,10-bis(trifluoroethenyl)phenanthrene (40)
and 1,2,2,3,3,4-hexafluoro-2,3-dihydrotriphenylene (41) as illustrated in Figure
2-6, an enthalpy of reaction range of 1 kcal/mol to -13 kcal/mol for the
cyclization may be predicted based on the previous arguments. The upper limit
of such an enthalpy difference is suitable to allow for potential study of forward
and reverse reactions under reasonable conditions and, ultimately, observation
of torquoelectronic effects in a higher substituted system such as illustrated in
Figure 2-7. Due to a straightforward synthetic route available into these
perfluoroalkenyl substituted aromatics, 40 was prepared for thermal study.
Figure 2-7. Unsymmetrically Substituted, Phenanthrene Annulated, 1,3(Z),5-
Triene/1,3-Cyclohexadiene Interconversion for Torquoelectronic Study.
Synthesis of 9.10-Bis(trifluoroethenyl)phenanthrene (401
9,10-Bis(trifluoroethenyl)phenanthrene (40) was synthesized in four
steps (Figure 2-8) and isolated in a 1% overall yield. The first two steps
involved literature procedures; bromination63 of phenanthrene (45) to yield 9-
bromophenanthrene (46, 90%), then nitration64 to yield 9-bromo-10-
nitrophenanthrene (47, 13%). The actual yield of 47 from this reaction was
higher. The isolated yield reflects some difficulty in obtaining this material pure
from the other major nitration product, 9-bromo-3-nitrophenanthrene. The next
step involved nucleophillic attack of iodide on the brominated C9 of 47 to yield


30
Br 02N Br
HN03, CH3C02H
46 (90%)
(CH3C0)20, a \=/ \=
47 (13%)
ex. Nal, DMF, A
N02
XZnCF=CF2 (X = I, -CF=CF2)
40(16%)
cat. Pd(P(C6H5)3)4,
Triglyme, 110C
48 (42%)
Figure 2-8. Synthesis of 9,10-Bis(trifluoroethenyl)phenanthrene (40).
9-iodo-IO-nitrophenanthrene (48, 42%). The best literature procedure found
for preparation of 48 involved five steps and produced the target in 1% yield
from phenanthrene.65 Our procedure is a significant improvement even in this
unoptimized state involving three steps and producing 48 in 5% isolated yield
from phenanthrene. Preparation of 40 at this point was rather fortuitous. A
Pd(P(C6H5)3)4 catalyzed coupling between iodo aryls and XZnCF=CFY (X = I or
-CF=CFY, Y = F or Z{E)-CF3) was carried out on 48.66 From the reaction
mixture, 16% of 40 could be isolated on average. It was intended to isolate 9-
nitro-10-trifluoroethenylphenanthrene by this procedure, which through
subsequent steps could be converted to 9-iodo-10-trifluoroethenyl-
phenanthrene. This material would then provide the desired 40, 42, and 44
through the appropriate coupling procedure. Preparation of 40 by this coupling
procedure with 48 was found to be reproducible over a number of runs.
Although 9-nitro-10-trifluoroethenylphenanthrene was tentatively identified as a
component in the reaction mixture by 19F NMR, it was never isolated. Having


31
40 in hand a few steps earlier than anticipated, a study of it's thermal chemistry
was initiated.
Thermal Study of 9.10-Bis(trifluoroethenvl)phenanthrene (40)
The thermolysis 40 was studied from 140C up to 193C as 0.1 M
solutions in CeD6. Upon thermolysis of 40, four products could be observed in
solution and were isolated pure by preparative GLPC for characterization.
Figure 2-9 illustrates the percent composition of all reaction components versus
time for thermolysis at 180.0C. The reaction is quantitative with regard to
formation of C18H8F6 structural isomers through 19 hours of thermolysis at
180.0C and after 235 hours, a 78% yield of CiaH8F6 isomers is obtained as a
21:1 mixture of 1,2-(9,10-phenanthro)-3,5,5-trifluoro-4-trifluoromethyl-1,3-
cyclopentadiene (51) and 1,2,2,3,3,4-hexafluoro-2,3-dihydrotriphenylene (41).
To develop the scheme of overall transformations as shown in Figure 2-
9, it was necessary to thermolyze each of the intermediate materials; 41,
1,4,4,5,6,6-hexafluoro-2,3-(9,10-phenanthro)-bicyclo[3.1.0]hex-2-ene (49), and
4-difluoromethylidene-3,3,5,5-tetrafluoro-1,2-(9,10-phenanthro)cyclopent-1 -ene
(50), alone under conditions which had been used for the parent triene 40.
Thermolysis of 41 at 180.0C as a 6:1 purified mixture of 41:51 led to non
productive decomposition of 41 with no reaction of 51. Triene 40 was not
observed to be reversibly formed from the cyclized product 41, and neither 49
nor 50 were observed either. Thermolysis of purified 49 was observed at three
temperatures (180C, 185.0C, 192.5C) and found to form only 50 and 51.
The conversion of 49 to 50 and 51 is quantitative at the temperatures and
times observed. Figure 2-10 illustrates the percent composition of all reaction
components versus time for thermolysis of 49 at 180.0C. Thermolysis of 50,
as one can see at longer times in thermolysis of 40 (Figure 2-9, after 140 hours)


32
is observed to slowly form 51 In a near quantitative process. The possibility of
fluoride catalysis affording such a rearrangement was demonstrated by the
rapid conversion of 50 to 51 at 80C in the presence of added trace amounts of
CsF.
The possibility of fluoride catalysis effecting the reaction course of 40 at
early times was ruled out by thermolyzing a sample of 40 in DMF containing
CsF at 115C. After 3.5 hours, 70% of 40 had been consumed and three other
products were observed. Analysis of this mixture by GLPC and 19F NMR
showed that this fluoride catalyzed reaction process and the thermal process
had no products in common and was not further investigated.
The disappearance of 40 and 49 were both found to follow first-order
kinetics, and the corresponding first-order plots are given in Figure 2-11 and
Figure 2-12 respectively. Upon thermolysis of 40 up to 85% conversion, the
ratio of (49+50+51 )/41 was maintained at 4.42 0.19 at 180.0C, 5.03 0.11
at 184.5C, and 5.15 0.16 at 193.0C. Upon thermolysis of 49 through 70%
conversion, the ratio of (50/51) was maintained at 1.62 0.12 at the three
temperatures (180.0C, 185.0C, 192.5C) examined. As previously
mentioned, the reactions of 40 and 49 were found to be irreversible in
formation of their respective products. Assuming these reactions occurred via
irreversible, competitive first-order processes, rate constants for formation of 41
and 49 from 40, and 50 and 51 from 49 were obtained from the observed rate
constants for loss of 40 and 49, and the constant ratios of respective products
formed.67 Both the observed and separated rate constants for 40 are reported
in Figure 2-11, and for 49 in Figure 2-12.
The activation parameters (AH*, AS*) for the individual processes were
kT r.AHi'i r*sn
obtained from the Eyring expression68, k = e RT e R \ rearranged to the


33
form Ln(k/T) = -AH*/RT + AS*/R + Ln{k/h), where k = rate constant at absolute
temperature T, k= Boltzmann constant (1.381x1 O'23 J/K), h = Planck's constant
(6.626x10*34Jxs), and R = ideal gas constant (1.9872 cal/molxK). Linear least-
squares regression plots of Ln(k/T) versus 1/T yielded AH* and AS* from the
slope and intercept respectively of the fitted line for each system. Fit of the
separated rate constant k41 (Figure 2-13) at the three observed temperatures
yielded AH* = 29.9 0.1 kcal/mol and AS* = -19.6 0.3 cal/molxdeg, and for
k49 (Figure 2-13) yielded AH* = 34.4 2.8 kcal/mol and AS* = -6.6 6.0
cal/molxdeg. Fit of the separated rate constant k50 (Figure 2-14) yielded AH* =
31.3 0.4 kcal/mol and AS* = -12.7 0.9 cal/molxdeg, and for k5i (Figure 2-14)
yielded AH* = 31.4 0.1 kcal/mol and AS* = -13.4 0.1 cal/molxdeg.
Quantitative thermal studies of fluorinated 1,3,5-trienes have no
precedent in the literature, and the formation of bicyclo[3.1.0]hex-2-ene ring
structures from 1,3,5-triene thermolyses have no precedent in fluorocarbon
literature. There has been but one such case observed in the hydrocarbon
literature, and this will be discussed later. The novelty of the chemistry
presented above, along with the general absence of thermal studies of
fluorinated 1,3,5-trienes, led to examination of the system which will be
discussed next.
Thermal Study of an Acyclic Perfluorinated 1.3.5-Triene
The unexpected thermal results obtained in the case of 40 led to our
questioning as to whether an acyclic perfluorinated 1,3(Z),5-triene would also
undergo bicyclo[3.1.0]hex-2-ene ring formation in preference to the thermal
disrotatory 6n electrocyclic process. At the time this project began, the literature
contained only one relevant reference. Perfluoro-1,3,5-hexatriene had been
reported to afford an 84% yield of perfluoro-1,3-cyclohexadiene upon pyrolysis


34
Figure 2-9. Thermolysis of 9,10-Bis(trifluoroethenyl)phenanthrene (40) at
180.0C as a Solution in C6D6.


35
Hours
Figure 2-10. Thermolysis of MAS^.e-Hexafluoro^.S-^IO-phenanthro)-
bicyclo[3.1.0]hex-2-ene (49) at 180.0C as a Solution in CeD6.


36
T (C)
k40 (x105 sec1)
k4i (x105 sec-1)
l<49 (x10s sec'1)
180.0
0.991 0.12
0.183
0.808
184.5
1.55 0.01
0.257
1.29
193.0
2.93 0.06
0.476
2.45
50 + 51
Figure 2-11. First-Order Plots and Rate Constants for Loss of 9,10-
Bis(trifluoroethenyl)phenanthrene (40) and Derived First-Order Rate Constants
for Formation of 1,2,2,3,3,4-Hexafluoro-2,3-dihydrotriphenylene (41) and
1,4,4,5,6,6-Hexafluoro-2,3-(9,10-phenanthro)bicyclo[3.1.0]hex-2-ene (49).


37
T (C)
I<49(x105 see*1)
l<5o(x105 sec-1)
k5i(x105 sec'1)
180.0
1.96 0.02
1.21
0.751
185.0
2.92 0.01
1.81
1.11
192.5
5.14 0.08
3.17
1.97
Figure 2-12. First-Order Plots and Rate Constants for Loss of 1,4,4,5,6,6-
Hexafluoro-2,3-(9,10-phenanthro)bicyclo[3.1.0]hex-2-ene (49) and Derived
First-Order Rate Constants for Formation of 4-Difluoromethylidene-3,3,5,5-
tetrafluoro-1,2-(9,10-phenanthro)cyclopent-1-ene (50) and 1,2-(9,10-
Phenanthro)-3,5,5-trifluoro-4-trifluoromethyl-1,3-cyclopentadiene (51).


38
1/T
Figure 2-13. Eyring Plots for Separated Rate Constants k4-| and k4g.
Figure 2-14. Eyring Plots for Separated Rate Constants k50 and k51.


39
in a flow system at 450C.69 At this temperature, it is questionable whether this
is the primary process involved in this system. A lower temperature, more
quantitative study of an acyclic perfluorinated 1,3,5-triene was required.
A system whose synthetic approach potentially allowed for adaptation
into a variety of terminally substituted perfluoro-1,3,5-trienes was perfluoro-
E,Z,E- (and E,E,E-)4,5-dimethyl-2,4,6-octatriene (Z-56(E-56)). This system had
been previously synthesized and Figure 2-15 illustrates the chemistry
involved.70 This procedure was repeated and the isolated yield and product
composition obtained (60%, E,Z,E:E,E,E = 1.17:1) were similar to those reported
(68%, E,Z,E:E,E,E= 1.63:1).
Initially, an attempt was made to synthesize perfluoro-3,4-dimethyl-1,3,5-
hexatriene (58) by similar methodology; a process which had been discussed
Cd, DMF, RT
30 min.
CuBr, DMF, RT
TH?
Similar to Above
I^F
DMF, RT, 1 Hr
CU>
"X
=< F
57 CF*
*Perfluoro-Z-1-iodopropene (52) was synthesized in four steps from perfluoropropene.66
Figure 2-15. Synthesis of Perfluoro-E,Z,E(E,E,E)-4,5-dimethyl-2,4,6-octatriene
(Z-56(E-56)).


40
only to the point of the chain extended copper reagent 57 in the reference.
Following the reaction progress by 19F NMR, formation of 57 was observed, but
addition of a further equivalent of iodotrifluoroethylene afforded a 5% or less
yield of 52 in the reaction mixture, which for the purpose of this project was
synthetically useless. Not having obtained useful quantities of 58, the synthesis
of 56 was repeated and it's thermal chemistry investigated.
The thermolysis of 56 was studied from 149C to 202C as a 0.17 M
solution in n-pentane. Due to difficulty in separation of the triene E,Z,E and
E,E,E isomers, the typical synthetic mixture of isomers (E,Z,E:E,E,E ratio of
I.17:1) was used in all studies. At temperatures around 150C, E,Z,E-*E,E,E
isomerization was observed to occur. After longer times, one new product was
evident, being identified by 19F NMR in the reaction solution as a mixture of
periluoro-c/'s(and transj-l ,3,4-trimethyl-4-(E-1-propenyl)cyclobutene (59).
Figure 2-16 shows the percent composition versus time for thermolysis of 56 at
154C and then at 202C. E,Z,E->E,E,E isomerization is observed initially
followed by appearance of 59 after 50 hours at 154C. Raising the temperature
of the sample to 202C sets up an equilibrium mixture of E-56/59/Z-56 =
II.4/7.6/1. Thus, this system represents a second example where a highly
fluorinated 1,3(Z),5-triene underwent thermal chemistry other than the 6k
disrotatory formation of a 1,3-cyclohexadiene. Since the thermal 6k closure
seemed to be disfavored, we were interested to see whether the photochemical
6k conrotatory formation of 1,3-cyclohexadienes would occur in these
fluorinated systems.
Photochemical Rearrangements of 9.10-BisftrifluoroethenvnDhenanthrene (401
and Perfluoro-E.Z.E(EE.EM.5-dimethvl-2.4.6-octatriene (Z-56(E-56)1
Upon photochemical excitation, ground state 1,3,5-trienes may undergo


% Composition
41
Hours
E- 56
Figure 2-16. Thermolysis of Perfluoro-E,Z,E(E,E,£)-4,5-dimethyl-2,4,6-
octatriene (Z-56(f-56)) as a Solution in n-Pentane.


42
K-K* transformation to singlet excited states.71 These singlet excited states are
biradical in character and create a symmetry change in the 1,3,5-triene HOMO
from symmetric in the ground state to antisymmetric in the singlet state.
Woodward and Hoffman recognized that concerted photochemical 1,3,5-triene
cyclizations and 1,3-cyclohexadiene ring openings occurring by conrotatory
processes are an artifact of this change in the HOMO symmetry.34 More recent
theoretical study also recognizes a preferred photochemical conrotatory mode
of reaction.72 Experimentally it is found that the process occurs
stereospecifically in a conrotatory fashion as shown in Figure 2-17.73
CH,
c6h5
Figure 2-17. Photochemical 67t Conrotatory Processes.
Simple observation of 1,3(Z),5-triene/1,3-cyclohexadiene photo
processes are complicated in many cases by other reaction pathways available
to the high energy excited state. Figure 2-18 illustrates the variety of products
which have been observed in various 1,3,5-triene/1,3-cyclohexadiene
photochemical systems.74 A variety of factors are important in dictating the
product distribution and will be discussed later.


43
Figure 2-18. Photoproduct Variation in 1,3,5-Triene/1,3-Cyclohexadiene
Systems.
Having not observed the thermal 6tt disrotatory process to any significant
extent in the cases of 40 and Z-56 at the temperatures studied, it was of interest
to determine if the photochemical 6ti conrotatory process would occur. A
question of the relative ability of the two 6n transition states (thermal disrotatory
versus photochemical conrotatory) to accommodate fluorine emerged, and a
qualitative study of the two systems photo-processes was undertaken.
Photolysis of 9.10-Bis(trifluoroethenyDDhenanthrene (401
The photolysis of 40 was studied as a 0.05 M solution in n-pentane and
the samples were irradiated through Pyrex at room temperature by a heated-
cathode, low pressure mercury lamp. Four products are observed to arise from
the photolysis of 40. Figure 2-19 shows the percent composition of all reaction
components versus solution irradiation time. As found in the thermolysis of 40,
the bicyclo[3.1.0]hex-2-ene 49 is the major product from photolysis of 40. The
671 electrocyclic product 41 is formed in small and relatively constant
concentration throughout the photolysis. Two other [27i+2tc] type products,


44
1,4,5,5,6,6,-hexafluoro-2,3-(9,10-phenanthro)b¡cyclo[2.1.1 ]hex-2-ene (60) and
1 ,4,5,5,6,6-hexafluoro-2,3-(9,10-phenanthro)bicyclo[2.2.0]hex-2-ene (61) are
formed roughly in a ratio of 4.5(60): 1 (61) and account for 30% of the reaction
mixture after 93% conversion of 40. Independent photolysis of pure 41 under
similar conditions used for 40 led to formation of 61 in low yields; one hour of
photolysis of 41 yields 53% 41 remaining and 28% of 61 formed with a 19%
decrease in mass balance. Photolysis of 41 for two hours leads to decrease in
amounts of all materials and 60% reduction in mass balance. Reversibility of
41 back to triene 40 was not observed to any extent in these studies. Overall
photolysis of the parent triene is quite clean and after 21 hours with the
aforementioned light source, an 11% decrease in mass balance is observed
with 8% 40 remaining. Some extent of polymerization is occurring under these
conditions and is revealed by a small amount of solid white film appearing on
the walls of the photolysis vessel.
Attempts to isolate 60 and 61 failed. The preparative packed column
GLPC conditions necessary to elute these phenanthrene derivatives led to
decomposition of 60 and 61. It was found that thermolysis of a benzene
solution containing 49, 60, and 61 at 184C for 83 minutes led to a mixture
containing only 41,49, 50, and 51 with no 60 or 61 remaining and no new
products evident. This process was not quantified and other attempts at
isolation of 60 and 61 by TLC failed as the isomers could not be separated by
this technique.
Photolysis of Perfluoro-E.ZE(EE.F)-4.5-dimethvl-2.4.6-octatriene (Z-56(E-56))
The photolysis of 56 was studied as a 0.17 M solution in n-pentane and
the samples were irradiated through Pyrex at room temperature using a heated-
cathode, low pressure mercury lamp. Two products were observed and


45
isolated upon photolysis of 56. Figure 2-20 shows percent composition of all
materials versus solution irradiation time. Perfluoro-frans-2,3,5,6-tetramethyl-
1,3-cyclohexadiene (62) is the major photoproduct and is accompanied by
triene E,Z,E tetramethylbicyclo[2.2.0]hex-2-ene (63) is formed in the reaction mixture after
longer times and in small quantity when photolysis is carried out through Pyrex.
Photolysis of pure 62 through quartz under similar conditions used for 56 leads
exclusively to 63, and ring opening to 56 is not observed to any extent.
Attempts to obtain Diels-Alder adducts between 62 and dimethyl
acetylenedicarboxylate or N-phenyltriazoline dione in n-pentane at
temperatures up to 200C showed no reaction and 62 was also found to be
stable at 202C in n-pentane for 18 hours showing no rearrangement or
decomposition.
Discussion
The experimental data which have been presented point to an unique
disparity in the thermal and photochemical processes occurring in
perfluorinated 1,3,5-triene systems. While the observed photochemical
products will be shown to have related precedence in hydrocarbon 1,3,5-triene
transformations, the thermal rearrangements show little resemblance to those of
analogous hydrocarbons. It is recognized that upon such a drastic change as
perfluorination, anticipating similar results in these systems as those seen for
hydrocarbons is a dangerous assumption. As mentioned earlier, our motivation
for study of these perfluorinated systems was that they were easiest to obtain
synthetically while offering the widest variety of substitution possibilities, and
related precedence had been set in thermal studies of the 4jt perfluorinated 1,3-
diene/cyclobutene system. The results from photochemical and thermal studies


% Composition
46
Figure 2-19. Photolysis of 9,10-Bis(trifluoroethenyl)phenanthrene (40) as a
0.05 M Solution in n-Pentane by Low Pressure Mercury Lamp through Pyrex.


% Composition
47
Figure 2-20. Photolysis of Perfluoro-E,Z,E(E,E,E)-4,5-dimethyl-2,4,6-octatnene
(Z-56(E-56)) as a 0.17 M Solution in n-Pentane by Low Pressure Mercury
Lamp.


48
of perfluoro-E,E,E(E,Z,E)-4,5-dimethyl-2,4,6-octatriene (Z-56(£-56)) and 9,10-
bis(trifluoroethenyl)phenanthrene (40) will now be discussed in turn.
Discussion of the Photochemical Studies
Early studies in the photochemistry of Vitamin D and its many isomers
set the precedent for the possible complexities of 1,3,5-triene photochemistry.74
Previously, Figure 2-18 illustrated some of the types of products which have
been observed elsewhere in 1,3,5-triene photochemistry.
It is generally accepted that 1,3,5-triene photoproduct composition can
be directly related to the ground state conformational distribution of the system
by a principle known as the Non-Equilibration of Excited Rotamers (NEER).74
This principle states that in the excited state, an enhanced barrier for rotation
exists about the bonds which in the ground state are single bonds. Due to it's
limited lifetime, the acquiring of sufficient thermal energy by the excited state to
overcome such a barrier is unlikely. In effect, the photoproduct composition
should reflect a quantitative view of the ground state conformational equilibrium
which was irradiated. As illustrated in Figure 2-21, the ground state
conformations of Z-1,3,5-hexatriene will upon irradiation, lead in a specific
fashion to NEER dictated products.74
Although a seemingly trivial concept, the NEER principle turns out to
have good predictive value. Methods such as 1H NMR and UV spectroscopy
have been used to establish the preferred conformation in some hydrocarbon
1,3,5-trienes such as 64,7576 and 65-67,7477 and the corresponding 254 nm
primary photoproducts are shown in Figure 2-22. Absolute proof of an
mechanistic rationale is difficult and more so in the case of NEER because of
the number of relevant untested variables and alternate mechanistic proposals.
The possibility of equilibration of excited conformers has been addressed and


49
Figure 2-21. Three "Planar" Conformations of Z-1,3,5-Hexatriene and
Corresponding Photoproducts.
(H30)30 ^ ^--C(CH3)3
64
cZc
65
cZc
tEt
67
cZt
Major
Product Distribution
Minor
C(CH3)3
(H3C)3C
C(CH3)3
(H3C)3C
C(CH3)3
(H3C)3C/
J-
Figure 2-22. Examples of 1,3,5-Triene Preferred Ground State Conformations
and 254 nm Primary Photoproduct Distribution.


50
dismissed by a study of the influence of wavelength on the photoproduct
distribution at low percentage conversion.7478
The preferred ground state conformation of acyclic 1,3,5-trienes changes
considerably from the hydrocarbon to perfluorocarbon systems. A variety of
studies (UV and photoelectron spectra79, theoretical consideration6080) point
toward perfluoro-1,3-butadiene (75) existing in a cis-skew structure with torsion
angle 0 = 42 (Figure 2-23), whereas 1,3-butadiene (73) exists in a planar trans
conformation with 0 = 180. A significant hypsochromic shift is observed as the
series of fluoroethylenes (68 72) is transversed. This trend is also observed
between 73, 74, and 75, but here along with photoelectron spectral data, is
^max (nm)
Emax (L/molxcm)
0 (deg)
68
H2C
ch2
165
10,000
-
69
h2c
CHF
167
10,000
-
70
H2C-
cf2
165
7,900
-
71
FHC=
cf2
162
6,800
-
72
F2C
cf2
139
11,370
-
73
/
J
210
22,300
180
cf2
74
//
/
200
19,500
180
f2c
0
75
£
f/
162
m:f2
6,800
42
References: 6821
, 69-7281,'
7382, 7479,
75s2
Figure 2-23. UV Data for Fluoroethylenes and Fluorobutadienes.


51
proposed to be due to non-planarity in 75 relative to 73 and 74.79 Perfluoro-
1,3-butadiene (75) is observed to have a UV spectrum identical with HFC=CF2
(71), further indicating there is little interaction between the C1-C2 and C3-C4 n
systems. This non-planarity is displayed by models where a disadvantageous
interaction is observed between fluorines on C1 and C3, and C2 and C4 in the
planar trans conformation.83 Hypsochromic shifts attributed to non-planarity
have been observed in other non-planar polyenes such as 2,3-di-f-
butylbutadiene, where Xmax = 186 nm.84
Perfluoro-E-1,3,5-hexatriene (E-76) has been subjected to theoretical
conformational study at the ab initio level.60 Two torsional angles (0i, 02) exist
in this molecule and local minima were located for two structures with syn and
anti relations of the pendant alkenes relative to the plane formed by C2-C3-C4-
C5. Figure 2-24 illustrates the conformers and the relative energies calculated.
The lowest energy conformer of E-76 was found to be a syn-skew structure as
is observed with perfluoro-1,3-butadiene (Figure 2-23, 75).
F F F
F
F
F
E-76
01 (deg)
01 (deg)
AE (kcal/mol)
180
180
3.10
146
-146
2.29
146
146
2.01
53
-53
0.10
52
52
0.00
Figure 2-24. Relative Calculated Minima for Perfluoro-E-1,3,5-hexatriene (£-
76).


52
Photochemical Study of Perfluoro-EZ.E-(andE.E.a4.5-dimethvl-2.4.6-
octatriene (Z-56E-56))
Photolysis of perfluoro-E,Z,E-4,5-dimethyl-2,4,6-octatriene (Z-56) and
perfluoro-E,E,E-4,5-dimethyl-2,4,6-octatriene (E-56) yielded only two products;
perfluoro-irans-2,3,5,6-tetramethyl-1,3-cyclohexadiene (62) and perfluoro-
frans-1,2,3,4-tetramethylbicyclo[2.2.0]hex-2-ene (63) in good yield. The overall
transformation is illustrated in Figure 2-25. Triene E-56 has two possible
modes of reaction available by NEER type reasoning; 4n disrotatory ring
closure or C4-C5 double bond isomerization. The lowest energy conformer for
E-56 will most likely be similar to that of E-76, a skewed non-planar structure.
The An disrotatory photo-process leading to a 3-propenylcyclobutene would
require a tEc triene conformer which would be disfavored due to a repulsive
interaction between C2 fluorine and C5 trifluoromethyl groups. Therefore, the
observed process for E-56 is E,E,E->E,Z,E isomerization about the C4-C5
Figure 2-25. Photolysis of Perfluoro-E,Z,E(E,E,E)-4,5-dimethyl-2,4,6-octatriene
(Z-56(E-56)).
double bond to form Z-56. Cis triene Z-56 is found to undergo only 6n
conrotatory closure to yield 62. The lowest energy conformer of Z-56 most
likely involves skewing of the pendant E-perfluoropropenyl groups relative to
the C3-C4-C5-C6 plane, but whether it exists cis or trans skewed about the C3-
C4 and C5-C6 single bonds is unknown. It is noticed that a cis skewed


53
structure of Z-56 (Figure 2-26) is perfectly aligned with minimal repulsion to
undergo allowed 671 conrotatory bond formation between C2 and C7 leading
directly to 62.
Figure 2-26. C/s-Skewed Conformer of Perfluoro-£,Z,E-4,5-dimethyl-2,4,6-
octatriene (Z-56).
Perfluoro-i/'ans-2,3,5,6-tetramethyl-1,3-cyclohexadiene (62) undergoes a
further formal An disrotatory closure to form perfluoro-trans-1,2,3,4-tetramethyl-
bicyclo[2.2.0]hex-2-ene (63) in preference to ring opening to perfluoro-£,Z,E-
4,5-dimethyl-2,4,6-octatriene (Z-56). Using experimental results and NEER
type reasoning, it has been established for hydrocarbon photochemical 1,3-
cyclohexadiene processes that the preferred ground state conformation of the
system will control whether the 6rc conrotatory ring open 1,3(Z),5-triene or 4n
disrotatory ring closed bicyclo[2.2.0]hex-2-ene is observed.85 Studies have
shown that planar or half-boat type conformers (Figure 2-27) undergo
disrotatory closure to bicyclo[2.2.0]hex-2-enes and half-chair type conformers
prefer conrotatory ring opening to 1,3(Z),5-trienes.


54
Planar Half-boat
Q
\ I
bicyclo[2.2.0]hex-2-ene
Half-chair
Half-chair
<=7
Z-1,3,5-Triene
Figure 2-27. Conformationally Controlled Photo-processes of 1,3-
Cyclohexadienes.
With this precedent, it is surprising that cyclohexadiene 62 does not
undergo ring opening. Model studies83 indicate the most favored conformer of
62 (Figure 2-28) is one in which trifluoromethyl steric repulsions are minimized
in a half chair ring orientation with di-pseudoaxial C5 and C6 trifluoromethyl
groups and a C1-C2-C3-C4 torsion angle larger than that found in 1,3-
cyclohexadiene.
Figure 2-28. Favored Half-Chair Conformer of Perfluoro-frans-2,3,5,6-
tetramethyl-1,3-cyclohexadiene (62).


55
The photochemical results obtained with fluorinated triene 56 are
consistent with the few other fluorinated examples found in the literature.
Recently, it has been reported that perfluoro-Z-1,3,5-hexatriene (Z-76)
undergoes double bond isomerization and An and 6n photoclosures (Figure 2-
29) to yield a mixture of perfluoro-E-1,3,5-hexatriene (E-76), perfluoro-1,3-
cyclohexadiene (77) and perfluoro-3-ethenylcyclobutene (78).86 At low percent
conversions of Z-76, only E-76 and 77 are identified in the reaction mixture.
When the reaction is carried out to completion a mixture containing 25% 77,
40% 78, and 35% perfluoro[2.2.0]bicyclohex-2-ene (79) is obtained.
An inconsistency exists in that the formation of the perfluoro-3-
ethenylcyclobutene (78) ring structure was not observed in the case of 56. As
already discussed, E-56 will not populate the tZc conformation for steric
reasons and undergoes E,E,E->E,Z,E isomerization only. It is difficult to see
why Z-56 is not observed to form An cyclization products as are observed in the
£-76 Z- 76
\ /
78
Figure 2-29. Photoproducts Obtained from Perfluoro-Z-1,3,5-hexatriene (Z-76).
case of Z-76. Models indicate the cZt conformation of Z-56 may exist as it
must for Z-76 with little crowding of the trifluoromethyl substituents. A possible
explanation arises if one assumes only the fluorinated E-trienes are undergoing


56
the 4n cyclization. In this case, cEt E-76 can undergo 4n closure or EZ
isomerization, whereas tEt E-56 affords only Z-56. It is unproved whether such
an argument applies, but if so, it would be unique to these perfluorinated 1,3,5-
trienes as both E and Z hydrocarbon 1,3,5-trienes are observed to form 3-
alkenylcyclobutenes as primary photoproducts (Figure 2-22).
Photolysis of perfluoro-1,3-cyclohexadiene (77) using a low pressure
mercury lamp has been previously reported to quantitatively yield 79 as the
sole photoproduct.87 In contrast to the previous fluorinated 1,3-cyclohexadiene
results, photolysis of perfluorotricyclo[6.2.2.02-7]dodeca-2,6,9-triene (Figure 2-
30, 80) yields bicyclo[3.1.0]hex-2-ene type isomers 82 and 83. These products
are proposed to be originating from the ring opened triene 81, a species which
was never observed in this study.88 Due to the rigidity of the bicyclohexene ring
structure of 80, the cyclohexadiene ring will be very nearly planar. The
formation of 1,3,5-hexadiene 81 goes counter to the NEER predicted product
for this system, which would be formation of a bicyclo[2.2.0]hex-2-ene (Figure 2-
27) type ring structure.
83
Figure 2-30. Photolysis of Perfluorotricyclo[6.2.2.027]dodeca-2,6,9-triene (80).


57
Photochemical Study of 9.10-Bis(trifluoroethenyl)phenanthrene (40)
Photolysis of 9,10-bis(trifluoroethenyl)phenanthrene (40) led to formation
of four structural isomers; 41, 49, 60, and 61 as illustrated in Figure 2-31.
Figure 2-31. Photolysis of 9,10-Bis(trifluoroethenyl)phenanthrene (40).
9,10-Bis(trifluoroethenyl)phenanthrene (40) was observed by 19F NMR to
exist as a pair of torsional diastereomers with a substantial energy barrier to
interconversion, a discussion of which has been published.89 The 19F NMR
spectrum of 40 at 25C showed signals corresponding to two types of non
equivalent trifluoroethenyl groups. Such a spectrum is believed to arise from a
substantial thermal barrier due to restricted rotation between conformers
involving an syn and anti relationship of the trifluoroethenyl substituents relative
to the plane of the phenanthrene ring. Observation of the 19F NMR spectra of
40 over the temperature range of -17C to 84C and application of classical
theory with respect to equilibrium and NMR spectra allowed an estimation of
AG* = 15 kcal/mol for interconversion of the isomers. Molecular mechanics


58
calculations estimated AHRXn = 0.7 kcal/mol for anti-40->syn-40 with AH* =
16.01 kcal/mol.90 Local minima for syn {syn-40) and anti {anti-AO) type
conformers were located (Figure 2-32) with trifluoroethenyl torsional angles
relative to the aromatic ring plane (tZt structure) for the anti conformer of 50 and
-75, and for the syn conformer of 62 and 119.
syn-40
Figure 2-32. Conformational Equilibrium of 9,10-Bis(trifluoroethenyl)-
phenanthrene (40).


59
The formation of the observed photoproducts from 40 has some
precedent from the hydrocarbon literature. Photochemical studies of 1,2-
diethenylbenzene (84, Figure 2-33) have been reported by a few authors.91'92 93
One study found that photolysis of 84 with a medium pressure mercury arc
through Pyrex yielded benzobicyclo[3.1.0]hex-2-ene (83) as the major product
in a low overall yield process (20% max) with smaller amounts of tetralin, 1,2-
dihydronaphthalene, and naphthalene observed arising from 2,3-
dihydronaphthalene (85).91 1,2-Diethenylbenzene-c4 with four terminal
methylene deuterons was also studied to establish a carbon skeletal
rearrangement via 86 to 83, disproving a mechanism involving hydrogen
migration.91
Tetralin
- 1,2-Dihydronaphthalene
Naphthalene
- CE7
83
Figure 2-33. Photolysis of 1,2-Diethenylbenzene (84).
Photolysis of 9,10-diethenylphenanthrene has been reported and studies
under a variety of conditions did not lead to the observation of any cyclization.94
In this case, polymerization was the only process which was observed.
The photoproducts observed from 9,10-bis(trifluoroethenyl)phenanthrene
(40) are consistent with the above hydrocarbon system results and they can
potentially be seen as arising from a NEER dictated process. Figure 2-34
shows the proposed overall primary and secondary processes. Conformer
anti-40 can form three primary photoproducts; 41,60, and 88.


60
Bicyclo[2.1.1]hex-2-ene 60 may be formed from the pendant alkenes reacting in
a photo-allowed 27ts+27ts cycloaddition and cyclohexadiene 41 may arise from
a 671 conrotatory electrocyclization. Initial formation of bicyclo[3.1.0]hex-2-ene
88 may occur through either the anti-40 or syn-40 conformers and the true
nature of the photochemical mechanism involving formation of
bicyclo[3.1.0]hex-2-enes has been the subject of much debate.
*AII bonds to fluorine except for the 1 through 8 positions of the phenanthrene ring systems.
Figure 2-34. Primary and Secondary Processes and Final Product Distribution
for Photolysis of 9,10-Bis(trifluoroethenyl)phenanthrene (40).
Photochemical formation of bicyclo[3.1,0]hex-2-enes are formally
Woodward and Hoffman allowed 4Jts+2Jta or 4Jta+2Jts processes.34 Establishing


61
the true nature of the mechanism requires labels with which to follow the
stereochemical course of the process. While there are examples of 4rts+2rta
and 47ta+2*s photoisomerizations,95'96 there are also examples of disallowed
4Jla+2Jta processes.97 Further, an explanation exists based on "cross-
bicyclization in linear conjugated polyenes" where the author's rationalization
allows for concerted 4*8+2,18 photo-processes.98 Other arguments have
involved a stepwise process which involves a concerted conrotatory closure of
the three membered ring followed by closure of the five membered ring,8599 and
sudden polarization of the 1,3(Z),5-triene from a C3-C4 twisted diradical to a
charge separated zwitterion which undergoes closure.100'101102
Primary photoproduct 88 was never observed most likely due to thermal
instability caused by strain in this spiro-fused system and loss of aromaticity
from the central phenanthrene ring. Under the reaction conditions, 88 most
likely undergoes a vinylcyclopropane-cyclopentene rearrangement to 49 as
rapidly as it is formed. Photolysis of 40 was attempted at -50C looking for 88
by low temperature 19F NMR but only 49 was observed. Lower temperature
studies were abandoned due to equipment difficulties. Bicyclo[2.2.0]hex-2-ene
61 may be formed by a photo-allowed 2*s+2*s cycloaddition from syn-40 or a
secondary process involving a 4n disrotatory electrocyclization of 41. This was
found to be occurring as photolysis of pure samples of 41 led in low yield to 61
and showed no reversibility to the parent triene 40.
Discussion of Thermal Studies
The initial assumption that a suitably tailored fluorinated 1,3(Z),5-triene
system would allow for probing of the torquoelectronic effect in triene 6k thermal
chemistry turned out to be incorrect in the case of the phenanthrene annulated
system. Investigation of the thermal rearrangements of 9,10-bis(trifluoro-


62
ethenyl)phenanthrene (40) and perfluoro-E,Z,E(and E,E,E)-4,5-dimethyl-2,4,6-
octatriene (Z-56(E-56)) revealed that rearrangement pathways for these
systems have little in common with the corresponding hydrocarbons.
Thermolysis of Perfluoro-EZEfand E.EEV4.5-dimethvl-2.4.6-octatriene (Z-
Thermolysis of the mixture of Z-56 and E-56 led to initial C4-C5 Z/E
double bond isomerization at temperatures above 150C. The hydrocarbon
analog, Z-1,3,5-hexatriene, forms 1,3-cyclohexadiene with Ea = 29.3 kcal/mol,
while C3-C4 E to Z double bond isomerization requires temperatures in excess
of 250C with Ea = 45.5 kcal/mol.57 Thus, the hydrocarbon Z-triene undergoes
the 6k electrocyclic process exclusively due to the AEa = 16 kcal/mol difference
between it's concerted ring closure and it's C3-C4 double bond isomerization.
Although alkyl substitution can lower the Ea for C3-C4 double bond
isomerization of 1,3,5-hexatriene by approximately 6 kcal/mol57 and
perfluorination of 2-butene leads to a lowering of the E<-Z isomerization by 6.4
kcal/mol versus the hydrocarbon,103 it is inconceivable that the fluorination of Z-
56 will lead to lowering in energy of the C4-C5 double bond Z->E isomerization
so as to make this process exclusively preferred over the 671 ring closure.
The next process observed to occur is a 4k cyclization of triene 56. An
equilibrium ratio of 1.64:1 was established between 56 (E and Z) and 59 at
202C in n-pentane as illustrated in Figure 2-35.
Perfluoro-1,3,5-hexatriene (76) has been reported in a patent to afford
an 84% yield of perfluoro-1,3-cyclohexadiene (77) upon pyrolysis at 450C in a
flow system.69 Concurrent to this thesis project, a thermal study of perfluoro-
1,3,5-hexatriene at lower temperatures was reported.86 These authors offered
similar results to those obtained in our study of 56. Thermolysis of


63
Figure 2-35. Mixture Obtained from Thermolysis of Perfluoro-E,Z,E(E,E,E)-4,5-
dimethyl-2,4,6-octatriene (Z-56(E-56)) at 202.0C in n-Pentane.
perfluoro-1,3,5-hexatriene at 160C established an equilibrium mixture
consisting of 9% perfluoro-1,3,5-hexatriene and 90% perfluoro-3-
ethenylcyclobutene (78). Thermolysis of perfluoro-1,3,5-hexatriene at 220C
was reported to irreversibly yield perfluoro-1,3-cyclohexadiene.
In the fluorinated 1,3,5-triene systems, formation of 3-
alkenylcyclobutenes in preference to 1,3-cyclohexadienes upon thermolysis
leads to the conclusion that the energy surfaces for the hydrocarbon and
fluorocarbon systems are quite different. It is informative to observe the
enthalpy diagram (Figure 2-36)57 for the hydrocarbon CeH8 system. Formation
of 3-ethenylcyclobutene (89) by a 4n conrotatory electrocyclic process is not
observed in hydrocarbon 1,3,5-triene thermal studies. E-1,3,5-Hexatriene (36)
isomerizes to the Z-triene (37) which then undergoes the 6n ring closure to 1,3-
cylohexadiene (38). Both processes are preferred over the 4n cyclization.
Perfluoro-1,3,5-hexatriene is seen to form perfluoro-1,3-cyclohexadiene at
higher temperatures and it is likely that perfluoro-E,Z,E-4,5-dimethyl-2,4,6-
octatriene (Z-56) would have exhibited a similar reaction path had the system
been investigated at higher temperatures.


64
Figure 2-36. Enthalpy Diagram for C6H8 Transformations.
The data obtained from these perfluoro-1,3,5-triene systems, although
qualitative in nature, require changes in the energy profile for fluorinated 1,3,5-
triene transformations (Figure 2-37). The thermal equilibrium rich in perfluoro-
3-alkenylcyclobutenes in the cases of perfluoro-1,3,5-hexatriene (76) and
perfluoro-E,Z,E(and E,E,E)-4,5,-dimethyl-2,4,6-octatriene (Z-56(£-56)) lead to
a lowering of the AHp of the perfluoro-3-alkenylcyclobutenes relative to the
perfluoro-1,3,5-trienes. Such a change in the relative enthalpy has precedent
in the case of the earlier discussed fluorinated cyclobutene/1,3-diene
interconversions (Chapter One, Table 1-6 and Figure 1-12). In these examples,
it was found that the perfluorinated cyclobutenes were lower in energy than the
perfluoro-1,3-dienes with AAHRon the order of 17 kcal/mol between the
hydrocarbon and fluorocarbon systems. Irreversible formation of perfluoro-1,3-
cyclohexadienes from the fluoro-1,3(Z),5-trienes only in the high temperature
runs leads to these species having the most negative AHf of the isomers, but
with a raised energy barrier to the 6k disrotatory transition state.


65
Figure 2-37. Enthalpy Diagram for Perfluoro-1,3,5-triene Transformations.
Thermolysis of 9.10-Bis(trifluoroethenvnDhenanthrene (40)
Thermolysis of 9,10-bis(trifluoroethenyl)phenanthrene (40) was found to
form the desired 1,2,2,3,3,4-hexafluoro-2,3-dihydrotriphenylene (41), but only
as a small component in a very complicated overall reaction process. A virtually
unprecedented process for 1,3(Z),5-triene thermal chemistry, leading to
bicyclo[3.1.0]hex-2-ene 49 and subsequent rearrangement of this species, was
observed to comprise the major reaction pathway of 40.
Thermal studies of 1,2-dialkenyl aromatics are only rarely encountered in
the literature. Any attempt to investigate the electrocyclic chemistry of such
systems would be expected to be complicated by the instability of the cyclized
non-aromatic products under the reaction conditions and the facility of these
products to undergo further rearrangement. Thermal studies of a series of 1,2-
dipropenylbenzenes has been reported.104 These systems first show pendant
alkene isomerization which was proven to occur by [1,7]-sigmatropic hydrogen
shifts. Higher temperatures yield 1,2-dihydronaphthalenes and alkyl 1,2-
dihydronaphthalenes which arise from disrotatory ring closure followed by an


66
[1,5]-sigmatropic hydrogen shift. The mechanistic nature of these processes
was established by studying suitably deuterium labeled species, and a
mechanistic rationale was proposed as seen in Figure 2-38.104
Figure 2-38. Thermal Processes Observed for 1,2-Dipropenylbenzenes.
One instance of the thermolysis of 9,10-diethenylphenanthrene at 210C
has been reported to yield 35% triphenylene, apparently arising from formation
of the unstable 2,3-dihydrotriphenylene, which undergoes loss of hydrogen.94
From the thermodynamic argument offered early in this chapter, it was
believed that 9,10-diperfluoroalkenylphenanthrenes offered a chance to
observe a reversible thermal 6n electrocyclization in a 1,3(Z),5-triene system.
The thermodynamics seemed favorable and the potential for relatively
unprecedented fluorine shifts nonexistent due to the greater strength of the C-F
versus C-H bond. In this light, it was initially discouraging to observe such a
complex mixture upon thermolysis of 40.


67
Thermolysis of 9,10-bis(trifluoroethenyl)phenanthrene (40) led to
formation of two primary products and two secondary products as illustrated in
Figure 2-39. One of the primary thermal products, 1,2,2,3,3,4-hexafluoro-2,3-
dihydrotriphenylene (41), was observed to be formed to no more than 15% in
the reaction mixture over the temperatures examined. Contrary to expectations,
thermolysis of purified 41 under identical conditions used for cyliization of the
parent triene demonstrated that the cyclization was irreversible. The cyclized
Figure 2-39. Transformations Observed Upon Thermolysis of 9,10-
Bis(trifluoroethenyl)phenanthrene (40).
product 41 was predicted to be in an enthalpy range of 1 to -13 kcal/mol relative
to the parent triene 40. The fact that reversibility is not observed to any extent in
this system leads to the conclusion that this process is occurring with AHR< -5
kcal/mol. A higher temperature study of this material was not undertaken as
significant non-productive decomposition was found to be occurring at
temperatures used to study 40. As discussed earlier, having observed a good
fit to first-order theory for the loss of 40 and a constant ratio of (49+50+51 )/41
over the individual runs examined, activation parameters of AH* = 29.9 0.1


68
kcal/mol and AS* = -19.6 0.3 cal/molxdeg were obtained for formation of 41
from 40. Such parameters for the formation of 41, being formally a 6k
disrotatory process from 40, are difficult to rationalize as no comparative kinetic
data exists for cyclization of any other fluorinated 1,3(Z),5-triene system.
Formation of 1,4,4,5,6,6-hexafluoro-2,3-(9,10-phenanthro)bicyclo[3.1.0]-
hex-2-ene (49) was observed to be the major process early in the reaction of
40. This thermal cyclization of a fluorinated 1,3(Z),5-triene to form a fluorinated
bicyclo[3.1.0]hex-2-ene is unprecedented in fluorocarbon literature and only
one example, accompanied by minimal discussion, has been found in the
corresponding hydrocarbon literature and is illustrated in Figure 2-40.105 As
Figure 2-40. Thermal and Photoproducts of £-1-(f-Butylamino)-1,3(Z),5-
hexatriene.
discussed earlier, the activation parameters obtained for formation of 49 from
40 are AH* = 34.4 2.8 kcal/mol and AS* = -6.6 6.0 cal/molxdeg. The
unprecedented nature of this transformation does not allow for conjecture as to
the mechanistic significance of these values. Thus, potential processes
involved will be offered, with rationalization of the activation parameters left to
the future.
The thermal closure of a 1,3(Z),5-triene system to a bicyclo[3.1.0]hex-2-
ene ring is formally a Woodward and Hoffman allowed 47ta + 2na or 4rcs + 2ns
process.34 Determining the true stereochemical nature of the process requires
at a minimum, labels at each terminus of the reacting 1,3,5-triene system. Due
to the unprecedented nature of this thermal process, and the lack of


69
stereochemical labels in the aforementioned and 40 systems, the question of
symmetry conservation can not begin to be addressed. The formation of 49
from 40 involves a further complication as the necessary primary intermediate
88 (Figure 2-41) has still to undergo a vinylcyclopropane-cyclopentene
rearrangement to afford 49. Figure 2-41 offers a representation of the potential
processes involved in formation of 41 and 49. Direct 4na + 2na or 47is + 2ns
Figure 2-41. Mechanistic Rationale for Formation of 41 and 49.
cyclization of anti-40 could yield the primary intermediate 88. As previously
discussed, this material was also assumed to be a primary intermediate upon
photolysis of 40. Since this intermediate was not observed under the much
lower temperature photolysis conditions, it would certainly not be observable
under the thermolysis conditions. A vinylcyclopropane-cyclopentene


70
rearrangement must spontaneously occur as 88 is formed to relieve the strain
in this spiro-fused system and restore aromaticity to the central phenanthrene
ring. An alternate diradical process from anf/-40 may occur with formation of
the intermediate 90. In this case, closure of the terminus of one trifluoroethenyl
substituent on the second at its carbon attached to the phenanthrene ring would
yield the biradical 90 which may then recombine to 88 and rearrange to the
observed product 49.
1,4,4,5,6,6-Hexafluoro-2,3-(9,10-phenanthro)bicyclo[3.1.0]hex-2-ene
(49) was observed to further rearrange under the thermolysis conditions to form
50 and 51 (Figure 2-39). Since 49 was unreactive with trace fluoride at lower
temperatures and since disappearance of 49 follows first-order kinetics and
yields linear Eyring plots over the temperatures and through the 70% extent of
reaction examined, a mechanism involving fluoride catalysis can effectively be
ruled out.
A hydrocarbon analog, bicyclo[3.1.0]hex-2-ene (91, Figure 2-42), is
known to undergo thermal C1-C5 cyclopropane bond homolysis to yield
biradical 92, in which 1,2-H shifts may occur in two possible directions leading
to the observed products 1,4- and 1,3-cyclohexadiene (93, 94).54
91
94
Figure 2-42. Thermolysis of Bicyclo[3.1.0]hex-2-ene (91).


71
Thermolysis of benzobicyclo[3.1.0]hex-2-ene (95, Figure 2-43) has been
studied by the flash vacuum technique.106 Over the high temperatures
investigated (500-900C), it was found that the major primary product was
FVT
700C
96 (30%)
84 (5%)
+ Naphthalene (12%)
95
97 (8%)
98 (1%)
Figure 2-43. Flash Vacuum Thermolysis of Benzobicyclo[3.1.0]hex-2-ene (95).
1,2-dihydronaphthalene (96) with a variety of minor products (84, 97, 98) also
observed. These products were proposed as arising from homolytic cleavage
of the appropriate cyclopropane ring bond followed by a hydrogen shift (96, 97,
98) and electrocyclic process (84).
Gas and solution phase thermal rearrangement of
perfluorobenzobicyclo[3.1.0]hex-2-ene (100, Figure 2-44) has been reported in
a study addressing the reaction of perfluoroindene (99) with sources of
difluorocarbene.107108 Perfluoroindene (99) was found to react with
difluorocarbene generated from thermolysis of hexafluoropropylene oxide
(HFPO). At lower temperatures, perfluorobenzobicyclo[3.1.0]hex-2-ene (100)
was found to be the major product with smaller amounts of
perfluorodihydronaphthalenes (101, 102) and perfluoro-2-methylindene (103)
also being observed. Thermolysis of 100 was also independently investigated.
Thermolysis of neat 100 at 230C yielded an 1:1:7 mixture of 99:102:103 and
thermolysis at 670C in a flow system yielded an 3:1 mixture of 99:103.


72
HFPO, 670C
Figure 2-44. Reaction of Perfluoroindene (99) with Difluorocarbene and
Thermolysis of Perfluorobenzobicyclo[3.1.0]hex-2-ene (100).
Elimination of difluorocarbene6 can be a facile process in highly
fluorinated cyclopropanes and was observed in the thermal study of
perfluorobenzobicyclo[3.1.0]hex-2-ene (100), albeit at higher temperatures
than were involved in our study of 49. This process was revealed by formation
of significant amounts of perfluoroindene 99 upon thermolysis of 100. The
analogous compound in the case of 49 was never observed in any of the
thermolysis runs with 40 or 49. On these grounds, a mechanism involving
difluorocarbene can be ruled out.
Considering the above results, the observed thermal rearrangement of
49 to form 50 and 51 is not out of character. Figure 2-45 illustrates the
possible mechanistic route involved. Homolytic cleavage of only one out of the
three cyclopropane bonds in 49 is found to productively lead to products.
Cleavage of bonds a (104) or b (105) leads to biradicals which in both cases


73
Figure 2-45. Mechanistic Rationale for Thermal Decomposition of 1,4,4,5,6,6-
Hexafluoro-2,3-(9,10-phenanthro)bicyclo[3.1.0]hex-2-ene (49).
have one benzylic center; the other being on a secondary (104) and primary
(105) carbon. Appreciable overlap with the C9-C10 phenanthrene k system
early in cleavage of bond b may also facilitate such a process relative to
cleavage of bond a or c. Geminal difluorination of cyclopropanes is known to
weaken the C-C bond opposite to the fluorinated site and those adjacent to the
fluorinated site, although the weakening of the opposite bond is significantly
greater.6 Such an effect may be thought to possibly lead to facilitation of
cleavage of bond a. Here this factor is unlikely to be significant since this
cyclopropane system also contains fluorine at sites p to the geminally
difluorinated site which would counter such a disparity in bond strengths. The


74
final observed products require a 1,2-fluorine atom shift from the intermediate
biradical. A 1,2-fluorine atom shift in the case of 104 will be a higher energy
process than one in 105 due to the cleavage of the stronger C-F bond at the
difluorinated site in the former. This fact together with the stereoelectronic
preference for bond b cleavage and benzylic stabilization in 105 leads to
observation of products arising only from cleavage of 49 to 105. The other
possible ring cleavage route cto form biradical 106 is disfavored as such a
system affords no benzylic stabilization. The final observed products 50 and
51 then arise from 1,2-fluorine atom shifts of Fa (Figure 2-45) in one of two
directions in 105. The slightly favored product 50 is formed by shift towards the
stabilized radical center.
Fluorine atom shifts lack unambigous precedent in the literature.
Thermal [1,3] and [1,5]-fluorine atom shifts have been invoked in studies
involving isomerizations of dihydrohexafluorocyclohexa-1,3-dienes109 and
perfluoroisoindenes.110 Photochemical [1,5]-fluorine atom shifts have been
invoked in the isomerization of perfluoroindene to perfluoroisoindene111 and a
rearrangement of perfluorotricyclo[5.2.2.02-6]undeca-2,5,8-triene (107) to
perfluorotricyclo[5.2.2.026]undeca-2,3,8-triene (108).88
Figure 2-46. Photochemical [1,5]-Fluorine Atom Shift in Perfluorotricyclo-
[5.2.2.02-6]undeca-2,5,8-triene (107).


75
Steric Effects in Thermal 1.3(Z).5-Triene Electrocyclizations
The rule of orbital symmetry conservation for a concerted process
requires that C1-C6 bond formation in the thermal rearrangement of a 1,3(Z),5-
triene to a 1,3-cyclohexadiene occur by overlap of n orbitals on the same side of
the triene plane; hence defining a disrotatory process. A consequence of this
type of process is that 1,3(Z),5-triene C1 and C6 cis substituents are forced into
a more crowded position in the transition state than in the ground state. It is
found that higher activation energies are required to bring C1 and C6 within
bonding distance in the transition state due to this crowding, and often the
energy of the 6tc process will be sufficiently high so that alternate processes are
observed to varying extents.
Activation parameters for a variety of systems in the literature
demonstrate this steric effect and a few examples are given in Figure 2-47.
Many of the examples found (109,52 110,52 111,112 112112) show little change in
activation entropy, indicating similar transition state geometry and timing is
being maintained, therefore, the strain being built into the transition state is
manifesting itself as a measurable increase in activation enthalpy. Sufficiently
hindered systems (11373) often do not undergo 6k cyclization from the initial
1,3(Z),5-triene, but rearrange by other processes such as hydrogen shifts to
trienes which are more suited for the disrotatory process.
An interesting result has been reported for the thermal study of 6k ring
closure in a C1 and C6 deuterated Z-1,3,5-hexatriene (Figure 2-48).113
Secondary isotope effects (kH/ko) of 1.05 for 1E,5E-D2 (114) and 0.88 for 1Z,5Z-
D2 (115) were observed. The two transition states involved are
diastereomerically related with respect to the deuterium substituents. Due to
the different stereochemical environments in the transition state, an increase in


76
intramolecular non-bonding interactions was proposed to increase the force
constants in the case of the terminally c/'s-deuterated material 115 and give rise
to the inverse kn/ko effect observed .
AH* (kcal/mol)
28.6
32
28.2
AS* (eu)
-7
-6
-1
34 -1
c6h5
^%^ceHs
CH2CH3
Figure 2-47. Activation Parameters for Non-Hindered versus Hindered 1,3(Z),5-
Triene Cyclizations.
Figure 2-48. 1E,5E-D2 (114) and 1Z.5Z-D2-1,3(Z),5-Hexatriene (115).
1,3(Z),5-Triene cyclizations have received considerable theoretical
interest. In calculated transition states for the disrotatory 6rc 1,3(Z),5-triene
electrocyclization, a definite steric crowding in is found between the C1 and C6


77
cis substituents.72'113'114'115'116 The transition state is a boat-like ring conformation
(Figure 2-49) with C1 and C6 cis hydrogens twisted in and separated by less
than the sum of their van der Waal's radii.
Figure 2-49. Approximate Representation of the Calculated 1,3(Z),5-Triene
Disrotatory Transition State.
Conclusions
It is believed that for the cases of the fluorinated 1,3(Z),5-trienes
examined in this study and found in the literature; 9,10-
bis(trifluoroethenyl)phenanthrene (40), perfluoro- E,Z,£-4,5-dim ethyl-2,4,6-
octatriene (Z-56), and perfluoro-Z-1,3,5-hexatriene (76), significant repulsion
must develop between the C1 and C6 1,3(Z),5-triene cis fluorines upon
approach to the boat-like disrotatory transition state. This repulsion leads to an
increase in the energy barrier for this process and subsequently, increased
potential for occurrence of competing processes. The observation of
cyclobutene products from An conrotatory ring closure in these systems seems
reasonable in light of this increased barrier. Closure in a An conrotatory
manner is proposed to have a transition state which does not contain crowding
of the terminal cis substituents as illustrated in Figure 2-50.117'118 This together
with the observed reversal of the relative thermodynamics in the perfluorinated


78
and hydrocarbon cyclobutene/1,3-diene systems lead to An closures as facile
and primary processes in the thermolysis of fluorinated 1,3(Z),5-trienes.
Figure 2-50. Approximate Representation of the Calculated 1,3-Diene
Conrotatory Transition State.
An analogous process to the reported 6tc thermal closure of perfluoro-Z-
1,3,5-hexatriene at higher temperatures was never observed in thermal studies
of perfluoro-E,Z,E-4,5-dimethyl-2,4,6-octatriene (Z-56) most likely because
sufficiently high temperatures were not used in the study of this material.
The fact that terminal cis fluorines impede the 1,3(Z),5-triene disrotatory
process should not be surprising in light of the previous discussions. It is
surprising though, in terms of the magnitude of the effect. The fact is that in
these fluorinated systems, An cyclization is favored over 671, and occurring
roughly at temperatures necessary for the hydrocarbon 6n rearrangement. This
large deviation in the thermal chemistry of fluorocarbon from hydrocarbon
precedent upon terminal 1,3(Z),5-triene cis fluorination created the impetus for
further study of fluorine's effect on thermal processes involving disrotatory and
conrotatory transition states. Out of this interest, a strategy designed to provide
more insight to this seeming steric influence of fluorine was developed and it's
study is described in Chapter 3.


CHAPTER 3
[3,3]-SIGMATROPIC REARRANGEMENTS OF
TERMINALLY FLUORINATED 1,5-DIENES
Introduction
The observation that 6n thermal disrotatory closure of perfluorinated
1,3(Z),5-trienes is disfavored to such an extent that other primary processes
occur exclusively, is unprecedented and encouraged further attention. The
usual strong electronic influence of fluorine on a reaction process seemed in
the disrotatory process to be offset by an factor more steric in origin. As
discussed in Chapter 1, such influences are rarely responsible for the course of
reaction in fluorinated organic systems due to the small difference between
fluorine and hydrogen in size and bond length to carbon. Nevertheless, the
tightly bound nature of the concerted transition state which is required for
1,3(Z),5-triene disrotatory cyclization leads to a twisting in and crowding of the
terminal cis substituents which is believed to be at least partially responsible for
the observed deviation of perfluorocarbon chemistry from that of analogous
hydrocarbons. While precedent from the hydrocarbon literature indicated
destabilization of such a transition state by groups substantially larger than
hydrogen at the 1,3(Z),5-triene terminal cis positions, it seemed surprising that
upon substitution of hydrogen by fluorine at these positions, rather than
observing an higher energy disrotatory process, alternate rearrangements were
observed. It was then the intention to study another system with a lesser degree
of fluorination rearranging from a specific conformation which would allow a
79


80
more quantitative understanding of the effect terminal fluorination has on
pericyclic processes.
The f3.31-Siqmatropic Shift of 1.5-Dienes: The Cope Rearrangement
A hydrocarbon system which has been thoroughly scrutinized
experimentally and theoretically is the Cope Rearrangement. This process is
formally a subset of the family of sigmatropic shifts, which involve migration of a
a bonded atom or n system from one terminus of a conjugated n system to the
other in a concerted fashion. The all carbon [3,3]-sigmatropic shift was
discovered by Hurd119 and later by Cope120 and the most simple case involving
the degenerate rearrangement of 1,5-hexadiene is illustrated in Figure 3-1.
5
1
4%^ 6
5
Figure 3-1. The Cope Rearrangement of 1,5-Hexadiene.
Orbital symmetry considerations dictate that the process occur in a [3S,3S]
fashion, meaning that bonding occurs from the same face at the terminus of
each three carbon fragment.34 Such a restriction still allows for the
rearrangement to occur through a number of viable conformations of the 1,5-
diene system. Among the conformations available to this system, it has been
experimentally demonstrated that the Cope rearrangement occurs preferentially
through a chair conformation transition state except in cases where the system
is geometrically constrained so as to make the chair inaccessible. A variety of
studies involving stereochemically labeled 1,5-diene systems have


81
demonstrated the exclusive nature of this process and estimate the chair is
favored over a boat conformation transition state by at least 6 kcal/mol in
enthalpy.54 Semiempirical121 and more recent ab initio122 123 level theoretical
studies confirm by similar barriers the experimental preference found for the
chair over the boat transition state conformation. The energy difference and
hence the exclusive chair transition state for this process is rationalized as
being due to a through space, destabilizing antibonding interaction between
orbitals on C2 and C5 in the boat conformation.34124 Although there is no
question as to the preferred conformation of the transition state, the aspect of
synchronicity or bond timing in this concerted process has been under
continuous debate. Such mechanistic finepoints will be addressed later in
discussion but at this point, only the aspect of favored conformation will be
considered.
The Cope system appears to be ideal for study of the effect of terminal
fluorination, as the transition state geometries (Figure 3-2) contain the same
bulk structural features which were rationalized as influencing the fluorinated
thermal electrocyclic processes discussed in Chapter 2. The calculated
transition state conformation for the thermal 6k disrotatory process113 is
structurally similar to a boat Cope process121-122 and the photochemical 6k
conrotatory process125 is similar to the chair Cope process.121-122 The Cope
system surpasses the electrocyclic process in terms of utility for thermal study in
that both the boat and chair Cope processes are orbital symmetry allowed
thermal processes, whereas the electrocyclic disrotatory and conrotatory
processes are allowed only for thermal and photochemical excitation
respectively. The fundamental differences between the ground and excited
state processes in the 6k electrocyclic study do not allow for easy comparison of
activation parameters or discussion of steric and electronic effects of terminal


82
substituents between the two conformations. Seeing as both conformations may
undergo symmetry allowed thermal Cope processes, design of appropriate
terminally fluorinated 1,5-dienes and measurement of the activation parameters
for Cope rearrangement would allow for a more quantitative understanding as
to the effect of terminal fluorination on these transition state conformations.
Figure 3-2. 6k Electrocyclic and Cope Transition State Conformations.
Fluorinated Cope Systems
The thermal study of fluorinated 1,5-dienes has received little qualitative
or quantitative attention. Two recent reviews offer the minimal literature
available addressing qualitative aspects of [3,3]-sigmatropic processes in
fluorinated 1,5-dienes,126 allylvinyl ethers,126 and carbanions.127
The observation of the effect of terminal fluorine on a chair constrained
thermal Cope process was most easily studied by synthesizing terminally
fluorinated dienes which would complement hydrocarbon systems for which
reliable activation parameters had been previously reported. Due to the
degeneracy in the system, the parent 1,5-hexadiene had been studied as


83
1,1-dideutereo-1,5-hexadiene (Figure 3-3, 116).128 The partially fluorinated E-
and Z-1-fluoro-1,5-hexadiene129 (118, 119), and 1,1-difluoro-1,5-hexadiene129
(121) thermal studies had already been reported in the literature with reliable
activation parameters. To complete the simple 1,5-hexadiene series required
synthesis and thermal study of 1,1,6,6-tetrafluoro-1,5-hexadiene (123).
Figure 3-3. Fluorinated 1,5-Hexadiene Cope Processes of Interest.
The experimental study of boat constrained Cope systems has received
a variety of interest, and again, systems were chosen for mechanistic novelty,
activation parameter reliability of the reported hydrocarbons, and synthetic
simplicity. Two hydrocarbon systems (Figure 3-4) which have been
investigated where geometrical constraints force a boat conformation Cope
rearrangement are 1,4-dimethylenecyclohexanes130131 such as 125, and meso-
1-(2-methylidenecyclopentyl)-2-methylidenecyclopentane132 (meso-126). An
artifact of the synthetic route into meso-126, the d,/-1 -(2-methylidene-
cyclopentyl)-2-methylidenecyclopentane isomer d,l-126 is also afforded. This


84
diastereomer is constrained to undergo the Cope rearrangement through a
chair conformation, creating another system for comparison with those of Figure
3-3.
d,A126
Figure 3-4. Cope Rearrangements in Conformationally Constrained Systems.
There is a subtle but important difference between the two boat
conformations involved with 125 and meso-126. Due to the symmetry of the
system, the boat type transition state for 125 will constrain the two terminal
methylenes to approach one another in a coplanar eclipsed fashion with no
twisting in of terminal substituents. In contrast, the meso-
bismethylenecyclopentane meso-126 will be able to accommodate a true boat
transition state which involves a significant turning in of the two terminal cis
substituents. A thermal study of 1,4-dideuteriomethylidenecyclohexane (125)
has been reported as has a study of the hydrocarbon d,l- and


85
meso-bismethylenecyclopentanes {d,l-126, meso-126), and all are reported
with reliable activation parameters.
The materials then of interest in this study are illustrated in Figure 3-5. To
probe the effect of terminal fluorination in these different systems, the synthesis
of a variety of materials was required to complete each series from
hydrocarbon, to terminally gem-difluorinated, to terminally bis-gem-difluorinated
1,5-diene. Having reliable reported activation parameters for 116, 121, 125,
and meso and cf,/-126, it was necessary to carry out syntheses and thermal
studies of 123, 128, 129, meso and d,l-130, and meso and cf,/-131.
Although interest existed in meso and d,l-130, this system was not studied
due to time limitations. The synthetic routes and thermal results for 123, 128,
129, and meso and d,l-131 will now be discussed.
Figure 3-5. Three Hydrocarbon to Terminally Fluorinated 1,5-Diene Series.


86
Synthesis and Thermolysis of Terminally Gem-difluorinated 1.5-Diene Systems
1.1.6.6-Tetrafluoro-1,5-hexadiene (123)
1,1,6,6*Tetrafluoro-1,5-hexacliene (123) was synthesized in six steps
from 1,4-butanediol in an overall isolated yield of 6%. The reaction sequence is
illustrated in Figure 3-6. 4-[(Tetrahydro-2/-/-pyran-2-yl)oxy]-1-butanal (132) was
prepared by a literature procedure133 from 1,4-butanediol in two steps and
subjected to a Wittig-type fluoroolefination134 to yield 5-[(tetrahydro-2F/-pyran-2-
yl)oxy]-1,1-difluoropent-1-ene (133). Deprotection to 5,5-difluoro-4-penten-1-ol
(134) and pyridinium dichromate (PDC) oxidation yielded 5,5-difluoro-4-
pentenal (135). Wittig-type fluoroolefination then afforded the desired 1,1,6,6-
tetrafluoro-1,5-hexadiene (123). Initial attempts to obtain 123 through Wittig-
type fluoroolefination of 1,4-butanedial did not afford any amount of fluoroolefin
and was not further pursued.
H
132
OTHP
Figure 3-6. Synthesis of 1,1,6,6-Tetrafluoro-1,5-hexadiene (123).
Due to appreciable volatility, the thermolysis of 123 was examined in the
gas phase as described in Appendix A. Quantitative conversion of 123 to


Ln[%123]
87
207.2C
216.2C
224.4C
228.8C
235.7C
241.6C
Temperature (c)
k (x105 sec'1)
R2
207.2
2.24 0.01
0.9999
216.2
4.13 0.05
0.9993
224.4
6.88 0.07
0.9996
228.8
8.87 0.12
0.9993
235.7
13.68 0.07
0.9999
241.6
19.76 0.10
0.9999
k^CF2 ^ %^CF2
123 124
Figure 3-7. First-Order Rate Plots and Rate Constants for Thermolysis of
1,1,6,6-Tetrafluoro-1,5-hexadiene (123).


88
3,3,4,4-tetrafluoro-l,5-hexadiene (124, Figure 3-7) was observed. The
thermolysis was examined at six temperatures from 207.2C to 241.6C and the
conversion was observed to follow first-order kinetics with no degree of
reversibility observed. Figure 3-7 offers the first-order plots and rate constants
for the temperatures examined.
The activation parameters (AH*, AS*) for the cyclization were obtained
kJ [.AH] [ASM
using the Eyring expression,68 k = e^ RT V R rearranged to the form
h
Ln(k/T) = -AH*/RT + AS*/R + Ln{k/h), where k = rate constant at absolute
temperature T, k = Boltzmann constant (1.381x10 23 J/K), h = Planck's constant
(6.626x10-34 Jxs), and R = ideal gas constant (1.9872 cal/moIxK). A linear least-
squares regression plot of Ln(k/T)versus 1/T, as illustrated in Figure 3-8, yielded
AH* = 29.9 0.2 kcal/mol and AS* = -18.5 0.5 cal/molxdeg for the Cope
rearrangement of 123 to 124 with the errors reported as one standard
deviation.
Figure 3-8. Eyring Plot for Thermolysis of 1,1,6,6-Tetrafluoro-1,5-hexadiene
(123).


89
1-Difluoromethylidene-4-methvl¡denecvclohexane (1281
1-Difluoromethylidene-4-methyl¡denecyclohexane (128) was prepared
in three steps from 1,4-cyclohexanedione mono-ethylene ketal (136) in a 37%
isolated yield. The reaction sequence is illustrated in Figure 3-9.
136
(C6H5)3PCH3Br
n-BuLi, THF, 0C
^-CX
137 (69%)
15% H2S04
Silica Gel
CH2CI2
138 (90%)
P(N(CH3)2)3
CF2Br2
THF, 0C-RT, 4 hr
128 (38%)
Figure 3-9. Synthesis of 1-Difluoromethylidene-4-methylidenecyclohexane
(128).
4-Methylidene-1-cyclohexanone ethylene ketal (137) was prepared from 1,4-
cyclohexanedione mono-ethylene ketal (136) by a Wittig reaction135 then
deprotected136 to yield 4-methylidenecyclohexanone (138). This material was
subjected to Wittig-type fluoroolefination134 to yield the desired 128.
Due to appreciable volatility, the thermolysis of 128 was examined in the
gas phase as described in Appendix A. Quantitative conversion of 128 to 1,1-
difluoro-2,5-dimethylidenecyclohexane (139, Figure 3-10) was observed. The
thermolysis was examined at six temperatures from 279.9C to 309.1C. The
conversion was observed to follow first-order kinetics and no degree of
reversibility was observed. Figure 3-10 offers the first-order plots and rate
constants for the temperatures examined.


90
Temperature (C)
k (x10s sec1)
R2
279.9
3.78 0.09
0.9976
287.8
6.72 0.04
0.9998
292.1
8.88 0.19
0.9977
297.6
12.51 0.19
0.9989
303.0
18.12 0.15
0.9996
309.1
25.72 0.16
0.9998
cf2
A
^^CF2
128
139
Figure 3-10. First-Order Plots and Rate Constants for Thermolysis of
1 -Difluoromethylidene-4-methylidenecyclohexane (128).
279.7C
287.8C
292.1 C
297.6C
303.0C
309.1 C


Full Text

PAGE 1

7+(50$/ $1' 3+272&+(0,&$/ 678',(6 2) %,675,)/8252(7+(1
PAGE 2

72 '$' 020 -$&48(/,1( +(/(1 $1' .$5<1

PAGE 3

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nV 3LFN XS WKH WRROV WR 0RPfV 6WRS SURFUDVWLQDWLQJ DQG JHW WR \RXU KRPHZRUNHFKR LQ P\ KHDG IURP WLPH WR WLPH DQG UDLVH P\ OHYHO RI SURGXFWLYLW\ 7KH IULHQGV DQG FROOHDJXHV KDYH PHW VLQFH DW WKH 8QLYHUVLW\ RI )ORULGD 'HSDUWPHQW RI &KHPLVWU\ DUH QXPHURXV *UHDWO\ DSSUHFLDWHG DUH WKH H[FHSWLRQDO IDFXOW\ PHPEHUV KDYH KDG WKH RSSRUWXQLW\ WR LQWHUDFW ZLWK DQG ZKRVH FRXUVHV KHOSHG WR IRUP WKH FRUH RI P\ FKHPLFDO LQWXLWLRQ 'XH WR P\ H[WHQGHG VWD\ LQ WKH 'ROELHU JURXS WKDQNV DUH UHTXLUHG WR D QXPEHU RI

PAGE 4

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

PAGE 5

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

PAGE 6

'cGcIOXRURPHWK\OcGHQHfF\FORKH[DQH PHVR DQG F'LIOXRUFPHWK\OLGHQHF\FORSHQW\Of GLIOXRURPHWK\OLGHQHF\FORSHQWDQH 'LVFXVVLRQ &RQFOXVLRQV (;3(5,0(17$/ *HQHUDO 0HWKRGV ([SHULPHQWDO 3URFHGXUHV $33(1',; $ *$6 3+$6( 7+(502/<6,6 $33$5$786 $33(1',; % 6(/(&7(' ) 105 63(&75$ 5()(5(1&(6 %,2*5$3+,&$/ 6.(7&+ 9,

PAGE 7

$EVWUDFW RI 'LVVHUWDWLRQ 3UHVHQWHG WR WKH *UDGXDWH 6FKRRO RI WKH 8QLYHUVLW\ RI )ORULGD LQ 3DUWLDO )XOILOOPHQW RI WKH 5HTXLUHPHQWV IRU WKH 'HJUHH RI 'RFWRU RI 3KLORVRSK\ 7+(50$/ $1' 3+272&+(0,&$/ 678',(6 2) %,675,)/8252(7+(1@KH[HQH E\ LUUHYHUVLEOH FRPSHWLWLYH ILUVWRUGHU SURFHVVHV 7KH FRPSHWLWLYH IRUPDWLRQ RI KH[DIOXRUR SKHQDQWKURfELF\FOR>@KH[HQH LV YLUWXDOO\ XQSUHFHGHQWHG LQ WULHQH WKHUPDO FKHPLVWU\ ZLWK RQO\ RQH VLPLODU F\FOL]DWLRQ IRXQG LQ WKH K\GURFDUERQ OLWHUDWXUH 7KHUPRO\VLV RI KH[DIOXRURSKHQDQWKURf ELF\FOR>@KH[HQH OHG WR IXUWKHU UHDUUDQJHPHQW DQG ZDV H[DPLQHG LQ VROXWLRQ EHWZHHQ r& DQG r& 7KLV PDWHULDO ZDV IRXQG WR UHDUUDQJH WR GLIOXRURPHWK\OLGHQHWHWUDIOXRURSKHQDQWKURfF\FORSHQW HQH YLL

PAGE 8

DQG SKHQDQWKURfWULIOXRURWULIOXRURPHWK\OF\FORSHQWDGLHQH WKURXJK LUUHYHUVLEOH FRPSHWLWLYH ILUVWRUGHU SURFHVVHV 3KRWRO\VLV RI ELVWULIOXRURHWKHQ\OfSKHQDQWKUHQH LQ VROXWLRQ OHG WR KH[DIOXRURSKHQDQWKURfELF\FOR>@KH[HQH DV WKH PDMRU SURGXFW ZLWK KH[DIOXRURGLK\GURWULSKHQ\OHQH DQG >QQ@ F\FORDGGLWLRQ SURGXFWV KH[DIOXRURSKHQDQWKURf ELF\FOR>@KH[HQH DQG KH[DIOXRURSKHQDQWKURf ELF\FOR>@KH[HQH EHLQJ REVHUYHG LQ PLQRU DPRXQWV 7KHUPRO\VLV RI SHUIOXRUR(=( DQG (((GLPHWK\ORFWDWULHQH ZDV VWXGLHG LQ VROXWLRQ EHWZHHQ r& DQG r& DQG LQLWLDOO\ IRXQG WR XQGHUJR && GRXEOH ERQG LVRPHUL]DWLRQ $W KLJKHU WHPSHUDWXUHV DQ HTXLOLEULXP EHWZHHQ WKH SHUIOXRURRFWDWULHQH DQG SHUIOXRURFnV DQG IUDQV WULPHWK\O(SURSHQ\OfF\FOREXWHQH LV HVWDEOLVKHG UHTXLULQJ DQ UF HOHFWURQ FRQURWDWRU\ HOHFWURF\FOLF SURFHVV 3KRWRO\VLV RI SHUIOXRUR(=( DQG (((GLPHWK\ORFWDWULHQH LQ VROXWLRQ OHDGV WR IRUPDWLRQ RI SHUIOXRURIUDQVWHWUDPHWK\O F\FORKH[DGLHQH E\ D WW HOHFWURQ FRQURWDWRU\ HOHFWURF\FOLF SURFHVV 7KLV PDWHULDO ZDV IRXQG WR XQGHUJR IXUWKHU SKRWRF\FOL]DWLRQ WR SHUIOXRURWUDQV WHWUDPHWK\OELF\FOR>@KH[HQH WKURXJK D F HOHFWURQ GLVURWDWRU\ HOHFWURF\FOLF SURFHVV 5HOXFWDQFH RI WKHVH SHUIOXRULQDWHG=fWULHQHV WR XQGHUJR WKH WKHUPDO Q HOHFWURQ GLVURWDWRU\ HOHFWURF\FOL]DWLRQ YLD WKH UHTXLUHG ERDW WUDQVLWLRQ VWDWH ZDV HYLGHQW DV ZDV WKH IDFLOLW\ RI WKH SKRWRSURFHVV WR RFFXU WKURXJK WKH SKRWRDOORZHG Q HOHFWURQ FRQURWDWRU\ HOHFWURF\FOL]DWLRQ YLD D FKDLU WUDQVLWLRQ VWDWH 7KLV GLVSDULW\ ZDV EHOLHYHG WR DULVH IURP D GHWULPHQWDO LQWHUDFWLRQ EHWZHHQ WHUPLQDO FLV IOXRULQHV DV WKH =fWULHQH DSSURDFKHV WKH ERDWOLNH GLVURWDWRU\ WUDQVLWLRQ VWDWH DQG UHTXLUHG IXUWKHU VWXG\ 9,,,

PAGE 9

7KH V\VWHP FKRVHQ WR SUREH WKLV HIIHFW ZDV WKH WKHUPDO >@VLJPDWURSLF UHDUUDQJHPHQW RI WHUPLQDOO\ JHPGLIOXRULQDWHG GLHQHV 6\QWKHVLV DQG JDV SKDVH WKHUPDO VWXG\ RI WHWUDIOXRURKH[DGLHQH GLIOXRUR PHWK\OLGHQHPHWK\OLGHQHF\FORKH[DQH GLGLIOXRURPHWK\OLGHQHfF\FOR KH[DQH DQG VROXWLRQ SKDVH WKHUPDO VWXG\ RI PHVR DQG DIr GLIOXRURPHWK\OLGHQHF\FORSHQW\Of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

PAGE 10

&+$37(5 $1 29(59,(: 2) )/825,1( 68%67,78(17 ())(&76 ,1 25*$1,& 6<67(06 ,QWURGXFWLRQ 7KH LVRODWLRQ RI IOXRULQH E\ +HQUL 0RLVVDQ RQ -XQH FUHDWHG FRQVLGHUDEOH DFDGHPLF LQWHUHVW DQG OHG WR UDSLG DGYDQFHV LQ WKH ILHOG RI IOXRULQH FKHPLVWU\ ,Q 0LGJHO\ DQG +HQQH GHYHORSHG &)&, DV D FKHDS DQG VDIH UHIULJHUDQW WR UHSODFH WKH WR[LF JDV DPPRQLD ZKLFK HOHYDWHG IOXRULQH FKHPLVWU\ RXW RI LWn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

PAGE 11

HOHPHQWV ZLWK D 3DXOLQJ VFDOH YDOXH RI DV FRPSDUHG ZLWK R[\JHQ f FKORULQH f EURPLQH f FDUERQ f DQG K\GURJHQ f 6WURQJ SRODUL]DWLRQ RI IOXRULQDWHG PROHFXOHV WKURXJK WKH D ERQGLQJ IUDPHZRUN DQG WKURXJK VSDFH ILHOG HIIHFWVf DUH UHVXOWV RI IOXRULQHnV ODUJH HOHFWURQHJDWLYLW\ 7KH DWRP LV PRQRYDOHQW DQG DFFRPPRGDWHV WKUHH QRQERQGHG HOHFWURQ SDLUV LQ RUELWDOV RI VLPLODU GLPHQVLRQ WR K\EULGL]HG RUELWDOV RQ FDUERQ %HFDXVH RI WKHVH WZR SUHFHGLQJ IDFWRUV IOXRULQH H[KLELWV DQ LQWHUHVWLQJ GRQRUDFFHSWRU FRQWUDGLFWLRQ XQGHU FHUWDLQ FLUFXPVWDQFHV LQ WKDW WKH VWURQJ UHPRYDO RI HOHFWURQ GHQVLW\ IURP D ERXQG DWRP FDQ EH RIIVHW GXH WR EDFN GRQDWLRQ RI GHQVLW\ IURP WKH QRQERQGHG HOHFWURQV 7KH YDQ GHU :DDOV UDGLXV RI IOXRULQH LV ƒ &RPSDUHG ZLWK WKH RWKHU KDORJHQV FDUERQ DQG K\GURJHQ YDQ GHU :DDOV UDGLL &O ƒ %U ƒ ƒ &DLLSKD_& ƒ + ƒf IOXRULQH VKRXOG H[KLELW PLQLPDO VSDWLDO UHTXLUHPHQWV DV D VXEVWLWXHQW D IDFW ZKLFK KDV DOORZHG IRU FRPSOHWH VXEVWLWXWLRQ RI K\GURJHQ E\ IOXRULQH LQ PDQ\ K\GURFDUERQ V\VWHPV 7KLV KDV HQDEOHG WKH FRPSOHWHO\ V\QWKHWLF ILHOG RI SHUIOXRURFDUERQ FKHPLVWU\ WR EH GHYHORSHG DQG H[SORLWHG E\ LQGXVWU\ DQG DFDGHPLFV ZLWK VXEVWDQWLDO ILQDQFLDO DQG VFKRODUO\ VXFFHVV 7KH HIIHFWV RI IOXRULQH DV D VXEVWLWXHQW LQ RUJDQLF V\VWHPV KDYH EHHQ WKH VXEMHFW RI D QXPEHU RI UHYLHZVnnnn WKRVH RI 6PDUW EHLQJ PRVW LQVLJKWIXO 7KLV LQWURGXFWLRQ ZLOO GHPRQVWUDWH WKH ZD\V LQ ZKLFK IOXRULQH VXEVWLWXWLRQ SHUWXUEV WKH VWUXFWXUH DQG UHDFWLYLW\ RI VLPSOH K\GURFDUERQV )OXRURDONDQHV 7KH VHULHV RI IOXRULQDWHG PHWKDQHV VKRZ DQ LQWHUHVWLQJ WUHQG LQ &) ERQGLQJ 7DEOH LOOXVWUDWHV WKH VWUHQJWKHQLQJ DQG LQFUHPHQWDO VKRUWHQLQJ RI WKH &) ERQG LQ WKLV VHULHV 7KLV WUHQG RI ERQG VWUHQJWKHQLQJ ZLWK LQFUHDVHG

PAGE 12

7DEOH &) %RQG /HQJWKV DQG 'LVVRFLDWLRQ (QHUJLHV LQ )OXRURPHWKDQHV )OXRURPHWKDQH U &)f L$O 'r&)f NFDOPROf FKI FKI FKI FI 7DEOH %RQG /HQJWKV DQG 'LVVRFLDWLRQ (QHUJLHV LQ )OXRURHWKDQHV )OXRURHWKDQH U &&fM$O 'r&&f NFDOPROf 'rI&)f NFDOPROf FKFK FKFKI FKFKI 8QNQRZQ FKFI IFKFI &+)f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

PAGE 13

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fn I ) )LJXUH )OXRULQH 'RXEOHERQG 1RERQG 5HVRQDQFH $V WKH GHJUHH RI JHPLQDO IOXRULQDWLRQ LQFUHDVHV WKH QXPEHU RI YDOHQFH ERQG VWUXFWXUHV LQYROYLQJ GRXEO\ ERXQG IOXRULQH LQFUHDVHV DQG WKH &) ERQGV DUH LQFUHDVLQJO\ VKRUWHU DQG VWURQJHU 7KHRUHWLFDO FDOFXODWLRQV DW WKH DE LQLWLR OHYHO KDYH FRQILUPHG VXFK D ERQGLQJ VFKHPH ZKHUH LW LV IRXQG WKDW WKH VWDELOL]LQJ LQWHUDFWLRQ DULVHV IURP EDFNGRQDWLRQ RI D IOXRULQH ORQH SDLU LQWR DQ DQWLERQGLQJ RrFI RUELWDOnf 7KLV H[SODQDWLRQ EDVHG RQ IOXRULQH QRQERQGHG HOHFWURQ LQWHUDFWLRQV WR UDWLRQDOL]H WKH REVHUYHG ERQGLQJ DQG JHRPHWU\ FKDUDFWHULVWLFV LQ IOXRURRUJDQLFV LV FRPSOHPHQWHG E\ RWKHU DUJXPHQWV ZKLFK LQKHUHQWO\ GR QRW LQYROYH WKH QRQERQGLQJ HOHFWURQV RQ IOXRULQH 2QH VXFK DUJXPHQW VXJJHVWV WKDW ZKHQ FDUERQ LV ERXQG WR PRUH HOHFWURQHJDWLYH HOHPHQWV DWRPLF S FKDUDFWHU FRQFHQWUDWHV LQ RUELWDOV GLUHFWHG WRZDUGV WKH HOHFWURQHJDWLYH VSHFLHV

PAGE 14

VLQFH S HOHFWURQV DUH OHVV WLJKWO\ ERXQG WKDQ V HOHFWURQVn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f ƒ U&)f ƒ +&+ GHJ +&) GHJ )&) GHJ 'rQ NFDOPRO 8QNQRZQ 8QNQRZQ

PAGE 15

JHPLQDOO\ GLIOXRULQDWHG ROHILQV FRQWDLQ )&) ERQG DQJOHV ZKLFK DUH PXFK VPDOOHU WKDQ HWK\OHQH DQG YHU\ FORVH WR WKH WHWUDKHGUDO YDOXH RI r 7KHRUHWLFDO DE LQLWLR OHYHO FDOFXODWLRQV VKRZ WKH &) ERQG VKRUWHQLQJ FDQ EH DWWULEXWHG WR IOXRULQH QRQERQGHG HOHFWURQ GHORFDOL]DWLRQ LQWR WKH WF Ff PROHFXODU RUELWDO DV GHSLFWHG LQ D YDOHQFH ERQG IDVKLRQ E\ )LJXUH n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nV GRXEOH ERQG VXFK DV EURPLQDWLRQ FKORULQDWLRQ +; ; %U &O ,f DGGLWLRQ DQG SRO\PHUL]DWLRQ DUH DOO LQ H[FHVV RI NFDOPRO PRUH H[RWKHUPLF WKDQ WKH FRUUHVSRQGLQJ UHDFWLRQ ZLWK HWK\OHQH &\FOREXWHQH WR EXWDGLHQH LVRPHUL]DWLRQV 7DEOH f LOOXVWUDWH D UHYHUVH LQ WKHUPDO VWDELOLW\ EHWZHHQ WKH K\GURFDUERQ f DQG SHUIOXRULQDWHG f FDVH 3HUIOXRUREXWDGLHQH f LV IRXQG WR EH NFDOPRO OHVV VWDEOH WKDQ SHUIOXRURF\FOREXWHQH D UHVXOW ZKLFK LV LQ OLQH ZLWK WKH LQFUHDVHG H[RWKHUPLFLW\

PAGE 16

7DEOH )OXRURDONHQH +HDWV RI +\GURJHQDWLRQ $ONHQH $+r+ NFDOPR2 FK FK FK FKI FK FI FKI FI 7DEOH )OXRULQDWHG &\FOREXWHQH'LHQH 7KHUPDO ,VRPHUL]DWLRQV F $ % e $+ NFDOPRK .HJBr&f + + + + ) ) ) ) + + ) ) FK + ) ) FKFK + ) ) UHYHDOHG E\ $+rK XSRQ WUDQVFHQGLQJ WKH VHULHV RI IOXRURHWK\OHQHV LQ 7DEOH $OWKRXJK ,, &0 ; R R &0 ; R ; &) LV NFDOPRO PRUH H[RWKHUPLF WKDQ HWK\OHQH LVRPHUL]DWLRQ LQ WKH FDVH RI WHWUDIOXRURF\FOREXWHQH f IDYRUV WKH GLHQH LQGLFDWLQJ WKH IOXRURDONHQH LV ORZHU LQ HQHUJ\ 6LPSOH DON\O VXEVWLWXWLRQ DW & LQ WHWUDIOXRURF\FOREXWHQH DV VHHQ ZLWK DQG GUDPDWLFDOO\ VKLIW WKH HTXLOLEULXP WRZDUGV WKH F\FOREXWHQH FUHDWLQJ GRXEW DV WR WKH XVHIXOQHVV RI WKLV V\VWHP LQ GHPRQVWUDWLQJ WKH WKHUPRG\QDPLF LQIOXHQFH RI IOXRULQH RQ DQ ROHILQ 2WKHU V\VWHPV DV LOOXVWUDWHG LQ )LJXUH LQGLFDWH JHPGLIOXRURROHILQV DUH

PAGE 17

GHVWDELOL]HG UHODWLYH WR WKH VDWXUDWHG VSHFLHV 5HVXOWV SHUWDLQLQJ WR WKH VWDELOLW\ RI PRQRIOXRULQDWHG DONHQHV DUH FRQWUDGLFWRU\ EXW LW LV JHQHUDOO\ DFFHSWHG WKDW PRQRIOXRULQDWLRQ VWDELOL]HV D GRXEOH ERQG UHODWLYH WR WKH VDWXUDWHG VWDWHf IF FKFK $ O +&)&+ &+ $+r NFDOPRO IA&) $ AFI $+r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nV QRQERQGHG HOHFWURQ LQWHUDFWLRQV ZLWK DGMDFHQW RFFXSLHG DQG QRQRFFXSLHG RUELWDO V\VWHPV LV ZDUUDQWHG LQ OLJKW RI WKH DIRUHPHQWLRQHG TXHVWLRQ RI IOXRURROHILQ GHVWDELOL]DWLRQ 'HVWDELOL]DWLRQ RI Q V\VWHPV KDV UHODWHG SUHFHGHQW LQ WKH FDVH RI DIOXRUR FDUEDQLRQV 6XFK V\VWHPV DUH IRXQG WR EH GHVWDELOL]HG LQ VLWXDWLRQV ZKHUH WKH FDUERQ EHDULQJ WKH QHJDWLYH FKDUJH DQG IOXRULQH DUH SODQDU )LJXUH

PAGE 18

2+ 2+ ) S.D LQ b (W2+ DW r& ) &O %U )LJXUH 'HVWDELOL]DWLRQ LQ 3ODQDU D)OXRURFDUEDQLRQV LOOXVWUDWHV WKH GHFUHDVH LQ DFLGLW\ LQ IOXRURSKHQRO f UHODWLYH WR SKHQRO DQG UDWH LQKLELWLRQ LQ LVRWRSH H[FKDQJH LQ IOXRURIOXRUHQH UHODWLYH WR IOXRUHQHG f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

PAGE 19

7DEOH & 105 6KLIWV MPVf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f ERQGLQJ *HQHUDOO\ WKH GHJUHH WR ZKLFK FDUERFDWLRQV DUH VWDELOL]HG E\ K\GURJHQ IOXRULQH DQG DON\O ZLOO EH IRXQG WR IROORZ WKH RUGHU &+ &) &5

PAGE 20

D)OXRULQH FKDQJHV WKH JHRPHWU\ RI PHWK\O UDGLFDO IURP SODQDU WR S\UDPLGDO ZKLFK LV SURSRVHG WR EH GXH WR UHSXOVLRQ EHWZHHQ WKH UDGLFDO DQG IOXRULQH QRQERQGHG SDLUVn 6WDELOLW\ RI D DQG IOXRUR UDGLFDOV DV HVWDEOLVKHG IURP ERQG GLVVRFLDWLRQ HQHUJLHV LV UHODWLYHO\ XQFKDQJHG IURP K\GURFDUERQ DQDORJV DQG WKHUPDO UHDUUDQJHPHQW RI WR RFFXUV ZLWK DFWLYDWLRQ SDUDPHWHUV ZKLFK DUH DOPRVW LGHQWLFDO ZKHQ ; + RU ) 7KH RYHUDOO HIIHFW RI IOXRULQDWLRQ RQ WKH VWDELOLW\ RI IUHH UDGLFDOV LV EHOLHYHG WR EH PLQLPDOn )LJXUH 7KHUPDO 5HDUUDQJHPHQW RI 0HWK\OLGHQHELF\FOR>@KHSWDQH f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f UHDFWLYLW\ LQ D V\VWHP GXH VROHO\ WR WKH UHODWLYH VL]H DQG FKDUJH GHQVLW\ RI IOXRULQH YHUVXV K\GURJHQ 7KH SRWHQWLDO HQHUJ\ EDUULHU IRU URWDWLRQ RI WKH && ERQG LQ &+&+ LV NFDOPRO ZKHUHDV LQ &)&) LW LV LQFUHDVHG WR NFDOPRO 5HSXOVLRQ

PAGE 21

EHWZHHQ IOXRULQHV LQ SHUIOXRURQDONDQHV OHDGV WR D WZLVWLQJ LQ WKH FDUERQ EDFNERQH 6XFK DQ HIIHFW LV VDLG WR EH HYLGHQFHG E\ SRO\WHWUDIOXRURHWK\OHQH ZKLFK EHORZ r& FRQWDLQV D r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f ZKLFK ZDV DEOH WR EH IRUPHG XS WR b ZHLJKWf LQ VROXWLRQ DQG FRXOG EH GLOXWHG LQ WKH RSHQ DLU DQG GLVVROYHG LQ JRRG K\GURJHQ GRQRU VROYHQWV OLNH WROXHQH RU KHDWHG WR r& ZLWKRXW 5LQJ )OLS N+NS DW r& 6 &+A V 5LQJ )OLS $*r Q Q Q NFDOPRO )LJXUH ,QIOXHQFH RI )OXRULQH RQ &RQIRUPDWLRQDO 3URFHVVHV )LJXUH $ 3HUVLVWHQW 3HUIOXRURDON\O 5DGLFDO f

PAGE 22

GHVWUR\LQJ WKH (65 VLJQDOV 7KH VWDELOLW\ RI WKLV VSHFLHV ZDV DWWULEXWHG WR WKH VKHOWHULQJ RI WKH UDGLFDO FHQWHU SURYLGHG E\ WKH SHUIOXRURHWK\O DQG SHUIOXRURLVRSURS\O JURXSV )URP 7DIW (V YDOXHV WKH &) JURXS LV IRXQG WR EH ODUJHU WKDQ &+&)Of DQG WKH &)&)f JURXS LV VLPLODU LQ VL]H WR &&),f 6WHULF HIIHFWV DWWULEXWHG WR IOXRULQH DUH PRVW RFFXUUHQW DQG GRFXPHQWHG LQ WKH FDVH RI SHUIOXRULQDWHG V\VWHPV )RU IOXRULQH WR H[KLELW D VWHULF HIIHFW LQ D PRQR RU SDUWLDOO\ IOXRULQDWHG V\VWHP WKH PROHFXOH PXVW H[LVW ZLWK YHU\ VPDOO VSDWLDO WROHUDQFH ZKHUHE\ VXEVWLWXWLRQ RI K\GURJHQ E\ IOXRULQH OHDGV WR GHVWDELOL]DWLRQ 7KLV ZRXOG EH WKH UHVXOW RI DWWHPSWHG GLUHFW RYHUODS RI QXFOHL RU PRUH OLNHO\ HOHFWURVWDWLF UHSXOVLRQ EHWZHHQ D VXEVWLWXHQW DQG IOXRULQHn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nV LQLWLDO SURMHFW &KDSWHU f ZDV GHYHORSHG WR IXUWKHU DGGUHVV $Q HOHFWURF\FOLF UHDUUDQJHPHQW LV D VXEVHW RI WKH SHULF\FOLF FODVV RI UHDFWLRQV ZKLFK LQYROYH ERQGLQJ FKDQJHV LQ D FRQFHUWHG IDVKLRQ WKURXJK D FORVHG F\FOH RI DWRPV 7KH HOHFWURF\FOLF UHDUUDQJHPHQW LQYROYHV WKH IRUPDWLRQ RI D D ERQG EHWZHHQ WKH WHUPLQL RI D FRQMXJDWHG OLQHDU Q V\VWHP ZKLFK UHVXOWV LQ WKH IRUPDWLRQ RI D ULQJ FRQWDLQLQJ RQH IHZHU Q ERQG 7KH UHDFWLRQ LV SRWHQWLDOO\

PAGE 23

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f LV D UHVXOW RI WKH FRQURWDWRU\ QDWXUH RI WKLV SURFHVV :RRGZDUG DQG +RIIPDQQ SURSRVHG WKDW FRQVHUYDWLRQ RI RUELWDO V\PPHWU\ IURP UHDFWDQWV WR SURGXFWV LV WKH ORZHVW HQHUJ\ SDWK E\ ZKLFK WKH SURFHVV PD\ RFFXU 7R PDLQWDLQ V\PPHWU\ IRU WKH WKHUPDO N SURFHVV & DQG & RI F\FOREXWHQH RU WHUPLQDO FDUERQV LQ EXWDGLHQHf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

PAGE 24

6WHUHRFKHPLVWU\ RI EXWDGLHQH SURGXFWV IURP HDUO\ WKHUPDO VWXGLHV RI & DQG & DON\ODWHG F\FOREXWHQHV ZHUH UDWLRQDOL]HG EDVHG RQ D VWHULF DUJXPHQW 7KH & DQG & PHWK\ODWHG F\FOREXWHQHV )LJXUH f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b RI WKH SURGXFW ZKHUH WKLV YHU\ EXON\ JURXS KDV URWDWHG LQZDUG 0RUH LQWULJXLQJ H[DPSOHV KDYH IROORZHG DV LOOXVWUDWHG LQ )LJXUH ,Q HDFK FDVH WKH UHDFWLRQ LV b VWHUHRVHOHFWLYH DQG RFFXUV FRQWUDU\ WR H[SHFWDWLRQV EDVHG RQ VWHULF LQWHUDFWLRQV 7KHUPDO 6WXG\ RI WKH )OXRULQDWHG &\FOREXWHQH'LHQH ,QWHUFRQYHUVLRQ 7KH XQTXDQWLILHG QDWXUH RI WKH V\VWHP DQG DQ LQWHUHVW LQ IOXRULQH VXEVWLWXHQW HIIHFWV OHG 'ROELHU HW DO WR LQYHVWLJDWH WKH WKHUPRG\QDPLFV DQG

PAGE 25

NLQHWLFV RI WKH SURFHVV IRU D VHULHV RI IOXRULQDWHG PDWHULDOV LQ WKH PLGVn )DLUO\ UDSLGO\ VWXGLHV LQ WKH IOXRURFDUERQ V\VWHPV VKRZHG GUDVWLF GHYLDWLRQV IURP WKH FRUUHVSRQGLQJ K\GURFDUERQV 2QH RI WKH PDMRU GLIIHUHQFHV LV WKDW WKH UHODWLYH WKHUPRG\QDPLFV RI WKH SHUIOXRURFDUERQ V\VWHPV DUH UHYHUVHG IURP WKH K\GURFDUERQV DW HTXLOLEULXP PDLQO\ SHUIOXRURF\FOREXWHQHV H[LVWf 7KH = ( 5DWLR RI 3URGXFWV 5 = ( (WK\O Q3URS\O 3URS\O I%XW\O )LJXUH 7KHUPDO 5LQJ 2SHQLQJ RI 'LDON\OF\FOREXWHQHV ] RFK ‘&&+f $ $ &22+ 5HIHUHQFHV )LJXUH &RQWUDVWHULF 6WHUHRVHOHFWLYH 7KHUPDO 5LQJ 2SHQLQJV LQ 6XEVWLWXWHG &\FOREXWHQHV

PAGE 26

K\GURFDUERQ F\FOREXWHQH ULQJ RSHQLQJ LV IRXQG WR RFFXU ZLWK $+r NFDOPRO $6r FDOPRO[GHJ DQG LV LUUHYHUVLEOH DW UHDVRQDEOH WHPSHUDWXUHV GXH WR DQ H[RWKHUPLFLW\ RI NFDOPRO 7KH H[RWKHUPLFLW\ RI WKH K\GURFDUERQ SURFHVV DULVHV URXJKO\ IURP GLIIHUHQFHV LQ UHOHDVH RI F\FOREXWHQH ULQJ VWUDLQ NFDOPROf DQG RYHUDOO ERQGLQJ FKDQJH RI D W NFDOPROf IRU D D NFDOPROf ERQG 7KLV H[RWKHUPLFLW\ LV RIIVHW LQ WKH FDVH RI WKH SHUIOXRULQDWHG VSHFLHV E\ WKH SUHIHUHQFH RI IOXRULQH WR EH ERXQG WR FDUERQ RUELWDOV K\EULGL]HG ZLWK PD[LPDO S FKDUDFWHU 7KLV IDFWRU DPRXQWV WR NFDOPRO XSRQ FRQYHUVLRQ RI D JHPGLIOXRURDONHQH WR DONDQH DV GLVFXVVHG HDUOLHU )LJXUH f )LJXUH VKRZV VRPH RI WKH V\VWHPV UHSRUWHG E\ 'ROELHU HW DO ,Q DOO RI WKH V\VWHPV IOXRULQH NLQHWLFDOO\ SUHIHUV RXWZDUG URWDWLRQ DQG LQ VRPH FDVHV RXWZDUG URWDWLRQ RI IOXRULQH LV IDYRUHG HYHQ DW WKH VWHULF H[SHQVH RI URWDWLQJ WKH EXONLHU &) JURXS LQZDUG )RUPDWLRQ RI WKH =DONHQHV f IURP WKHUPRO\VLV RI DQG RFFXU ZLWK DFWLYDWLRQ HQHUJLHV DQG NFDOPRO UHVSHFWLYHO\ ORZHU WKDQ WKH DOWHUQDWH SURFHVVHV OHDGLQJ WR WKH ( DONHQHV f 7KLV FRUUHVSRQGV WR UDWLRV RI UDWHV IRU = DQG (GLHQH IRUPDWLRQ N]NIf RI DQG [ UHVSHFWLYHO\ IRU WKHVH WZR V\VWHPV DW r& :LWK RQO\ RQH SRVVLEOH EXWDGLHQH DYDLODEOH IURP ERWK FRQURWDWRU\ SURFHVVHV XQGHUJRHV ULQJ RSHQLQJ WR VWHUHRVSHFLILFDOO\ \LHOG ZLWK UHODWLYH QRUPDO DFWLYDWLRQ SDUDPHWHUV 7KH SDUWLDOO\ IOXRULQDWHG F\FOREXWHQHV DQG ZHUH LQYHVWLJDWHG WR TXDQWLWDWLYHO\ GHWHUPLQH WKH HIIHFW RI D VLQJOH IOXRUR RU WULIOXRURPHWK\O VXEVWLWXHQW )OXRURF\FOREXWHQH f ZDV IRXQG WR RSHQ VWHUHRVSHFLILFDOO\ WR ZLWK DQ DFWLYDWLRQ HQHUJ\ NFDOPRO ORZHU WKDQ WKDW UHTXLUHG IRU ULQJ RSHQLQJ RI WKH ODUJH GLIIHUHQFH LQ DFWLYDWLRQ HQHUJLHV DULVLQJ IURP LQZDUG URWDWLRQ RI D IOXRULQH LQ YHUVXV 7R GHPRQVWUDWH WKDW WKHUPRG\QDPLF IDFWRUV ZHUH QRW FRQWULEXWLQJ WR WKH VWHUHRVSHFLILFLWLHV LQ ULQJ RSHQLQJ RI DQG LRGLQH FDWDO\]HG WKHUPDO

PAGE 27

) ) $S) ,) rOn) &) f f &) ) f f ) ) f b DW r&f &) b f)RUPDW LV (D LQ NFDOPRO $6r FDOPREFGHJf 5HODWLYH $+ LQ NFDOPRO LV VKRZQ EHORZ VWUXFWXUHV IRU 5HIHUHQFHV f f )LJXUH 7KHUPDO )OXRURF\FOREXWHQH)OXRUR'LHQH ,QWHUFRQYHUVLRQV 6WXGLHG E\ 'ROELHU HW DO

PAGE 28

HTXLOLEULD RI HDFK EXWDGLHQH V\VWHP ZDV H[DPLQHG =)OXRUREXWDGLHQH ZDV IRXQG WR EH PRUH VWDEOH WKDQ WKH (GLHQH ZLWK .]S RI DW r& DQG (WULIOXRURSHQWDGLHQH f ZDV PRUH VWDEOH WKDQ = ZLWK $+ NFDOPRO IRU WKH (}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f DQG /802 /RZHVW 8QRFFXSLHG

PAGE 29

n6WDELOL]DWLRQ Dr /802f 'HVWDELOL]DWLRU D +202f )LJXUH 5HSUHVHQWDWLRQ RI 'RQRU 2UELWDO ,QWHUDFWLRQV ZLWK WKH +202 DQG /802 RI WKH &\FOREXWHQH &RQURWDWRU\ 7UDQVLWLRQ 6WUXFWXUH 0ROHFXODU 2UELWDOf IRU WKH F\FOREXWHQH WKHUPDO HOHFWURF\FOLF FRQURWDWRU\ ULQJ RSHQLQJ WUDQVLWLRQ VWUXFWXUH ZLWK WKH GRQRU RUELWDO V\VWHP LQGLFDWHG IRU HLWKHU RXWZDUG RU LQZDUG URWDWLRQ 8SRQ LQZDUG URWDWLRQ D GRQRU RUELWDO UFF+ RQ &+ RU D ORQH SDLU RI HOHFWURQV RQ D KHWHURDWRPf GHVWDELOL]HV WKH WUDQVLWLRQ VWDWH GXH WR D UHSXOVLYH LQWHUDFWLRQ ZLWK WKH RFFXSLHG ERQGLQJ R RUELWDO ZKLOH PLQLPDO LQWHUDFWLRQ H[LVWV ZLWK Dr DV WKH GRQRU RUELWDO LV GLUHFWHG DW WKH QRGDO VXUIDFH 2XWZDUG URWDWLRQ RI D GRQRU LV VOLJKWO\ VWDELOL]LQJ GXH WR RYHUODS ZLWK WKH Dr DQG WKH IDFW WKDW WKH GRQRU RUELWDO H[SHULHQFHV OHVV UHSXOVLRQ ZLWK D XSRQ URWDWLQJ RXW ,QWHUDFWLRQ RI DFFHSWRUV FRQWDLQLQJ D Q ERQG LV PRUH FRPSOLFDWHG GXH WR WKH LQWHUDFWLRQV RI RFFXSLHG Q ERQGLQJ DQG XQRFFXSLHG Qr DQWLERQGLQJ RUELWDOV ZLWK WKH D DQG Rr RUELWDOV RI WKH F\FOREXWHQH WUDQVLWLRQ VWDWH 7KH PD[LPDO VWDELOL]LQJ LQWHUDFWLRQ LQ WKH FDVH RI DFFHSWRUV FRQWDLQLQJ D Q ERQG LV SURSRVHG WR RFFXU XSRQ LQZDUG URWDWLRQ 7KH WZR HOHFWURQ LQWHUDFWLRQ EHWZHHQ WKH F\FOREXWHQH

PAGE 30

&& D RUELWDO DQG WKH Qr RUELWDO RQ WKH DFFHSWRU OHDGV WR D VPDOO SUHIHUHQFH IRU LQZDUG URWDWLRQ ([SHULPHQWDOO\ DFFHSWRUV VKRZ OLWWOH SUHIHUHQFH IRU LQZDUG RU RXWZDUG URWDWLRQ WKH UHDVRQ EHLQJ WKDW WKH VWDELOL]LQJ QrR LQWHUDFWLRQ LV FRXQWHUHG E\ D UHSXOVLYH LQWHUDFWLRQ EHWZHHQ WKH RFFXSLHG Q RUELWDO DQG && D RUELWDO RI WKH F\FOREXWHQH WUDQVLWLRQ VWUXFWXUH 5RQGDQ DQG +RXN VXJJHVWHG D SRZHUIXO HOHFWURQ DFFHSWRU VXFK DV WKH HPSW\ S RUELWDO RQ D %+ JURXS ZRXOG IDYRU LQZDUG URWDWLRQ GXH WR WKH VWURQJ LQWHUDFWLRQ ZLWK WKH RFFXSLHG F\FOREXWHQH D ERQGLQJ RUELWDO 7DEOH LOOXVWUDWHV FDOFXODWHG $(DnV IRU LQZDUG YHUVXV RXWZDUG URWDWLRQ IRU %+ DQG RWKHU GRQRU DQG DFFHSWRU VXEVWLWXHQWV ZKLFK IXUWKHU GHPRQVWUDWH VWURQJ URWDWLRQDO VHOHFWLYLWLHV 7DEOH &DOFXODWHG $(DnV IRU ,QZDUG YHUVXV 2XWZDUG 5RWDWLRQ LQ 6XEVWLWXWHG &\FOREXWHQHV 6XEVWLWXHQWV (DrXW e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

PAGE 31

&RQFOXVLRQ 7KH SUHFHGLQJ GLVFXVVLRQV KDYH LQWURGXFHG WKH YDULHW\ DQG IDVKLRQ LQ ZKLFK IOXRULQH VXEVWLWXWLRQ FDQ SHUWXUE K\GURFDUERQ FKHPLVWU\ DQG DLG LQ PHFKDQLVWLF LQWHUSUHWDWLRQ 7KH ERG\ RI WKLV WKHVLV ZLOO DGGUHVV H[SHULPHQWDO UHVXOWV REWDLQHG IURP WKH VWXG\ RI IOXRULQH DV D VXEVWLWXHQW LQ WKHUPDO DQG SKRWRFKHPLFDO HOHFWURF\FOLF &KDSWHU f DQG WKHUPDO >@VLJPDWURSLF UHDUUDQJHPHQWV &KDSWHU f

PAGE 32

&+$37(5 7+(50$/ $1' 3+272&+(0,&$/ 5($55$1*(0(176 2) %,675,)/8252(7+(1
PAGE 33

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fWULHQHF\FORKH[DGLHQH LQWHUFRQYHUVLRQ ZDV SURSRVHG :RRGZDUG DQG +RIIPDQ GHVFULEHG WKH WKHUPDO =fWULHQH WR F\FORKH[DGLHQH UHDFWLRQ DV RFFXUULQJ WKURXJK DQ RUELWDO V\PPHWU\ DOORZHG GLVURWDWRU\ SDWKZD\ ([SHULPHQWDOO\ LW LV IRXQG WKDW WKH F\FOL]HG SURGXFWV DUH IRUPHG LQ D VWHUHRVSHFLILF IDVKLRQ LQ OLQH ZLWK D GLVURWDWRU\ FORVXUH LQYROYLQJ URWDWLRQ RI WHUPLQDO =fWULHQH VXEVWLWXHQWV LQ DQ RSSRVLWH VHQVH DV LOOXVWUDWHG E\ WKH H[DPSOHV LQ )LJXUH )LJXUH 6WHUHRVSHFLILF 7KHUPDO 'LVURWDWRU\ WW (OHFWURF\FOL]DWLRQV

PAGE 34

)RU K\GURFDUERQ =fWULHQHV D ZLGH YDULHW\ RI VXEVWLWXWHG V\VWHPV KDYH EHHQ LQYHVWLJDWHG WR HVWDEOLVK WKH UHODWLRQVKLS EHWZHHQ WULHQH VWUXFWXUH DQG UHDFWLYLW\ WRZDUGV F\FOL]DWLRQ 2EVHUYLQJ WRUTXHRHOHFWURQLFV LQ WKHUPDO ULQJ RSHQLQJ RI WKLV F V\VWHP LV XQOLNHO\ DV WKH WKHUPRG\QDPLFV IRU FRQYHUVLRQ RI F\FORKH[DGLHQH f WR = KH[DWULHQH f DUH XQIDYRUDEOH 7KH HQWKDOS\ GLDJUDP LQ )LJXUH LOOXVWUDWHV WKH FRQYHUVLRQ RI WR LV NFDOPRO H[RWKHUPLF GXH WR ORVV RI $+ NFDOPROf )LJXUH (QWKDOS\ 'LDJUDP IRU ( DQG =+H[DWULHQH f DQG &\FORKH[DGLHQH f WKH FRQMXJDWHG WULHQH GRXEOH ERQG DQG IRUPDWLRQ RI D R ERQG LQ F\FORKH[DGLHQH =f7ULHQH =A( LVRPHUL]DWLRQ }f GRHV QRW FRPSHWH ZLWK WW F\FOL]DWLRQ DW ORZHU WHPSHUDWXUHV DV VXFK D SURFHVV LQYROYHV KRPRO\WLF FOHDYDJH RI WKH FHQWUDO GRXEOH ERQG RFFXUULQJ ZLWK D WUDQVLWLRQ VWDWH NFDOPRO KLJKHU LQ HQHUJ\ WKDQ WKDW UHTXLUHG IRU WKH HOHFWURF\FOLF SURFHVV 7KH ODUJH H[RWKHUPLFLW\ REVHUYHG IRU =KH[DWULHQH F\FOL]DWLRQ OHDGV WR DQ HVWLPDWHG $+r NFDOPRO IRU ULQJ RSHQLQJ RI F\FORKH[DGLHQH 7KLV PDJQLWXGH RI DQ HQHUJ\ EDUULHU IRU ULQJ RSHQLQJ DOVR DFFRPPRGDWHV D YDULHW\ RI

PAGE 35

VLJPDWURSLF VKLIW SURFHVVHV 5HWURF\FOL]DWLRQV RI VXEVWLWXWHG F\FORKH[DGLHQHV KDYH EHHQ REVHUYHG DW KLJKHU WHPSHUDWXUHV EXW VWHUHRFKHPLFDO DQDO\VLV RI WKH IRUPHG =fWULHQHV LQ VHDUFK RI WRUTXRHOHFWURQLF HIIHFWV LV IXWLOH GXH WR FRPSHWLQJ UHDUUDQJHPHQWV 5LQJ RSHQLQJ RI )LJXUH f DW r& OHG WR FRPSOHWH HTXLOLEUDWLRQ RI WKH ODEHOV DQG ZDV UDWLRQDOL]HG DV RFFXUULQJ WKURXJK UHWURF\FOL]DWLRQV DQG >@+'f )LJXUH 7KHUPDO 5LQJ 2SHQLQJ RI D &\FORKH[DGLHQH VKLIWV 7ULHQH =!( LVRPHUL]DWLRQV ZLOO DOVR EH FRPSHWLWLYH DW WKHVH HOHYDWHG WHPSHUDWXUHV DQG FUHDWH DQRWKHU VRXUFH RI VWHUHRFKHPLFDO VFUDPEOLQJn ,W LV REYLRXV IURP WKH SUHFHGLQJ GLVFXVVLRQ WKDW SURGXFWLYH ULQJ RSHQLQJ DQG REVHUYDWLRQ RI WRUTXRHOHFWURQLFV LQ VXEVWLWXWHG F\FORKH[DGLHQHV ZLOO UHTXLUH DQ DGMXVWPHQW LQ WKH WKHUPRG\QDPLFV RI WKLV V\VWHP ,Q HIIHFW UHGXFWLRQ RU UHYHUVDO RI WKH HQWKDOS\ GLIIHUHQFH EHWZHHQ D =fWULHQH DQG F\FORKH[DGLHQH ZRXOG DOORZ UHWURF\FOL]DWLRQ WR EH REVHUYHG 7KH DFKLHYHPHQW RI VXFK D VLWXDWLRQ ZRXOG DOORZ IRU ULQJ RSHQLQJ RI D F\FORKH[DGLHQH V\VWHP WR RFFXU DW D UHDVRQDEOH WHPSHUDWXUH DQG DOORZ VWXG\ RI WRUTXRHOHFWURQLF HIIHFWV

PAGE 36

E\ REVHUYLQJ WKH =fWULHQH VWHUHRFKHPLVWU\ DQG DFWLYDWLRQ SDUDPHWHUV UHTXLUHG 'HYHORSPHQW RI D 6XLWDEOH =f7ULHQH&YFORKH[DGLHQH 6\VWHP ,Q WKHRU\ WKH H[RWKHUPLFLW\ RI =fWULHQH F\FOL]DWLRQ PD\ EH RIIVHW E\ JURXQG VWDWH VWDELOL]DWLRQ RI WKH =fWULHQH GHVWDELOL]DWLRQ RI WKH F\FORKH[DGLHQH RU VRPH FRPELQDWLRQ RI ERWK $ V\VWHP LQ ZKLFK WKH WKHUPRG\QDPLFV VHHP IDYRUDEOH IRU REVHUYLQJ ULQJ RSHQLQJ RI D F\FORKH[DGLHQH LV RQH LQ ZKLFK WKH =fWULHQH F\FORKH[DGLHQH V\VWHP VKDUHV D Q ERQG ZLWK DQ DURPDWLF ULQJ DV LOOXVWUDWHG IRU D JHQHUDO FDVH LQ )LJXUH &\FOL]DWLRQ LQ WKLV FDVH LV LPSHGHG E\ ORVV RI WKH DURPDWLF ULQJ Q ERQG LQ HIIHFW GHVWUR\LQJ WKH UHVRQDQFH HQHUJ\ IRU WKDW ULQJ LQ WKH DURPDWLF V\VWHP %\ VHOHFWLQJ WKH DSSURSULDWH DURPDWLF V\VWHP DQG )LJXUH $URPDWLF $QQXODWHG =f7ULHQH&\FORKH[DGLHQH 6\VWHP SODFHPHQW F\FORKH[DGLHQH ULQJ RSHQLQJ FDQ EHFRPH D FRPSHWLWLYH SURFHVV ZLWK =fWULHQH F\FOL]DWLRQ DW ORZHU WHPSHUDWXUHV %XLOGLQJ D IOXRULQDWHG =fWULHQH V\VWHP LQWR DQ SKHQDQWKUHQH ULQJ ZDV EHOLHYHG WR EH WKH EHVW VXLWHG HQWU\ LQWR WKHUPDO VWXG\ RI F\FORKH[DGLHQH ULQJ RSHQLQJ $V SUHYLRXVO\ GLVFXVVHG =KH[DWULHQH F\FOL]DWLRQ LV H[RWKHUPLF E\ NFDOPRO DQG WHUPLQDO JHPGLIOXRULQDWLRQ RU WULIOXRULQDWLRQ RI DQ SHQGDQW DONHQH ZLOO LQFUHDVH WKLV YDOXH E\ NFDOPRO SHUDONHQH ,Q OLQH ZLWK WKH && D ERQG VWUHQJWKHQLQJ WUHQG REVHUYHG IRU WKH VHULHV RI IOXRULQDWHG HWKDQHV &KDSWHU 7DEOH f WKH && D ERQG LQ WKH F\FORKH[DGLHQH SURGXFW ZLOO EH

PAGE 37

VWURQJHU WKDQ WKH FRUUHVSRQGLQJ && D ERQG LQ WKH K\GURFDUERQ 6XFK DQ HIIHFW LV GLIILFXOW WR TXDQWL]H GXH WR WKH QRQOLQHDU HQHUJ\ FKDQJHV LQ JHPLQDO ERQG VWUHQJWKV XSRQ VXFFHVVLYH IOXRULQDWLRQ $Q LQFUHDVH LQ WKH H[RWKHUPLFLW\ RI WKH F\FOL]DWLRQ SURFHVV IURP IRUPDWLRQ RI WKH WHWUDIOXRULQDWHG && D ERQG FDQ EH HVWLPDWHG WR KDYH DQ XSSHU OLPLW RI NFDOPRO REWDLQHG IURP WKH GLIIHUHQFH LQ && D ERQG VWUHQJWK EHWZHHQ &+&+ DQG &)&) &KDSWHU 2QH 7DEOH f 7KLV \LHOGV DQ SRWHQWLDO HQWKDOS\ RI UHDFWLRQ UDQJH RI NFDOPRO WR NFDOPRO IRU F\FOL]DWLRQ RI WKH K\SRWKHWLFDO KH[DIOXRUR =fKH[DWULHQH $OWKRXJK FRQFHSWXDOO\ VWUDLJKWIRUZDUG HVWLPDWLRQ RI WKLV $+rU XVLQJ $+rI RI HDFK VSHFLHV WKURXJK %HQVRQ W\SH JURXS YDOXHV FDQQRW EH SHUIRUPHG EHFDXVH RI WKH PLVVLQJ JURXSV &'&'f)f &'&f)f DQG & &f&'f)f)f /LNHZLVH WKHRUHWLFDO FRPSXWDWLRQV DW DQ\ OHYHO OHVV WKDQ DE LQLWLR OHDG WR ZRHIXOO\ LQFRUUHFW HQHUJ\ SDUDPHWHUV IRU IOXRULQDWHG PDWHULDOV 7KH UHVRQDQFH HQHUJ\ IRU SKHQDQWKUHQH LV REVHUYHG WR EH NFDOPRO /RVV RI SKHQDQWKUHQHnV && GRXEOH ERQG LV DFFRPSDQLHG E\ DQ NFDOPRO LQFUHDVH LQ HQWKDOS\ RU WKH GLIIHUHQFH LQ UHVRQDQFH HQHUJ\ EHWZHHQ SKHQDQWKUHQH DQG ELSKHQ\Of &RQVLGHULQJ WKH HQHUJHWLFV RI WKH =fIOXRURWULHQH F\FOL]DWLRQ DQG GLVUXSWLRQ RI SKHQDQWKUHQH UHVRQDQFH HQHUJ\ E\ && N ERQG FOHDYDJH )LJXUH 3URSRVHG 7KHUPDO (OHFWURF\FOLF ,QWHUFRQYHUVLRQ EHWZHHQ %LVWULIOXRURHWKHQ\OfSKHQDQWKUHQH f DQG +H[DIOXRURGLK\GUR WULSKHQ\OHQH f

PAGE 38

WRJHWKHU LQ D VLQJOH V\VWHP VXFK DV ELVWULIOXRURHWKHQ\OfSKHQDQWKUHQH f DQG KH[DIOXRURGLK\GURWULSKHQ\OHQH f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f 7ULHQH&\FORKH[DGLHQH ,QWHUFRQYHUVLRQ IRU 7RUTXRHOHFWURQLF 6WXG\ 6\QWKHVLV RI %LVWULIOXRURHWKHQ\OfSKHQDQWKUHQH %LVWULIOXRURHWKHQ\OfSKHQDQWKUHQH f ZDV V\QWKHVL]HG LQ IRXU VWHSV )LJXUH f DQG LVRODWHG LQ D b RYHUDOO \LHOG 7KH ILUVW WZR VWHSV LQYROYHG OLWHUDWXUH SURFHGXUHV EURPLQDWLRQ RI SKHQDQWKUHQH f WR \LHOG EURPRSKHQDQWKUHQH bf WKHQ QLWUDWLRQ WR \LHOG EURPR QLWURSKHQDQWKUHQH bf 7KH DFWXDO \LHOG RI IURP WKLV UHDFWLRQ ZDV KLJKHU 7KH LVRODWHG \LHOG UHIOHFWV VRPH GLIILFXOW\ LQ REWDLQLQJ WKLV PDWHULDO SXUH IURP WKH RWKHU PDMRU QLWUDWLRQ SURGXFW EURPRQLWURSKHQDQWKUHQH 7KH QH[W VWHS LQYROYHG QXFOHRSKLOOLF DWWDFN RI LRGLGH RQ WKH EURPLQDWHG & RI WR \LHOG

PAGE 39

%U 1 %U +1 &+&+ bf &+&f D ? ? bf H[ 1DO '0) $ 1 ;=Q&) &) ; &) &)f bf FDW 3G3&+ff 7ULJO\PH r& bf )LJXUH 6\QWKHVLV RI %LVWULIOXRURHWKHQ\OfSKHQDQWKUHQH f LRGR,2QLWURSKHQDQWKUHQH bf 7KH EHVW OLWHUDWXUH SURFHGXUH IRXQG IRU SUHSDUDWLRQ RI LQYROYHG ILYH VWHSV DQG SURGXFHG WKH WDUJHW LQ b \LHOG IURP SKHQDQWKUHQH 2XU SURFHGXUH LV D VLJQLILFDQW LPSURYHPHQW HYHQ LQ WKLV XQRSWLPL]HG VWDWH LQYROYLQJ WKUHH VWHSV DQG SURGXFLQJ LQ b LVRODWHG \LHOG IURP SKHQDQWKUHQH 3UHSDUDWLRQ RI DW WKLV SRLQW ZDV UDWKHU IRUWXLWRXV $ 3G3&+ff FDWDO\]HG FRXSOLQJ EHWZHHQ LRGR DU\OV DQG ;=Q&) &)< ; RU &) &)< < ) RU =^(f&)f ZDV FDUULHG RXW RQ )URP WKH UHDFWLRQ PL[WXUH b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

PAGE 40

LQ KDQG D IHZ VWHSV HDUOLHU WKDQ DQWLFLSDWHG D VWXG\ RI LWnV WKHUPDO FKHPLVWU\ ZDV LQLWLDWHG 7KHUPDO 6WXG\ RI %LVWULIOXRURHWKHQYOfSKHQDQWKUHQH f 7KH WKHUPRO\VLV ZDV VWXGLHG IURP r& XS WR r& DV 0 VROXWLRQV LQ &H' 8SRQ WKHUPRO\VLV RI IRXU SURGXFWV FRXOG EH REVHUYHG LQ VROXWLRQ DQG ZHUH LVRODWHG SXUH E\ SUHSDUDWLYH */3& IRU FKDUDFWHUL]DWLRQ )LJXUH LOOXVWUDWHV WKH SHUFHQW FRPSRVLWLRQ RI DOO UHDFWLRQ FRPSRQHQWV YHUVXV WLPH IRU WKHUPRO\VLV DW r& 7KH UHDFWLRQ LV TXDQWLWDWLYH ZLWK UHJDUG WR IRUPDWLRQ RI &+) VWUXFWXUDO LVRPHUV WKURXJK KRXUV RI WKHUPRO\VLV DW r& DQG DIWHU KRXUV D b \LHOG RI &LD+) LVRPHUV LV REWDLQHG DV D PL[WXUH RI SKHQDQWKURfWULIOXRURWULIOXRURPHWK\O F\FORSHQWDGLHQH f DQG KH[DIOXRURGLK\GURWULSKHQ\OHQH f 7R GHYHORS WKH VFKHPH RI RYHUDOO WUDQVIRUPDWLRQV DV VKRZQ LQ )LJXUH LW ZDV QHFHVVDU\ WR WKHUPRO\]H HDFK RI WKH LQWHUPHGLDWH PDWHULDOV KH[DIOXRURSKHQDQWKURfELF\FOR>@KH[HQH f DQG GLIOXRURPHWK\OLGHQHWHWUDIOXRURSKHQDQWKURfF\FORSHQW HQH f DORQH XQGHU FRQGLWLRQV ZKLFK KDG EHHQ XVHG IRU WKH SDUHQW WULHQH 7KHUPRO\VLV RI DW r& DV D SXULILHG PL[WXUH RI OHG WR QRQn SURGXFWLYH GHFRPSRVLWLRQ RI ZLWK QR UHDFWLRQ RI 7ULHQH ZDV QRW REVHUYHG WR EH UHYHUVLEO\ IRUPHG IURP WKH F\FOL]HG SURGXFW DQG QHLWKHU QRU ZHUH REVHUYHG HLWKHU 7KHUPRO\VLV RI SXULILHG ZDV REVHUYHG DW WKUHH WHPSHUDWXUHV r& r& r&f DQG IRXQG WR IRUP RQO\ DQG 7KH FRQYHUVLRQ RI WR DQG LV TXDQWLWDWLYH DW WKH WHPSHUDWXUHV DQG WLPHV REVHUYHG )LJXUH LOOXVWUDWHV WKH SHUFHQW FRPSRVLWLRQ RI DOO UHDFWLRQ FRPSRQHQWV YHUVXV WLPH IRU WKHUPRO\VLV RI DW r& 7KHUPRO\VLV RI DV RQH FDQ VHH DW ORQJHU WLPHV LQ WKHUPRO\VLV RI )LJXUH DIWHU KRXUVf

PAGE 41

LV REVHUYHG WR VORZO\ IRUP ,Q D QHDU TXDQWLWDWLYH SURFHVV 7KH SRVVLELOLW\ RI IOXRULGH FDWDO\VLV DIIRUGLQJ VXFK D UHDUUDQJHPHQW ZDV GHPRQVWUDWHG E\ WKH UDSLG FRQYHUVLRQ RI WR DW r& LQ WKH SUHVHQFH RI DGGHG WUDFH DPRXQWV RI &V) 7KH SRVVLELOLW\ RI IOXRULGH FDWDO\VLV HIIHFWLQJ WKH UHDFWLRQ FRXUVH RI DW HDUO\ WLPHV ZDV UXOHG RXW E\ WKHUPRO\]LQJ D VDPSOH RI LQ '0) FRQWDLQLQJ &V) DW r& $IWHU KRXUV b RI KDG EHHQ FRQVXPHG DQG WKUHH RWKHU SURGXFWV ZHUH REVHUYHG $QDO\VLV RI WKLV PL[WXUH E\ */3& DQG ) 105 VKRZHG WKDW WKLV IOXRULGH FDWDO\]HG UHDFWLRQ SURFHVV DQG WKH WKHUPDO SURFHVV KDG QR SURGXFWV LQ FRPPRQ DQG ZDV QRW IXUWKHU LQYHVWLJDWHG 7KH GLVDSSHDUDQFH RI DQG ZHUH ERWK IRXQG WR IROORZ ILUVWRUGHU NLQHWLFV DQG WKH FRUUHVSRQGLQJ ILUVWRUGHU SORWV DUH JLYHQ LQ )LJXUH DQG )LJXUH UHVSHFWLYHO\ 8SRQ WKHUPRO\VLV RI XS WR b FRQYHUVLRQ WKH UDWLR RI f ZDV PDLQWDLQHG DW s DW r& s DW r& DQG s DW r& 8SRQ WKHUPRO\VLV RI WKURXJK b FRQYHUVLRQ WKH UDWLR RI f ZDV PDLQWDLQHG DW s DW WKH WKUHH WHPSHUDWXUHV r& r& r&f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r $6rf IRU WKH LQGLYLGXDO SURFHVVHV ZHUH N7 U$+LnL UrVQ REWDLQHG IURP WKH (\ULQJ H[SUHVVLRQ N f§H 57 H 5 ? UHDUUDQJHG WR WKH

PAGE 42

IRUP /QN7f $+r57 $6r5 /Q^NKf ZKHUH N UDWH FRQVWDQW DW DEVROXWH WHPSHUDWXUH 7 N %ROW]PDQQ FRQVWDQW [ 2n -.f K 3ODQFNnV FRQVWDQW [r-[Vf DQG 5 LGHDO JDV FRQVWDQW FDOPRO[.f /LQHDU OHDVW VTXDUHV UHJUHVVLRQ SORWV RI /QN7f YHUVXV 7 \LHOGHG $+r DQG $6r IURP WKH VORSH DQG LQWHUFHSW UHVSHFWLYHO\ RI WKH ILWWHG OLQH IRU HDFK V\VWHP )LW RI WKH VHSDUDWHG UDWH FRQVWDQW N )LJXUH f DW WKH WKUHH REVHUYHG WHPSHUDWXUHV \LHOGHG $+r s NFDOPRO DQG $6r s FDOPRO[GHJ DQG IRU N )LJXUH f \LHOGHG $+r s NFDOPRO DQG $6r s FDOPRO[GHJ )LW RI WKH VHSDUDWHG UDWH FRQVWDQW N )LJXUH f \LHOGHG $+r s NFDOPRO DQG $6r s FDOPRO[GHJ DQG IRU NL )LJXUH f \LHOGHG $+r s NFDOPRO DQG $6r s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fWULHQH ZRXOG DOVR XQGHUJR ELF\FOR>@KH[HQH ULQJ IRUPDWLRQ LQ SUHIHUHQFH WR WKH WKHUPDO GLVURWDWRU\ Q HOHFWURF\FOLF SURFHVV $W WKH WLPH WKLV SURMHFW EHJDQ WKH OLWHUDWXUH FRQWDLQHG RQO\ RQH UHOHYDQW UHIHUHQFH 3HUIOXRURKH[DWULHQH KDG EHHQ UHSRUWHG WR DIIRUG DQ b \LHOG RI SHUIOXRURF\FORKH[DGLHQH XSRQ S\URO\VLV

PAGE 43

)LJXUH 7KHUPRO\VLV RI %LVWULIOXRURHWKHQ\OfSKHQDQWKUHQH f DW r& DV D 6ROXWLRQ LQ &'

PAGE 44

+RXUV )LJXUH 7KHUPRO\VLV RI 0$6AH+H[DIOXRURA6A,2SKHQDQWKURf ELF\FOR>@KH[HQH f DW r& DV D 6ROXWLRQ LQ &H'

PAGE 45

7 r&f N [ VHFf NL [ VHFf O [V VHFnf s s s )LJXUH )LUVW2UGHU 3ORWV DQG 5DWH &RQVWDQWV IRU /RVV RI %LVWULIOXRURHWKHQ\OfSKHQDQWKUHQH f DQG 'HULYHG )LUVW2UGHU 5DWH &RQVWDQWV IRU )RUPDWLRQ RI +H[DIOXRURGLK\GURWULSKHQ\OHQH f DQG +H[DIOXRURSKHQDQWKURfELF\FOR>@KH[HQH f

PAGE 46

7 r&f ,[ VHHrf OR[ VHFf NL[ VHFnf s s s )LJXUH )LUVW2UGHU 3ORWV DQG 5DWH &RQVWDQWV IRU /RVV RI +H[DIOXRURSKHQDQWKURfELF\FOR>@KH[HQH f DQG 'HULYHG )LUVW2UGHU 5DWH &RQVWDQWV IRU )RUPDWLRQ RI 'LIOXRURPHWK\OLGHQH WHWUDIOXRURSKHQDQWKURfF\FORSHQWHQH f DQG 3KHQDQWKURfWULIOXRURWULIOXRURPHWK\OF\FORSHQWDGLHQH f

PAGE 47

7 )LJXUH (\ULQJ 3ORWV IRU 6HSDUDWHG 5DWH &RQVWDQWV N_ DQG NJ )LJXUH (\ULQJ 3ORWV IRU 6HSDUDWHG 5DWH &RQVWDQWV N DQG N

PAGE 48

LQ D IORZ V\VWHP DW r& $W WKLV WHPSHUDWXUH LW LV TXHVWLRQDEOH ZKHWKHU WKLV LV WKH SULPDU\ SURFHVV LQYROYHG LQ WKLV V\VWHP $ ORZHU WHPSHUDWXUH PRUH TXDQWLWDWLYH VWXG\ RI DQ DF\FOLF SHUIOXRULQDWHG WULHQH ZDV UHTXLUHG $ V\VWHP ZKRVH V\QWKHWLF DSSURDFK SRWHQWLDOO\ DOORZHG IRU DGDSWDWLRQ LQWR D YDULHW\ RI WHUPLQDOO\ VXEVWLWXWHG SHUIOXRURWULHQHV ZDV SHUIOXRUR (=( DQG (((fGLPHWK\ORFWDWULHQH =(ff 7KLV V\VWHP KDG EHHQ SUHYLRXVO\ V\QWKHVL]HG DQG )LJXUH LOOXVWUDWHV WKH FKHPLVWU\ LQYROYHG 7KLV SURFHGXUH ZDV UHSHDWHG DQG WKH LVRODWHG \LHOG DQG SURGXFW FRPSRVLWLRQ REWDLQHG b (=(((( f ZHUH VLPLODU WR WKRVH UHSRUWHG b (=(((( f ,QLWLDOO\ DQ DWWHPSW ZDV PDGH WR V\QWKHVL]H SHUIOXRURGLPHWK\O KH[DWULHQH f E\ VLPLODU PHWKRGRORJ\ D SURFHVV ZKLFK KDG EHHQ GLVFXVVHG &Gr '0) 57 PLQ &X%U '0) 57 7+" 6LPLODU WR $ERYH ,A) '0) 57 +U &8! f; ) &)r r3HUIOXRUR=LRGRSURSHQH f ZDV V\QWKHVL]HG LQ IRXU VWHSV IURP SHUIOXRURSURSHQH )LJXUH 6\QWKHVLV RI 3HUIOXRUR(=((((fGLPHWK\ORFWDWULHQH =(ff

PAGE 49

RQO\ WR WKH SRLQW RI WKH FKDLQ H[WHQGHG FRSSHU UHDJHQW LQ WKH UHIHUHQFH )ROORZLQJ WKH UHDFWLRQ SURJUHVV E\ ) 105 IRUPDWLRQ RI ZDV REVHUYHG EXW DGGLWLRQ RI D IXUWKHU HTXLYDOHQW RI LRGRWULIOXRURHWK\OHQH DIIRUGHG D b RU OHVV \LHOG RI LQ WKH UHDFWLRQ PL[WXUH ZKLFK IRU WKH SXUSRVH RI WKLV SURMHFW ZDV V\QWKHWLFDOO\ XVHOHVV 1RW KDYLQJ REWDLQHG XVHIXO TXDQWLWLHV RI WKH V\QWKHVLV RI ZDV UHSHDWHG DQG LWnV WKHUPDO FKHPLVWU\ LQYHVWLJDWHG 7KH WKHUPRO\VLV RI ZDV VWXGLHG IURP r& WR r& DV D 0 VROXWLRQ LQ QSHQWDQH 'XH WR GLIILFXOW\ LQ VHSDUDWLRQ RI WKH WULHQH (=( DQG ((( LVRPHUV WKH W\SLFDO V\QWKHWLF PL[WXUH RI LVRPHUV (=(((( UDWLR RI ,f ZDV XVHG LQ DOO VWXGLHV $W WHPSHUDWXUHV DURXQG r& (=(r((( LVRPHUL]DWLRQ ZDV REVHUYHG WR RFFXU $IWHU ORQJHU WLPHV RQH QHZ SURGXFW ZDV HYLGHQW EHLQJ LGHQWLILHG E\ ) 105 LQ WKH UHDFWLRQ VROXWLRQ DV D PL[WXUH RI SHULOXRURFnVDQG WUDQVMO WULPHWK\O(SURSHQ\OfF\FOREXWHQH f )LJXUH VKRZV WKH SHUFHQW FRPSRVLWLRQ YHUVXV WLPH IRU WKHUPRO\VLV RI DW r& DQG WKHQ DW r& (=(!((( LVRPHUL]DWLRQ LV REVHUYHG LQLWLDOO\ IROORZHG E\ DSSHDUDQFH RI DIWHU KRXUV DW r& 5DLVLQJ WKH WHPSHUDWXUH RI WKH VDPSOH WR r& VHWV XS DQ HTXLOLEULXP PL[WXUH RI (= ,, 7KXV WKLV V\VWHP UHSUHVHQWV D VHFRQG H[DPSOH ZKHUH D KLJKO\ IOXRULQDWHG =fWULHQH XQGHUZHQW WKHUPDO FKHPLVWU\ RWKHU WKDQ WKH N GLVURWDWRU\ IRUPDWLRQ RI D F\FORKH[DGLHQH 6LQFH WKH WKHUPDO N FORVXUH VHHPHG WR EH GLVIDYRUHG ZH ZHUH LQWHUHVWHG WR VHH ZKHWKHU WKH SKRWRFKHPLFDO N FRQURWDWRU\ IRUPDWLRQ RI F\FORKH[DGLHQHV ZRXOG RFFXU LQ WKHVH IOXRULQDWHG V\VWHPV 3KRWRFKHPLFDO 5HDUUDQJHPHQWV RI %LVIWULIOXRURHWKHQYQ'KHQDQWKUHQH DQG 3HUIOXRUR(=((((0GLPHWKYORFWDWULHQH =(f 8SRQ SKRWRFKHPLFDO H[FLWDWLRQ JURXQG VWDWH WULHQHV PD\ XQGHUJR

PAGE 50

b &RPSRVLWLRQ +RXUV ( )LJXUH 7KHUPRO\VLV RI 3HUIOXRUR(=(((efGLPHWK\O RFWDWULHQH =Iff DV D 6ROXWLRQ LQ Q3HQWDQH

PAGE 51

..r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fWULHQHF\FORKH[DGLHQH SKRWRn SURFHVVHV DUH FRPSOLFDWHG LQ PDQ\ FDVHV E\ RWKHU UHDFWLRQ SDWKZD\V DYDLODEOH WR WKH KLJK HQHUJ\ H[FLWHG VWDWH )LJXUH LOOXVWUDWHV WKH YDULHW\ RI SURGXFWV ZKLFK KDYH EHHQ REVHUYHG LQ YDULRXV WULHQHF\FORKH[DGLHQH SKRWRFKHPLFDO V\VWHPV $ YDULHW\ RI IDFWRUV DUH LPSRUWDQW LQ GLFWDWLQJ WKH SURGXFW GLVWULEXWLRQ DQG ZLOO EH GLVFXVVHG ODWHU

PAGE 52

)LJXUH 3KRWRSURGXFW 9DULDWLRQ LQ 7ULHQH&\FORKH[DGLHQH 6\VWHPV +DYLQJ QRW REVHUYHG WKH WKHUPDO WW GLVURWDWRU\ SURFHVV WR DQ\ VLJQLILFDQW H[WHQW LQ WKH FDVHV RI DQG = DW WKH WHPSHUDWXUHV VWXGLHG LW ZDV RI LQWHUHVW WR GHWHUPLQH LI WKH SKRWRFKHPLFDO WL FRQURWDWRU\ SURFHVV ZRXOG RFFXU $ TXHVWLRQ RI WKH UHODWLYH DELOLW\ RI WKH WZR Q WUDQVLWLRQ VWDWHV WKHUPDO GLVURWDWRU\ YHUVXV SKRWRFKHPLFDO FRQURWDWRU\f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

PAGE 53

KH[DIOXRURSKHQDQWKURfEcF\FOR> @KH[HQH f DQG KH[DIOXRURSKHQDQWKURfELF\FOR>@KH[HQH f DUH IRUPHG URXJKO\ LQ D UDWLR RI f f DQG DFFRXQW IRU b RI WKH UHDFWLRQ PL[WXUH DIWHU b FRQYHUVLRQ RI ,QGHSHQGHQW SKRWRO\VLV RI SXUH XQGHU VLPLODU FRQGLWLRQV XVHG IRU OHG WR IRUPDWLRQ RI LQ ORZ \LHOGV RQH KRXU RI SKRWRO\VLV RI \LHOGV b UHPDLQLQJ DQG b RI IRUPHG ZLWK D b GHFUHDVH LQ PDVV EDODQFH 3KRWRO\VLV RI IRU WZR KRXUV OHDGV WR GHFUHDVH LQ DPRXQWV RI DOO PDWHULDOV DQG b UHGXFWLRQ LQ PDVV EDODQFH 5HYHUVLELOLW\ RI EDFN WR WULHQH ZDV QRW REVHUYHG WR DQ\ H[WHQW LQ WKHVH VWXGLHV 2YHUDOO SKRWRO\VLV RI WKH SDUHQW WULHQH LV TXLWH FOHDQ DQG DIWHU KRXUV ZLWK WKH DIRUHPHQWLRQHG OLJKW VRXUFH DQ b GHFUHDVH LQ PDVV EDODQFH LV REVHUYHG ZLWK b UHPDLQLQJ 6RPH H[WHQW RI SRO\PHUL]DWLRQ LV RFFXUULQJ XQGHU WKHVH FRQGLWLRQV DQG LV UHYHDOHG E\ D VPDOO DPRXQW RI VROLG ZKLWH ILOP DSSHDULQJ RQ WKH ZDOOV RI WKH SKRWRO\VLV YHVVHO $WWHPSWV WR LVRODWH DQG IDLOHG 7KH SUHSDUDWLYH SDFNHG FROXPQ */3& FRQGLWLRQV QHFHVVDU\ WR HOXWH WKHVH SKHQDQWKUHQH GHULYDWLYHV OHG WR GHFRPSRVLWLRQ RI DQG ,W ZDV IRXQG WKDW WKHUPRO\VLV RI D EHQ]HQH VROXWLRQ FRQWDLQLQJ DQG DW r& IRU PLQXWHV OHG WR D PL[WXUH FRQWDLQLQJ RQO\ DQG ZLWK QR RU UHPDLQLQJ DQG QR QHZ SURGXFWV HYLGHQW 7KLV SURFHVV ZDV QRW TXDQWLILHG DQG RWKHU DWWHPSWV DW LVRODWLRQ RI DQG E\ 7/& IDLOHG DV WKH LVRPHUV FRXOG QRW EH VHSDUDWHG E\ WKLV WHFKQLTXH 3KRWRO\VLV RI 3HUIOXRUR(=((()fGLPHWKYORFWDWULHQH =(ff 7KH SKRWRO\VLV RI ZDV VWXGLHG DV D 0 VROXWLRQ LQ QSHQWDQH DQG WKH VDPSOHV ZHUH LUUDGLDWHG WKURXJK 3\UH[ DW URRP WHPSHUDWXUH XVLQJ D KHDWHG FDWKRGH ORZ SUHVVXUH PHUFXU\ ODPS 7ZR SURGXFWV ZHUH REVHUYHG DQG

PAGE 54

LVRODWHG XSRQ SKRWRO\VLV RI )LJXUH VKRZV SHUFHQW FRPSRVLWLRQ RI DOO PDWHULDOV YHUVXV VROXWLRQ LUUDGLDWLRQ WLPH 3HUIOXRURIUDQVWHWUDPHWK\O F\FORKH[DGLHQH f LV WKH PDMRU SKRWRSURGXFW DQG LV DFFRPSDQLHG E\ WULHQH (=(UA((( && GRXEOH ERQG LVRPHUL]DWLRQ 3HUIOXRURIDQV WHWUDPHWK\OELF\FOR>@KH[HQH f LV IRUPHG LQ WKH UHDFWLRQ PL[WXUH DIWHU ORQJHU WLPHV DQG LQ VPDOO TXDQWLW\ ZKHQ SKRWRO\VLV LV FDUULHG RXW WKURXJK 3\UH[ 3KRWRO\VLV RI SXUH WKURXJK TXDUW] XQGHU VLPLODU FRQGLWLRQV XVHG IRU OHDGV H[FOXVLYHO\ WR DQG ULQJ RSHQLQJ WR LV QRW REVHUYHG WR DQ\ H[WHQW $WWHPSWV WR REWDLQ 'LHOV$OGHU DGGXFWV EHWZHHQ DQG GLPHWK\O DFHW\OHQHGLFDUER[\ODWH RU 1SKHQ\OWULD]ROLQH GLRQH LQ QSHQWDQH DW WHPSHUDWXUHV XS WR r& VKRZHG QR UHDFWLRQ DQG ZDV DOVR IRXQG WR EH VWDEOH DW r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

PAGE 55

b &RPSRVLWLRQ )LJXUH 3KRWRO\VLV RI %LVWULIOXRURHWKHQ\OfSKHQDQWKUHQH f DV D 0 6ROXWLRQ LQ Q3HQWDQH E\ /RZ 3UHVVXUH 0HUFXU\ /DPS WKURXJK 3\UH[

PAGE 56

b &RPSRVLWLRQ )LJXUH 3KRWRO\VLV RI 3HUIOXRUR(=((((fGLPHWK\ORFWDWQHQH =(ff DV D 0 6ROXWLRQ LQ Q3HQWDQH E\ /RZ 3UHVVXUH 0HUFXU\ /DPS

PAGE 57

RI SHUIOXRUR((((=(fGLPHWK\ORFWDWULHQH =eff DQG ELVWULIOXRURHWKHQ\OfSKHQDQWKUHQH f ZLOO QRZ EH GLVFXVVHG LQ WXUQ 'LVFXVVLRQ RI WKH 3KRWRFKHPLFDO 6WXGLHV (DUO\ VWXGLHV LQ WKH SKRWRFKHPLVWU\ RI 9LWDPLQ DQG LWfV PDQ\ LVRPHUV VHW WKH SUHFHGHQW IRU WKH SRVVLEOH FRPSOH[LWLHV RI WULHQH SKRWRFKHPLVWU\ 3UHYLRXVO\ )LJXUH LOOXVWUDWHG VRPH RI WKH W\SHV RI SURGXFWV ZKLFK KDYH EHHQ REVHUYHG HOVHZKHUH LQ WULHQH SKRWRFKHPLVWU\ ,W LV JHQHUDOO\ DFFHSWHG WKDW WULHQH SKRWRSURGXFW FRPSRVLWLRQ FDQ EH GLUHFWO\ UHODWHG WR WKH JURXQG VWDWH FRQIRUPDWLRQDO GLVWULEXWLRQ RI WKH V\VWHP E\ D SULQFLSOH NQRZQ DV WKH 1RQ(TXLOLEUDWLRQ RI ([FLWHG 5RWDPHUV 1((5f 7KLV SULQFLSOH VWDWHV WKDW LQ WKH H[FLWHG VWDWH DQ HQKDQFHG EDUULHU IRU URWDWLRQ H[LVWV DERXW WKH ERQGV ZKLFK LQ WKH JURXQG VWDWH DUH VLQJOH ERQGV 'XH WR LWn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f DQG DQG WKH FRUUHVSRQGLQJ QP SULPDU\ SKRWRSURGXFWV DUH VKRZQ LQ )LJXUH $EVROXWH SURRI RI DQ PHFKDQLVWLF UDWLRQDOH LV GLIILFXOW DQG PRUH VR LQ WKH FDVH RI 1((5 EHFDXVH RI WKH QXPEHU RI UHOHYDQW XQWHVWHG YDULDEOHV DQG DOWHUQDWH PHFKDQLVWLF SURSRVDOV 7KH SRVVLELOLW\ RI HTXLOLEUDWLRQ RI H[FLWHG FRQIRUPHUV KDV EHHQ DGGUHVVHG DQG

PAGE 58

)LJXUH 7KUHH 3ODQDU &RQIRUPDWLRQV RI =+H[DWULHQH DQG &RUUHVSRQGLQJ 3KRWRSURGXFWV +f A A&&+f F=F F=F W(W F=W 0DMRU 3URGXFW 'LVWULEXWLRQ 0LQRU &&+f +&f& &&+f +&f& &&+f +&f& )LJXUH ([DPSOHV RI 7ULHQH 3UHIHUUHG *URXQG 6WDWH &RQIRUPDWLRQV DQG QP 3ULPDU\ 3KRWRSURGXFW 'LVWULEXWLRQ

PAGE 59

GLVPLVVHG E\ D VWXG\ RI WKH LQIOXHQFH RI ZDYHOHQJWK RQ WKH SKRWRSURGXFW GLVWULEXWLRQ DW ORZ SHUFHQWDJH FRQYHUVLRQ 7KH SUHIHUUHG JURXQG VWDWH FRQIRUPDWLRQ RI DF\FOLF WULHQHV FKDQJHV FRQVLGHUDEO\ IURP WKH K\GURFDUERQ WR SHUIOXRURFDUERQ V\VWHPV $ YDULHW\ RI VWXGLHV 89 DQG SKRWRHOHFWURQ VSHFWUD WKHRUHWLFDO FRQVLGHUDWLRQf SRLQW WRZDUG SHUIOXRUREXWDGLHQH f H[LVWLQJ LQ D FLVVNHZ VWUXFWXUH ZLWK WRUVLRQ DQJOH r )LJXUH f ZKHUHDV EXWDGLHQH f H[LVWV LQ D SODQDU WUDQV FRQIRUPDWLRQ ZLWK r $ VLJQLILFDQW K\SVRFKURPLF VKLIW LV REVHUYHG DV WKH VHULHV RI IOXRURHWK\OHQHV f LV WUDQVYHUVHG 7KLV WUHQG LV DOVR REVHUYHG EHWZHHQ DQG EXW KHUH DORQJ ZLWK SKRWRHOHFWURQ VSHFWUDO GDWD LV APD[ QPf (PD[ /PRO[FPf GHJf +& FK KF &+) +& f§ FI )+& FI )& FI FI IF e I PI r 5HIHUHQFHV n V )LJXUH 89 'DWD IRU )OXRURHWK\OHQHV DQG )OXRUREXWDGLHQHV

PAGE 60

SURSRVHG WR EH GXH WR QRQSODQDULW\ LQ UHODWLYH WR DQG 3HUIOXRUR EXWDGLHQH f LV REVHUYHG WR KDYH D 89 VSHFWUXP LGHQWLFDO ZLWK +)& &) f IXUWKHU LQGLFDWLQJ WKHUH LV OLWWOH LQWHUDFWLRQ EHWZHHQ WKH && DQG && Q V\VWHPV 7KLV QRQSODQDULW\ LV GLVSOD\HG E\ PRGHOV ZKHUH D GLVDGYDQWDJHRXV LQWHUDFWLRQ LV REVHUYHG EHWZHHQ IOXRULQHV RQ & DQG & DQG & DQG & LQ WKH SODQDU WUDQV FRQIRUPDWLRQ +\SVRFKURPLF VKLIWV DWWULEXWHG WR QRQSODQDULW\ KDYH EHHQ REVHUYHG LQ RWKHU QRQSODQDU SRO\HQHV VXFK DV GLI EXW\OEXWDGLHQH ZKHUH ;PD[ QP 3HUIOXRUR(KH[DWULHQH (f KDV EHHQ VXEMHFWHG WR WKHRUHWLFDO FRQIRUPDWLRQDO VWXG\ DW WKH DE LQLWLR OHYHO 7ZR WRUVLRQDO DQJOHV L f H[LVW LQ WKLV PROHFXOH DQG ORFDO PLQLPD ZHUH ORFDWHG IRU WZR VWUXFWXUHV ZLWK V\Q DQG DQWL UHODWLRQV RI WKH SHQGDQW DONHQHV UHODWLYH WR WKH SODQH IRUPHG E\ &&& & )LJXUH LOOXVWUDWHV WKH FRQIRUPHUV DQG WKH UHODWLYH HQHUJLHV FDOFXODWHG 7KH ORZHVW HQHUJ\ FRQIRUPHU RI ( ZDV IRXQG WR EH D V\QVNHZ VWUXFWXUH DV LV REVHUYHG ZLWK SHUIOXRUREXWDGLHQH )LJXUH f ) ) ) ) ) ) ( GHJf GHJf $( NFDOPROf )LJXUH 5HODWLYH &DOFXODWHG 0LQLPD IRU 3HUIOXRUR(KH[DWULHQH e f

PAGE 61

3KRWRFKHPLFDO 6WXG\ RI 3HUIOXRUR(=(DQG((DGLPHWKYO RFWDWULHQH =(ff 3KRWRO\VLV RI SHUIOXRUR(=(GLPHWK\ORFWDWULHQH =f DQG SHUIOXRUR(((GLPHWK\ORFWDWULHQH (f \LHOGHG RQO\ WZR SURGXFWV SHUIOXRURLUDQVWHWUDPHWK\OF\FORKH[DGLHQH f DQG SHUIOXRUR IUDQVWHWUDPHWK\OELF\FOR>@KH[HQH f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fGLPHWK\ORFWDWULHQH =(ff GRXEOH ERQG WR IRUP = &LV WULHQH = LV IRXQG WR XQGHUJR RQO\ Q FRQURWDWRU\ FORVXUH WR \LHOG 7KH ORZHVW HQHUJ\ FRQIRUPHU RI = PRVW OLNHO\ LQYROYHV VNHZLQJ RI WKH SHQGDQW (SHUIOXRURSURSHQ\O JURXSV UHODWLYH WR WKH &&&& SODQH EXW ZKHWKHU LW H[LVWV FLV RU WUDQV VNHZHG DERXW WKH & & DQG && VLQJOH ERQGV LV XQNQRZQ ,W LV QRWLFHG WKDW D FLV VNHZHG

PAGE 62

VWUXFWXUH RI = )LJXUH f LV SHUIHFWO\ DOLJQHG ZLWK PLQLPDO UHSXOVLRQ WR XQGHUJR DOORZHG FRQURWDWRU\ ERQG IRUPDWLRQ EHWZHHQ & DQG & OHDGLQJ GLUHFWO\ WR )LJXUH &V6NHZHG &RQIRUPHU RI 3HUIOXRURe=(GLPHWK\O RFWDWULHQH =f 3HUIOXRURLnDQVWHWUDPHWK\OF\FORKH[DGLHQH f XQGHUJRHV D IXUWKHU IRUPDO $Q GLVURWDWRU\ FORVXUH WR IRUP SHUIOXRURWUDQVWHWUDPHWK\O ELF\FOR>@KH[HQH f LQ SUHIHUHQFH WR ULQJ RSHQLQJ WR SHUIOXRURe=( GLPHWK\ORFWDWULHQH =f 8VLQJ H[SHULPHQWDO UHVXOWV DQG 1((5 W\SH UHDVRQLQJ LW KDV EHHQ HVWDEOLVKHG IRU K\GURFDUERQ SKRWRFKHPLFDO F\FORKH[DGLHQH SURFHVVHV WKDW WKH SUHIHUUHG JURXQG VWDWH FRQIRUPDWLRQ RI WKH V\VWHP ZLOO FRQWURO ZKHWKHU WKH UF FRQURWDWRU\ ULQJ RSHQ =fWULHQH RU Q GLVURWDWRU\ ULQJ FORVHG ELF\FOR>@KH[HQH LV REVHUYHG 6WXGLHV KDYH VKRZQ WKDW SODQDU RU KDOIERDW W\SH FRQIRUPHUV )LJXUH f XQGHUJR GLVURWDWRU\ FORVXUH WR ELF\FOR>@KH[HQHV DQG KDOIFKDLU W\SH FRQIRUPHUV SUHIHU FRQURWDWRU\ ULQJ RSHQLQJ WR =fWULHQHV

PAGE 63

3ODQDU +DOIERDW 4 ? ELF\FOR>@KH[HQH +DOIFKDLU +DOIFKDLU =7ULHQH )LJXUH &RQIRUPDWLRQDOO\ &RQWUROOHG 3KRWRSURFHVVHV RI &\FORKH[DGLHQHV :LWK WKLV SUHFHGHQW LW LV VXUSULVLQJ WKDW F\FORKH[DGLHQH GRHV QRW XQGHUJR ULQJ RSHQLQJ 0RGHO VWXGLHV LQGLFDWH WKH PRVW IDYRUHG FRQIRUPHU RI )LJXUH f LV RQH LQ ZKLFK WULIOXRURPHWK\O VWHULF UHSXOVLRQV DUH PLQLPL]HG LQ D KDOI FKDLU ULQJ RULHQWDWLRQ ZLWK GLSVHXGRD[LDO & DQG & WULIOXRURPHWK\O JURXSV DQG D &&&& WRUVLRQ DQJOH ODUJHU WKDQ WKDW IRXQG LQ F\FORKH[DGLHQH )LJXUH )DYRUHG +DOI&KDLU &RQIRUPHU RI 3HUIOXRURIUDQV WHWUDPHWK\OF\FORKH[DGLHQH f

PAGE 64

7KH SKRWRFKHPLFDO UHVXOWV REWDLQHG ZLWK IOXRULQDWHG WULHQH DUH FRQVLVWHQW ZLWK WKH IHZ RWKHU IOXRULQDWHG H[DPSOHV IRXQG LQ WKH OLWHUDWXUH 5HFHQWO\ LW KDV EHHQ UHSRUWHG WKDW SHUIOXRUR=KH[DWULHQH =f XQGHUJRHV GRXEOH ERQG LVRPHUL]DWLRQ DQG $Q DQG Q SKRWRFORVXUHV )LJXUH f WR \LHOG D PL[WXUH RI SHUIOXRUR(KH[DWULHQH (f SHUIOXRUR F\FORKH[DGLHQH f DQG SHUIOXRURHWKHQ\OF\FOREXWHQH f $W ORZ SHUFHQW FRQYHUVLRQV RI = RQO\ ( DQG DUH LGHQWLILHG LQ WKH UHDFWLRQ PL[WXUH :KHQ WKH UHDFWLRQ LV FDUULHG RXW WR FRPSOHWLRQ D PL[WXUH FRQWDLQLQJ b b DQG b SHUIOXRUR>@ELF\FORKH[HQH f LV REWDLQHG $Q LQFRQVLVWHQF\ H[LVWV LQ WKDW WKH IRUPDWLRQ RI WKH SHUIOXRUR HWKHQ\OF\FOREXWHQH f ULQJ VWUXFWXUH ZDV QRW REVHUYHG LQ WKH FDVH RI $V DOUHDG\ GLVFXVVHG ( ZLOO QRW SRSXODWH WKH W=F FRQIRUPDWLRQ IRU VWHULF UHDVRQV DQG XQGHUJRHV (((!(=( LVRPHUL]DWLRQ RQO\ ,W LV GLIILFXOW WR VHH ZK\ = LV QRW REVHUYHG WR IRUP $Q F\FOL]DWLRQ SURGXFWV DV DUH REVHUYHG LQ WKH e = ? )LJXUH 3KRWRSURGXFWV 2EWDLQHG IURP 3HUIOXRUR=KH[DWULHQH =f FDVH RI = 0RGHOV LQGLFDWH WKH F=W FRQIRUPDWLRQ RI = PD\ H[LVW DV LW PXVW IRU = ZLWK OLWWOH FURZGLQJ RI WKH WULIOXRURPHWK\O VXEVWLWXHQWV $ SRVVLEOH H[SODQDWLRQ DULVHV LI RQH DVVXPHV RQO\ WKH IOXRULQDWHG (WULHQHV DUH XQGHUJRLQJ

PAGE 65

WKH Q F\FOL]DWLRQ ,Q WKLV FDVH F(W ( FDQ XQGHUJR Q FORVXUH RU (f§}= LVRPHUL]DWLRQ ZKHUHDV W(W ( DIIRUGV RQO\ = ,W LV XQSURYHG ZKHWKHU VXFK DQ DUJXPHQW DSSOLHV EXW LI VR LW ZRXOG EH XQLTXH WR WKHVH SHUIOXRULQDWHG WULHQHV DV ERWK ( DQG = K\GURFDUERQ WULHQHV DUH REVHUYHG WR IRUP DONHQ\OF\FOREXWHQHV DV SULPDU\ SKRWRSURGXFWV )LJXUH f 3KRWRO\VLV RI SHUIOXRURF\FORKH[DGLHQH f XVLQJ D ORZ SUHVVXUH PHUFXU\ ODPS KDV EHHQ SUHYLRXVO\ UHSRUWHG WR TXDQWLWDWLYHO\ \LHOG DV WKH VROH SKRWRSURGXFW ,Q FRQWUDVW WR WKH SUHYLRXV IOXRULQDWHG F\FORKH[DGLHQH UHVXOWV SKRWRO\VLV RI SHUIOXRURWULF\FOR>@GRGHFDWULHQH )LJXUH f \LHOGV ELF\FOR>@KH[HQH W\SH LVRPHUV DQG 7KHVH SURGXFWV DUH SURSRVHG WR EH RULJLQDWLQJ IURP WKH ULQJ RSHQHG WULHQH D VSHFLHV ZKLFK ZDV QHYHU REVHUYHG LQ WKLV VWXG\ 'XH WR WKH ULJLGLW\ RI WKH ELF\FORKH[HQH ULQJ VWUXFWXUH RI WKH F\FORKH[DGLHQH ULQJ ZLOO EH YHU\ QHDUO\ SODQDU 7KH IRUPDWLRQ RI KH[DGLHQH JRHV FRXQWHU WR WKH 1((5 SUHGLFWHG SURGXFW IRU WKLV V\VWHP ZKLFK ZRXOG EH IRUPDWLRQ RI D ELF\FOR>@KH[HQH )LJXUH f W\SH ULQJ VWUXFWXUH )LJXUH 3KRWRO\VLV RI 3HUIOXRURWULF\FOR>f@GRGHFDWULHQH f

PAGE 66

3KRWRFKHPLFDO 6WXG\ RI %LVWULIOXRURHWKHQ\OfSKHQDQWKUHQH f 3KRWRO\VLV RI ELVWULIOXRURHWKHQ\OfSKHQDQWKUHQH f OHG WR IRUPDWLRQ RI IRXU VWUXFWXUDO LVRPHUV DQG DV LOOXVWUDWHG LQ )LJXUH )LJXUH 3KRWRO\VLV RI %LVWULIOXRURHWKHQ\OfSKHQDQWKUHQH f %LVWULIOXRURHWKHQ\OfSKHQDQWKUHQH f ZDV REVHUYHG E\ ) 105 WR H[LVW DV D SDLU RI WRUVLRQDO GLDVWHUHRPHUV ZLWK D VXEVWDQWLDO HQHUJ\ EDUULHU WR LQWHUFRQYHUVLRQ D GLVFXVVLRQ RI ZKLFK KDV EHHQ SXEOLVKHG 7KH ) 105 VSHFWUXP RI DW r& VKRZHG VLJQDOV FRUUHVSRQGLQJ WR WZR W\SHV RI QRQn HTXLYDOHQW WULIOXRURHWKHQ\O JURXSV 6XFK D VSHFWUXP LV EHOLHYHG WR DULVH IURP D VXEVWDQWLDO WKHUPDO EDUULHU GXH WR UHVWULFWHG URWDWLRQ EHWZHHQ FRQIRUPHUV LQYROYLQJ DQ V\Q DQG DQWL UHODWLRQVKLS RI WKH WULIOXRURHWKHQ\O VXEVWLWXHQWV UHODWLYH WR WKH SODQH RI WKH SKHQDQWKUHQH ULQJ 2EVHUYDWLRQ RI WKH ) 105 VSHFWUD RI RYHU WKH WHPSHUDWXUH UDQJH RI r& WR r& DQG DSSOLFDWLRQ RI FODVVLFDO WKHRU\ ZLWK UHVSHFW WR HTXLOLEULXP DQG 105 VSHFWUD DOORZHG DQ HVWLPDWLRQ RI $*r NFDOPRO IRU LQWHUFRQYHUVLRQ RI WKH LVRPHUV 0ROHFXODU PHFKDQLFV

PAGE 67

FDOFXODWLRQV HVWLPDWHG $+r5;Q NFDOPRO IRU DQWL!V\Q ZLWK $+r NFDOPRO /RFDO PLQLPD IRU V\Q ^V\Qf DQG DQWL ^DQWL$2f W\SH FRQIRUPHUV ZHUH ORFDWHG )LJXUH f ZLWK WULIOXRURHWKHQ\O WRUVLRQDO DQJOHV UHODWLYH WR WKH DURPDWLF ULQJ SODQH W=W VWUXFWXUHf IRU WKH DQWL FRQIRUPHU RI r DQG r DQG IRU WKH V\Q FRQIRUPHU RI r DQG r V\Q )LJXUH &RQIRUPDWLRQDO (TXLOLEULXP RI %LVWULIOXRURHWKHQ\Of SKHQDQWKUHQH f

PAGE 68

7KH IRUPDWLRQ RI WKH REVHUYHG SKRWRSURGXFWV IURP KDV VRPH SUHFHGHQW IURP WKH K\GURFDUERQ OLWHUDWXUH 3KRWRFKHPLFDO VWXGLHV RI GLHWKHQ\OEHQ]HQH )LJXUH f KDYH EHHQ UHSRUWHG E\ D IHZ DXWKRUVn 2QH VWXG\ IRXQG WKDW SKRWRO\VLV RI ZLWK D PHGLXP SUHVVXUH PHUFXU\ DUF WKURXJK 3\UH[ \LHOGHG EHQ]RELF\FOR>@KH[HQH f DV WKH PDMRU SURGXFW LQ D ORZ RYHUDOO \LHOG SURFHVV b PD[f ZLWK VPDOOHU DPRXQWV RI WHWUDOLQ GLK\GURQDSKWKDOHQH DQG QDSKWKDOHQH REVHUYHG DULVLQJ IURP GLK\GURQDSKWKDOHQH f 'LHWKHQ\OEHQ]HQHF ZLWK IRXU WHUPLQDO PHWK\OHQH GHXWHURQV ZDV DOVR VWXGLHG WR HVWDEOLVK D FDUERQ VNHOHWDO UHDUUDQJHPHQW YLD WR GLVSURYLQJ D PHFKDQLVP LQYROYLQJ K\GURJHQ PLJUDWLRQ 7HWUDOLQ f§ 'LK\GURQDSKWKDOHQH 1DSKWKDOHQH &( )LJXUH 3KRWRO\VLV RI 'LHWKHQ\OEHQ]HQH f 3KRWRO\VLV RI GLHWKHQ\OSKHQDQWKUHQH KDV EHHQ UHSRUWHG DQG VWXGLHV XQGHU D YDULHW\ RI FRQGLWLRQV GLG QRW OHDG WR WKH REVHUYDWLRQ RI DQ\ F\FOL]DWLRQ ,Q WKLV FDVH SRO\PHUL]DWLRQ ZDV WKH RQO\ SURFHVV ZKLFK ZDV REVHUYHG 7KH SKRWRSURGXFWV REVHUYHG IURP ELVWULIOXRURHWKHQ\OfSKHQDQWKUHQH f DUH FRQVLVWHQW ZLWK WKH DERYH K\GURFDUERQ V\VWHP UHVXOWV DQG WKH\ FDQ SRWHQWLDOO\ EH VHHQ DV DULVLQJ IURP D 1((5 GLFWDWHG SURFHVV )LJXUH VKRZV WKH SURSRVHG RYHUDOO SULPDU\ DQG VHFRQGDU\ SURFHVVHV &RQIRUPHU DQWL FDQ IRUP WKUHH SULPDU\ SKRWRSURGXFWV DQG

PAGE 69

%LF\FOR>@KH[HQH PD\ EH IRUPHG IURP WKH SHQGDQW DONHQHV UHDFWLQJ LQ D SKRWRDOORZHG WVWV F\FORDGGLWLRQ DQG F\FORKH[DGLHQH PD\ DULVH IURP D FRQURWDWRU\ HOHFWURF\FOL]DWLRQ ,QLWLDO IRUPDWLRQ RI ELF\FOR>@KH[HQH PD\ RFFXU WKURXJK HLWKHU WKH DQWL RU V\Q FRQIRUPHUV DQG WKH WUXH QDWXUH RI WKH SKRWRFKHPLFDO PHFKDQLVP LQYROYLQJ IRUPDWLRQ RI ELF\FOR>@KH[HQHV KDV EHHQ WKH VXEMHFW RI PXFK GHEDWH r$,, ERQGV WR IOXRULQH H[FHSW IRU WKH WKURXJK SRVLWLRQV RI WKH SKHQDQWKUHQH ULQJ V\VWHPV )LJXUH 3ULPDU\ DQG 6HFRQGDU\ 3URFHVVHV DQG )LQDO 3URGXFW 'LVWULEXWLRQ IRU 3KRWRO\VLV RI %LVWULIOXRURHWKHQ\OfSKHQDQWKUHQH f 3KRWRFKHPLFDO IRUPDWLRQ RI ELF\FOR>@KH[HQHV DUH IRUPDOO\ :RRGZDUG DQG +RIIPDQ DOORZHG -WV-WD RU -WD-WV SURFHVVHV (VWDEOLVKLQJ

PAGE 70

WKH WUXH QDWXUH RI WKH PHFKDQLVP UHTXLUHV ODEHOV ZLWK ZKLFK WR IROORZ WKH VWHUHRFKHPLFDO FRXUVH RI WKH SURFHVV :KLOH WKHUH DUH H[DPSOHV RI UWVUWD DQG WDrV SKRWRLVRPHUL]DWLRQVn WKHUH DUH DOVR H[DPSOHV RI GLVDOORZHG -OD-WD SURFHVVHV )XUWKHU DQ H[SODQDWLRQ H[LVWV EDVHG RQ FURVV ELF\FOL]DWLRQ LQ OLQHDU FRQMXJDWHG SRO\HQHV ZKHUH WKH DXWKRUnV UDWLRQDOL]DWLRQ DOORZV IRU FRQFHUWHG r SKRWRSURFHVVHV 2WKHU DUJXPHQWV KDYH LQYROYHG D VWHSZLVH SURFHVV ZKLFK LQYROYHV D FRQFHUWHG FRQURWDWRU\ FORVXUH RI WKH WKUHH PHPEHUHG ULQJ IROORZHG E\ FORVXUH RI WKH ILYH PHPEHUHG ULQJf DQG VXGGHQ SRODUL]DWLRQ RI WKH =fWULHQH IURP D && WZLVWHG GLUDGLFDO WR D FKDUJH VHSDUDWHG ]ZLWWHULRQ ZKLFK XQGHUJRHV FORVXUHnf 3ULPDU\ SKRWRSURGXFW ZDV QHYHU REVHUYHG PRVW OLNHO\ GXH WR WKHUPDO LQVWDELOLW\ FDXVHG E\ VWUDLQ LQ WKLV VSLURIXVHG V\VWHP DQG ORVV RI DURPDWLFLW\ IURP WKH FHQWUDO SKHQDQWKUHQH ULQJ 8QGHU WKH UHDFWLRQ FRQGLWLRQV PRVW OLNHO\ XQGHUJRHV D YLQ\OF\FORSURSDQHF\FORSHQWHQH UHDUUDQJHPHQW WR DV UDSLGO\ DV LW LV IRUPHG 3KRWRO\VLV RI ZDV DWWHPSWHG DW r& ORRNLQJ IRU E\ ORZ WHPSHUDWXUH ) 105 EXW RQO\ ZDV REVHUYHG /RZHU WHPSHUDWXUH VWXGLHV ZHUH DEDQGRQHG GXH WR HTXLSPHQW GLIILFXOWLHV %LF\FOR>@KH[HQH PD\ EH IRUPHG E\ D SKRWRDOORZHG rVrV F\FORDGGLWLRQ IURP V\Q RU D VHFRQGDU\ SURFHVV LQYROYLQJ D Q GLVURWDWRU\ HOHFWURF\FOL]DWLRQ RI 7KLV ZDV IRXQG WR EH RFFXUULQJ DV SKRWRO\VLV RI SXUH VDPSOHV RI OHG LQ ORZ \LHOG WR DQG VKRZHG QR UHYHUVLELOLW\ WR WKH SDUHQW WULHQH 'LVFXVVLRQ RI 7KHUPDO 6WXGLHV 7KH LQLWLDO DVVXPSWLRQ WKDW D VXLWDEO\ WDLORUHG IOXRULQDWHG =fWULHQH V\VWHP ZRXOG DOORZ IRU SURELQJ RI WKH WRUTXRHOHFWURQLF HIIHFW LQ WULHQH N WKHUPDO FKHPLVWU\ WXUQHG RXW WR EH LQFRUUHFW LQ WKH FDVH RI WKH SKHQDQWKUHQH DQQXODWHG V\VWHP ,QYHVWLJDWLRQ RI WKH WKHUPDO UHDUUDQJHPHQWV RI ELVWULIOXRUR

PAGE 71

HWKHQ\OfSKHQDQWKUHQH f DQG SHUIOXRUR(=(DQG (((fGLPHWK\O RFWDWULHQH =(ff UHYHDOHG WKDW UHDUUDQJHPHQW SDWKZD\V IRU WKHVH V\VWHPV KDYH OLWWOH LQ FRPPRQ ZLWK WKH FRUUHVSRQGLQJ K\GURFDUERQV 7KHUPRO\VLV RI 3HUIOXRUR(=(IDQG (((9GLPHWKYORFWDWULHQH = 7KHUPRO\VLV RI WKH PL[WXUH RI = DQG ( OHG WR LQLWLDO && =( GRXEOH ERQG LVRPHUL]DWLRQ DW WHPSHUDWXUHV DERYH r& 7KH K\GURFDUERQ DQDORJ =KH[DWULHQH IRUPV F\FORKH[DGLHQH ZLWK (D NFDOPRO ZKLOH && ( WR = GRXEOH ERQG LVRPHUL]DWLRQ UHTXLUHV WHPSHUDWXUHV LQ H[FHVV RI r& ZLWK (D NFDOPRO 7KXV WKH K\GURFDUERQ =WULHQH XQGHUJRHV WKH N HOHFWURF\FOLF SURFHVV H[FOXVLYHO\ GXH WR WKH $(D NFDOPRO GLIIHUHQFH EHWZHHQ LWnV FRQFHUWHG ULQJ FORVXUH DQG LWnV && GRXEOH ERQG LVRPHUL]DWLRQ $OWKRXJK DON\O VXEVWLWXWLRQ FDQ ORZHU WKH (D IRU && GRXEOH ERQG LVRPHUL]DWLRQ RI KH[DWULHQH E\ DSSUR[LPDWHO\ NFDOPRO DQG SHUIOXRULQDWLRQ RI EXWHQH OHDGV WR D ORZHULQJ RI WKH (}= LVRPHUL]DWLRQ E\ NFDOPRO YHUVXV WKH K\GURFDUERQ LW LV LQFRQFHLYDEOH WKDW WKH IOXRULQDWLRQ RI = ZLOO OHDG WR ORZHULQJ LQ HQHUJ\ RI WKH && GRXEOH ERQG =!( LVRPHUL]DWLRQ VR DV WR PDNH WKLV SURFHVV H[FOXVLYHO\ SUHIHUUHG RYHU WKH ULQJ FORVXUH 7KH QH[W SURFHVV REVHUYHG WR RFFXU LV D N F\FOL]DWLRQ RI WULHQH $Q HTXLOLEULXP UDWLR RI ZDV HVWDEOLVKHG EHWZHHQ ( DQG =f DQG DW r& LQ QSHQWDQH DV LOOXVWUDWHG LQ )LJXUH 3HUIOXRURKH[DWULHQH f KDV EHHQ UHSRUWHG LQ D SDWHQW WR DIIRUG DQ b \LHOG RI SHUIOXRURF\FORKH[DGLHQH f XSRQ S\URO\VLV DW r& LQ D IORZ V\VWHP &RQFXUUHQW WR WKLV WKHVLV SURMHFW D WKHUPDO VWXG\ RI SHUIOXRUR KH[DWULHQH DW ORZHU WHPSHUDWXUHV ZDV UHSRUWHG 7KHVH DXWKRUV RIIHUHG VLPLODU UHVXOWV WR WKRVH REWDLQHG LQ RXU VWXG\ RI 7KHUPRO\VLV RI

PAGE 72

)LJXUH 0L[WXUH 2EWDLQHG IURP 7KHUPRO\VLV RI 3HUIOXRUR(=((((f GLPHWK\ORFWDWULHQH =(ff DW r& LQ Q3HQWDQH SHUIOXRURKH[DWULHQH DW r& HVWDEOLVKHG DQ HTXLOLEULXP PL[WXUH FRQVLVWLQJ RI b SHUIOXRURKH[DWULHQH DQG b SHUIOXRUR HWKHQ\OF\FOREXWHQH f 7KHUPRO\VLV RI SHUIOXRURKH[DWULHQH DW r& ZDV UHSRUWHG WR LUUHYHUVLEO\ \LHOG SHUIOXRURF\FORKH[DGLHQH ,Q WKH IOXRULQDWHG WULHQH V\VWHPV IRUPDWLRQ RI DONHQ\OF\FOREXWHQHV LQ SUHIHUHQFH WR F\FORKH[DGLHQHV XSRQ WKHUPRO\VLV OHDGV WR WKH FRQFOXVLRQ WKDW WKH HQHUJ\ VXUIDFHV IRU WKH K\GURFDUERQ DQG IOXRURFDUERQ V\VWHPV DUH TXLWH GLIIHUHQW ,W LV LQIRUPDWLYH WR REVHUYH WKH HQWKDOS\ GLDJUDP )LJXUH f IRU WKH K\GURFDUERQ &H+ V\VWHP )RUPDWLRQ RI HWKHQ\OF\FOREXWHQH f E\ D Q FRQURWDWRU\ HOHFWURF\FOLF SURFHVV LV QRW REVHUYHG LQ K\GURFDUERQ WULHQH WKHUPDO VWXGLHV (+H[DWULHQH f LVRPHUL]HV WR WKH =WULHQH f ZKLFK WKHQ XQGHUJRHV WKH Q ULQJ FORVXUH WR F\ORKH[DGLHQH f %RWK SURFHVVHV DUH SUHIHUUHG RYHU WKH Q F\FOL]DWLRQ 3HUIOXRURKH[DWULHQH LV VHHQ WR IRUP SHUIOXRURF\FORKH[DGLHQH DW KLJKHU WHPSHUDWXUHV DQG LW LV OLNHO\ WKDW SHUIOXRUR(=(GLPHWK\O RFWDWULHQH =f ZRXOG KDYH H[KLELWHG D VLPLODU UHDFWLRQ SDWK KDG WKH V\VWHP EHHQ LQYHVWLJDWHG DW KLJKHU WHPSHUDWXUHV

PAGE 73

)LJXUH (QWKDOS\ 'LDJUDP IRU &+ 7UDQVIRUPDWLRQV 7KH GDWD REWDLQHG IURP WKHVH SHUIOXRURWULHQH V\VWHPV DOWKRXJK TXDOLWDWLYH LQ QDWXUH UHTXLUH FKDQJHV LQ WKH HQHUJ\ SURILOH IRU IOXRULQDWHG WULHQH WUDQVIRUPDWLRQV )LJXUH f 7KH WKHUPDO HTXLOLEULXP ULFK LQ SHUIOXRUR DONHQ\OF\FOREXWHQHV LQ WKH FDVHV RI SHUIOXRURKH[DWULHQH f DQG SHUIOXRUR(=(DQG (((fGLPHWK\ORFWDWULHQH =eff OHDG WR D ORZHULQJ RI WKH $+rS RI WKH SHUIOXRURDONHQ\OF\FOREXWHQHV UHODWLYH WR WKH SHUIOXRURWULHQHV 6XFK D FKDQJH LQ WKH UHODWLYH HQWKDOS\ KDV SUHFHGHQW LQ WKH FDVH RI WKH HDUOLHU GLVFXVVHG IOXRULQDWHG F\FOREXWHQHGLHQH LQWHUFRQYHUVLRQV &KDSWHU 2QH 7DEOH DQG )LJXUH f ,Q WKHVH H[DPSOHV LW ZDV IRXQG WKDW WKH SHUIOXRULQDWHG F\FOREXWHQHV ZHUH ORZHU LQ HQHUJ\ WKDQ WKH SHUIOXRURGLHQHV ZLWK $$+r5RQ WKH RUGHU RI NFDOPRO EHWZHHQ WKH K\GURFDUERQ DQG IOXRURFDUERQ V\VWHPV ,UUHYHUVLEOH IRUPDWLRQ RI SHUIOXRUR F\FORKH[DGLHQHV IURP WKH IOXRUR=fWULHQHV RQO\ LQ WKH KLJK WHPSHUDWXUH UXQV OHDGV WR WKHVH VSHFLHV KDYLQJ WKH PRVW QHJDWLYH $+rI RI WKH LVRPHUV EXW ZLWK D UDLVHG HQHUJ\ EDUULHU WR WKH N GLVURWDWRU\ WUDQVLWLRQ VWDWH

PAGE 74

)LJXUH (QWKDOS\ 'LDJUDP IRU 3HUIOXRURWULHQH 7UDQVIRUPDWLRQV 7KHUPRO\VLV RI %LVWULIOXRURHWKHQYQ'KHQDQWKUHQH f 7KHUPRO\VLV RI ELVWULIOXRURHWKHQ\OfSKHQDQWKUHQH f ZDV IRXQG WR IRUP WKH GHVLUHG KH[DIOXRURGLK\GURWULSKHQ\OHQH f EXW RQO\ DV D VPDOO FRPSRQHQW LQ D YHU\ FRPSOLFDWHG RYHUDOO UHDFWLRQ SURFHVV $ YLUWXDOO\ XQSUHFHGHQWHG SURFHVV IRU =fWULHQH WKHUPDO FKHPLVWU\ OHDGLQJ WR ELF\FOR>@KH[HQH DQG VXEVHTXHQW UHDUUDQJHPHQW RI WKLV VSHFLHV ZDV REVHUYHG WR FRPSULVH WKH PDMRU UHDFWLRQ SDWKZD\ RI 7KHUPDO VWXGLHV RI GLDONHQ\O DURPDWLFV DUH RQO\ UDUHO\ HQFRXQWHUHG LQ WKH OLWHUDWXUH $Q\ DWWHPSW WR LQYHVWLJDWH WKH HOHFWURF\FOLF FKHPLVWU\ RI VXFK V\VWHPV ZRXOG EH H[SHFWHG WR EH FRPSOLFDWHG E\ WKH LQVWDELOLW\ RI WKH F\FOL]HG QRQDURPDWLF SURGXFWV XQGHU WKH UHDFWLRQ FRQGLWLRQV DQG WKH IDFLOLW\ RI WKHVH SURGXFWV WR XQGHUJR IXUWKHU UHDUUDQJHPHQW 7KHUPDO VWXGLHV RI D VHULHV RI GLSURSHQ\OEHQ]HQHV KDV EHHQ UHSRUWHG 7KHVH V\VWHPV ILUVW VKRZ SHQGDQW DONHQH LVRPHUL]DWLRQ ZKLFK ZDV SURYHQ WR RFFXU E\ >@VLJPDWURSLF K\GURJHQ VKLIWV +LJKHU WHPSHUDWXUHV \LHOG GLK\GURQDSKWKDOHQHV DQG DON\O GLK\GURQDSKWKDOHQHV ZKLFK DULVH IURP GLVURWDWRU\ ULQJ FORVXUH IROORZHG E\ DQ

PAGE 75

>@VLJPDWURSLF K\GURJHQ VKLIW 7KH PHFKDQLVWLF QDWXUH RI WKHVH SURFHVVHV ZDV HVWDEOLVKHG E\ VWXG\LQJ VXLWDEO\ GHXWHULXP ODEHOHG VSHFLHV DQG D PHFKDQLVWLF UDWLRQDOH ZDV SURSRVHG DV VHHQ LQ )LJXUH )LJXUH 7KHUPDO 3URFHVVHV 2EVHUYHG IRU 'LSURSHQ\OEHQ]HQHV 2QH LQVWDQFH RI WKH WKHUPRO\VLV RI GLHWKHQ\OSKHQDQWKUHQH DW r& KDV EHHQ UHSRUWHG WR \LHOG b WULSKHQ\OHQH DSSDUHQWO\ DULVLQJ IURP IRUPDWLRQ RI WKH XQVWDEOH GLK\GURWULSKHQ\OHQH ZKLFK XQGHUJRHV ORVV RI K\GURJHQ )URP WKH WKHUPRG\QDPLF DUJXPHQW RIIHUHG HDUO\ LQ WKLV FKDSWHU LW ZDV EHOLHYHG WKDW GLSHUIOXRURDONHQ\OSKHQDQWKUHQHV RIIHUHG D FKDQFH WR REVHUYH D UHYHUVLEOH WKHUPDO Q HOHFWURF\FOL]DWLRQ LQ D =fWULHQH V\VWHP 7KH WKHUPRG\QDPLFV VHHPHG IDYRUDEOH DQG WKH SRWHQWLDO IRU UHODWLYHO\ XQSUHFHGHQWHG IOXRULQH VKLIWV QRQH[LVWHQW GXH WR WKH JUHDWHU VWUHQJWK RI WKH &) YHUVXV &+ ERQG ,Q WKLV OLJKW LW ZDV LQLWLDOO\ GLVFRXUDJLQJ WR REVHUYH VXFK D FRPSOH[ PL[WXUH XSRQ WKHUPRO\VLV RI

PAGE 76

7KHUPRO\VLV RI ELVWULIOXRURHWKHQ\OfSKHQDQWKUHQH f OHG WR IRUPDWLRQ RI WZR SULPDU\ SURGXFWV DQG WZR VHFRQGDU\ SURGXFWV DV LOOXVWUDWHG LQ )LJXUH 2QH RI WKH SULPDU\ WKHUPDO SURGXFWV KH[DIOXRUR GLK\GURWULSKHQ\OHQH f ZDV REVHUYHG WR EH IRUPHG WR QR PRUH WKDQ b LQ WKH UHDFWLRQ PL[WXUH RYHU WKH WHPSHUDWXUHV H[DPLQHG &RQWUDU\ WR H[SHFWDWLRQV WKHUPRO\VLV RI SXULILHG XQGHU LGHQWLFDO FRQGLWLRQV XVHG IRU F\OLL]DWLRQ RI WKH SDUHQW WULHQH GHPRQVWUDWHG WKDW WKH F\FOL]DWLRQ ZDV LUUHYHUVLEOH 7KH F\FOL]HG )LJXUH 7UDQVIRUPDWLRQV 2EVHUYHG 8SRQ 7KHUPRO\VLV RI %LVWULIOXRURHWKHQ\OfSKHQDQWKUHQH f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f RYHU WKH LQGLYLGXDO UXQV H[DPLQHG DFWLYDWLRQ SDUDPHWHUV RI $+r s

PAGE 77

NFDOPRO DQG $6r s FDOPRO[GHJ ZHUH REWDLQHG IRU IRUPDWLRQ RI IURP 6XFK SDUDPHWHUV IRU WKH IRUPDWLRQ RI EHLQJ IRUPDOO\ D N GLVURWDWRU\ SURFHVV IURP DUH GLIILFXOW WR UDWLRQDOL]H DV QR FRPSDUDWLYH NLQHWLF GDWD H[LVWV IRU F\FOL]DWLRQ RI DQ\ RWKHU IOXRULQDWHG =fWULHQH V\VWHP )RUPDWLRQ RI KH[DIOXRURSKHQDQWKURfELF\FOR>@ KH[HQH f ZDV REVHUYHG WR EH WKH PDMRU SURFHVV HDUO\ LQ WKH UHDFWLRQ RI 7KLV WKHUPDO F\FOL]DWLRQ RI D IOXRULQDWHG =fWULHQH WR IRUP D IOXRULQDWHG ELF\FOR>@KH[HQH LV XQSUHFHGHQWHG LQ IOXRURFDUERQ OLWHUDWXUH DQG RQO\ RQH H[DPSOH DFFRPSDQLHG E\ PLQLPDO GLVFXVVLRQ KDV EHHQ IRXQG LQ WKH FRUUHVSRQGLQJ K\GURFDUERQ OLWHUDWXUH DQG LV LOOXVWUDWHG LQ )LJXUH $V )LJXUH 7KHUPDO DQG 3KRWRSURGXFWV RI eI%XW\ODPLQRf=f KH[DWULHQH GLVFXVVHG HDUOLHU WKH DFWLYDWLRQ SDUDPHWHUV REWDLQHG IRU IRUPDWLRQ RI IURP DUH $+r s NFDOPRO DQG $6r s FDOPRO[GHJ 7KH XQSUHFHGHQWHG QDWXUH RI WKLV WUDQVIRUPDWLRQ GRHV QRW DOORZ IRU FRQMHFWXUH DV WR WKH PHFKDQLVWLF VLJQLILFDQFH RI WKHVH YDOXHV 7KXV SRWHQWLDO SURFHVVHV LQYROYHG ZLOO EH RIIHUHG ZLWK UDWLRQDOL]DWLRQ RI WKH DFWLYDWLRQ SDUDPHWHUV OHIW WR WKH IXWXUH 7KH WKHUPDO FORVXUH RI D =fWULHQH V\VWHP WR D ELF\FOR>@KH[ HQH ULQJ LV IRUPDOO\ D :RRGZDUG DQG +RIIPDQ DOORZHG WD QD RU UFV QV SURFHVV 'HWHUPLQLQJ WKH WUXH VWHUHRFKHPLFDO QDWXUH RI WKH SURFHVV UHTXLUHV DW D PLQLPXP ODEHOV DW HDFK WHUPLQXV RI WKH UHDFWLQJ WULHQH V\VWHP 'XH WR WKH XQSUHFHGHQWHG QDWXUH RI WKLV WKHUPDO SURFHVV DQG WKH ODFN RI

PAGE 78

VWHUHRFKHPLFDO ODEHOV LQ WKH DIRUHPHQWLRQHG DQG V\VWHPV WKH TXHVWLRQ RI V\PPHWU\ FRQVHUYDWLRQ FDQ QRW EHJLQ WR EH DGGUHVVHG 7KH IRUPDWLRQ RI IURP LQYROYHV D IXUWKHU FRPSOLFDWLRQ DV WKH QHFHVVDU\ SULPDU\ LQWHUPHGLDWH )LJXUH f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

PAGE 79

UHDUUDQJHPHQW PXVW VSRQWDQHRXVO\ RFFXU DV LV IRUPHG WR UHOLHYH WKH VWUDLQ LQ WKLV VSLURIXVHG V\VWHP DQG UHVWRUH DURPDWLFLW\ WR WKH FHQWUDO SKHQDQWKUHQH ULQJ $Q DOWHUQDWH GLUDGLFDO SURFHVV IURP DQI PD\ RFFXU ZLWK IRUPDWLRQ RI WKH LQWHUPHGLDWH ,Q WKLV FDVH FORVXUH RI WKH WHUPLQXV RI RQH WULIOXRURHWKHQ\O VXEVWLWXHQW RQ WKH VHFRQG DW LWV FDUERQ DWWDFKHG WR WKH SKHQDQWKUHQH ULQJ ZRXOG \LHOG WKH ELUDGLFDO ZKLFK PD\ WKHQ UHFRPELQH WR DQG UHDUUDQJH WR WKH REVHUYHG SURGXFW +H[DIOXRURSKHQDQWKURfELF\FOR>@KH[HQH f ZDV REVHUYHG WR IXUWKHU UHDUUDQJH XQGHU WKH WKHUPRO\VLV FRQGLWLRQV WR IRUP DQG )LJXUH f 6LQFH ZDV XQUHDFWLYH ZLWK WUDFH IOXRULGH DW ORZHU WHPSHUDWXUHV DQG VLQFH GLVDSSHDUDQFH RI IROORZV ILUVWRUGHU NLQHWLFV DQG \LHOGV OLQHDU (\ULQJ SORWV RYHU WKH WHPSHUDWXUHV DQG WKURXJK WKH b H[WHQW RI UHDFWLRQ H[DPLQHG D PHFKDQLVP LQYROYLQJ IOXRULGH FDWDO\VLV FDQ HIIHFWLYHO\ EH UXOHG RXW $ K\GURFDUERQ DQDORJ ELF\FOR>@KH[HQH )LJXUH f LV NQRZQ WR XQGHUJR WKHUPDO && F\FORSURSDQH ERQG KRPRO\VLV WR \LHOG ELUDGLFDO LQ ZKLFK + VKLIWV PD\ RFFXU LQ WZR SRVVLEOH GLUHFWLRQV OHDGLQJ WR WKH REVHUYHG SURGXFWV DQG F\FORKH[DGLHQH f )LJXUH 7KHUPRO\VLV RI %LF\FOR>@KH[HQH f

PAGE 80

7KHUPRO\VLV RI EHQ]RELF\FOR>@KH[HQH )LJXUH f KDV EHHQ VWXGLHG E\ WKH IODVK YDFXXP WHFKQLTXH 2YHU WKH KLJK WHPSHUDWXUHV LQYHVWLJDWHG r&f LW ZDV IRXQG WKDW WKH PDMRU SULPDU\ SURGXFW ZDV )97 r& bf bf 1DSKWKDOHQH bf bf mbf )LJXUH )ODVK 9DFXXP 7KHUPRO\VLV RI %HQ]RELF\FOR>@KH[HQH f GLK\GURQDSKWKDOHQH f ZLWK D YDULHW\ RI PLQRU SURGXFWV f DOVR REVHUYHG 7KHVH SURGXFWV ZHUH SURSRVHG DV DULVLQJ IURP KRPRO\WLF FOHDYDJH RI WKH DSSURSULDWH F\FORSURSDQH ULQJ ERQG IROORZHG E\ D K\GURJHQ VKLIW f DQG HOHFWURF\FOLF SURFHVV f *DV DQG VROXWLRQ SKDVH WKHUPDO UHDUUDQJHPHQW RI SHUIOXRUREHQ]RELF\FOR>@KH[HQH )LJXUH f KDV EHHQ UHSRUWHG LQ D VWXG\ DGGUHVVLQJ WKH UHDFWLRQ RI SHUIOXRURLQGHQH f ZLWK VRXUFHV RI GLIOXRURFDUEHQHf 3HUIOXRURLQGHQH f ZDV IRXQG WR UHDFW ZLWK GLIOXRURFDUEHQH JHQHUDWHG IURP WKHUPRO\VLV RI KH[DIOXRURSURS\OHQH R[LGH +)32f $W ORZHU WHPSHUDWXUHV SHUIOXRUREHQ]RELF\FOR>@KH[HQH f ZDV IRXQG WR EH WKH PDMRU SURGXFW ZLWK VPDOOHU DPRXQWV RI SHUIOXRURGLK\GURQDSKWKDOHQHV f DQG SHUIOXRURPHWK\OLQGHQH f DOVR EHLQJ REVHUYHG 7KHUPRO\VLV RI ZDV DOVR LQGHSHQGHQWO\ LQYHVWLJDWHG 7KHUPRO\VLV RI QHDW DW r& \LHOGHG DQ PL[WXUH RI DQG WKHUPRO\VLV DW r& LQ D IORZ V\VWHP \LHOGHG DQ PL[WXUH RI

PAGE 81

+)32 r& )LJXUH 5HDFWLRQ RI 3HUIOXRURLQGHQH f ZLWK 'LIOXRURFDUEHQH DQG 7KHUPRO\VLV RI 3HUIOXRUREHQ]RELF\FOR>@KH[HQH f (OLPLQDWLRQ RI GLIOXRURFDUEHQH FDQ EH D IDFLOH SURFHVV LQ KLJKO\ IOXRULQDWHG F\FORSURSDQHV DQG ZDV REVHUYHG LQ WKH WKHUPDO VWXG\ RI SHUIOXRUREHQ]RELF\FOR>@KH[HQH f DOEHLW DW KLJKHU WHPSHUDWXUHV WKDQ ZHUH LQYROYHG LQ RXU VWXG\ RI 7KLV SURFHVV ZDV UHYHDOHG E\ IRUPDWLRQ RI VLJQLILFDQW DPRXQWV RI SHUIOXRURLQGHQH XSRQ WKHUPRO\VLV RI 7KH DQDORJRXV FRPSRXQG LQ WKH FDVH RI ZDV QHYHU REVHUYHG LQ DQ\ RI WKH WKHUPRO\VLV UXQV ZLWK RU 2Q WKHVH JURXQGV D PHFKDQLVP LQYROYLQJ GLIOXRURFDUEHQH FDQ EH UXOHG RXW &RQVLGHULQJ WKH DERYH UHVXOWV WKH REVHUYHG WKHUPDO UHDUUDQJHPHQW RI WR IRUP DQG LV QRW RXW RI FKDUDFWHU )LJXUH LOOXVWUDWHV WKH SRVVLEOH PHFKDQLVWLF URXWH LQYROYHG +RPRO\WLF FOHDYDJH RI RQO\ RQH RXW RI WKH WKUHH F\FORSURSDQH ERQGV LQ LV IRXQG WR SURGXFWLYHO\ OHDG WR SURGXFWV &OHDYDJH RI ERQGV D f RU E f OHDGV WR ELUDGLFDOV ZKLFK LQ ERWK FDVHV

PAGE 82

)LJXUH 0HFKDQLVWLF 5DWLRQDOH IRU 7KHUPDO 'HFRPSRVLWLRQ RI +H[DIOXRURSKHQDQWKURfELF\FOR>@KH[HQH f KDYH RQH EHQ]\OLF FHQWHU WKH RWKHU EHLQJ RQ D VHFRQGDU\ f DQG SULPDU\ f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

PAGE 83

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f LQ RQH RI WZR GLUHFWLRQV LQ 7KH VOLJKWO\ IDYRUHG SURGXFW LV IRUPHG E\ VKLIW WRZDUGV WKH VWDELOL]HG UDGLFDO FHQWHU )OXRULQH DWRP VKLIWV ODFN XQDPELJRXV SUHFHGHQW LQ WKH OLWHUDWXUH 7KHUPDO >@ DQG >@IOXRULQH DWRP VKLIWV KDYH EHHQ LQYRNHG LQ VWXGLHV LQYROYLQJ LVRPHUL]DWLRQV RI GLK\GURKH[DIOXRURF\FORKH[DGLHQHV DQG SHUIOXRURLVRLQGHQHV 3KRWRFKHPLFDO >@IOXRULQH DWRP VKLIWV KDYH EHHQ LQYRNHG LQ WKH LVRPHUL]DWLRQ RI SHUIOXRURLQGHQH WR SHUIOXRURLVRLQGHQH DQG D UHDUUDQJHPHQW RI SHUIOXRURWULF\FOR>@XQGHFDWULHQH f WR SHUIOXRURWULF\FOR>f@XQGHFDWULHQH f )LJXUH 3KRWRFKHPLFDO >@)OXRULQH $WRP 6KLIW LQ 3HUIOXRURWULF\FOR >@XQGHFDWULHQH f

PAGE 84

6WHULF (IIHFWV LQ 7KHUPDO =f7ULHQH (OHFWURF\FOL]DWLRQV 7KH UXOH RI RUELWDO V\PPHWU\ FRQVHUYDWLRQ IRU D FRQFHUWHG SURFHVV UHTXLUHV WKDW && ERQG IRUPDWLRQ LQ WKH WKHUPDO UHDUUDQJHPHQW RI D =f WULHQH WR D F\FORKH[DGLHQH RFFXU E\ RYHUODS RI Q RUELWDOV RQ WKH VDPH VLGH RI WKH WULHQH SODQH KHQFH GHILQLQJ D GLVURWDWRU\ SURFHVV $ FRQVHTXHQFH RI WKLV W\SH RI SURFHVV LV WKDW =f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f VKRZ OLWWOH FKDQJH LQ DFWLYDWLRQ HQWURS\ LQGLFDWLQJ VLPLODU WUDQVLWLRQ VWDWH JHRPHWU\ DQG WLPLQJ LV EHLQJ PDLQWDLQHG WKHUHIRUH WKH VWUDLQ EHLQJ EXLOW LQWR WKH WUDQVLWLRQ VWDWH LV PDQLIHVWLQJ LWVHOI DV D PHDVXUDEOH LQFUHDVH LQ DFWLYDWLRQ HQWKDOS\ 6XIILFLHQWO\ KLQGHUHG V\VWHPV f RIWHQ GR QRW XQGHUJR N F\FOL]DWLRQ IURP WKH LQLWLDO =fWULHQH EXW UHDUUDQJH E\ RWKHU SURFHVVHV VXFK DV K\GURJHQ VKLIWV WR WULHQHV ZKLFK DUH PRUH VXLWHG IRU WKH GLVURWDWRU\ SURFHVV $Q LQWHUHVWLQJ UHVXOW KDV EHHQ UHSRUWHG IRU WKH WKHUPDO VWXG\ RI N ULQJ FORVXUH LQ D & DQG & GHXWHUDWHG =KH[DWULHQH )LJXUH f 6HFRQGDU\ LVRWRSH HIIHFWV N+NRf RI IRU ((' f DQG IRU == f ZHUH REVHUYHG 7KH WZR WUDQVLWLRQ VWDWHV LQYROYHG DUH GLDVWHUHRPHULFDOO\ UHODWHG ZLWK UHVSHFW WR WKH GHXWHULXP VXEVWLWXHQWV 'XH WR WKH GLIIHUHQW VWHUHRFKHPLFDO HQYLURQPHQWV LQ WKH WUDQVLWLRQ VWDWH DQ LQFUHDVH LQ

PAGE 85

LQWUDPROHFXODU QRQERQGLQJ LQWHUDFWLRQV ZDV SURSRVHG WR LQFUHDVH WKH IRUFH FRQVWDQWV LQ WKH FDVH RI WKH WHUPLQDOO\ FnVGHXWHUDWHG PDWHULDO DQG JLYH ULVH WR WKH LQYHUVH NQNR HIIHFW REVHUYHG $+r NFDOPROf $6r HXf FK AbAFH+V &+&+ )LJXUH $FWLYDWLRQ 3DUDPHWHUV IRU 1RQ+LQGHUHG YHUVXV +LQGHUHG =f 7ULHQH &\FOL]DWLRQV )LJXUH ((' f DQG =='=f+H[DWULHQH f =f7ULHQH F\FOL]DWLRQV KDYH UHFHLYHG FRQVLGHUDEOH WKHRUHWLFDO LQWHUHVW ,Q FDOFXODWHG WUDQVLWLRQ VWDWHV IRU WKH GLVURWDWRU\ UF =fWULHQH HOHFWURF\FOL]DWLRQ D GHILQLWH VWHULF FURZGLQJ LQ LV IRXQG EHWZHHQ WKH & DQG &

PAGE 86

FLV VXEVWLWXHQWVnnnn 7KH WUDQVLWLRQ VWDWH LV D ERDWOLNH ULQJ FRQIRUPDWLRQ )LJXUH f ZLWK & DQG & FLV K\GURJHQV WZLVWHG LQ DQG VHSDUDWHG E\ OHVV WKDQ WKH VXP RI WKHLU YDQ GHU :DDOnV UDGLL )LJXUH $SSUR[LPDWH 5HSUHVHQWDWLRQ RI WKH &DOFXODWHG =f7ULHQH 'LVURWDWRU\ 7UDQVLWLRQ 6WDWH &RQFOXVLRQV ,W LV EHOLHYHG WKDW IRU WKH FDVHV RI WKH IOXRULQDWHG =fWULHQHV H[DPLQHG LQ WKLV VWXG\ DQG IRXQG LQ WKH OLWHUDWXUH ELVWULIOXRURHWKHQ\OfSKHQDQWKUHQH f SHUIOXRUR (=eGLP HWK\O RFWDWULHQH =f DQG SHUIOXRUR=KH[DWULHQH f VLJQLILFDQW UHSXOVLRQ PXVW GHYHORS EHWZHHQ WKH & DQG & =f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n 7KLV WRJHWKHU ZLWK WKH REVHUYHG UHYHUVDO RI WKH UHODWLYH WKHUPRG\QDPLFV LQ WKH SHUIOXRULQDWHG

PAGE 87

DQG K\GURFDUERQ F\FOREXWHQHGLHQH V\VWHPV OHDG WR $Q FORVXUHV DV IDFLOH DQG SULPDU\ SURFHVVHV LQ WKH WKHUPRO\VLV RI IOXRULQDWHG =fWULHQHV )LJXUH $SSUR[LPDWH 5HSUHVHQWDWLRQ RI WKH &DOFXODWHG 'LHQH &RQURWDWRU\ 7UDQVLWLRQ 6WDWH $Q DQDORJRXV SURFHVV WR WKH UHSRUWHG WF WKHUPDO FORVXUH RI SHUIOXRUR= KH[DWULHQH DW KLJKHU WHPSHUDWXUHV ZDV QHYHU REVHUYHG LQ WKHUPDO VWXGLHV RI SHUIOXRUR(=(GLPHWK\ORFWDWULHQH =f PRVW OLNHO\ EHFDXVH VXIILFLHQWO\ KLJK WHPSHUDWXUHV ZHUH QRW XVHG LQ WKH VWXG\ RI WKLV PDWHULDO 7KH IDFW WKDW WHUPLQDO FLV IOXRULQHV LPSHGH WKH =fWULHQH GLVURWDWRU\ SURFHVV VKRXOG QRW EH VXUSULVLQJ LQ OLJKW RI WKH SUHYLRXV GLVFXVVLRQV ,W LV VXUSULVLQJ WKRXJK LQ WHUPV RI WKH PDJQLWXGH RI WKH HIIHFW 7KH IDFW LV WKDW LQ WKHVH IOXRULQDWHG V\VWHPV $Q F\FOL]DWLRQ LV IDYRUHG RYHU DQG RFFXUULQJ URXJKO\ DW WHPSHUDWXUHV QHFHVVDU\ IRU WKH K\GURFDUERQ Q UHDUUDQJHPHQW 7KLV ODUJH GHYLDWLRQ LQ WKH WKHUPDO FKHPLVWU\ RI IOXRURFDUERQ IURP K\GURFDUERQ SUHFHGHQW XSRQ WHUPLQDO =fWULHQH FLV IOXRULQDWLRQ FUHDWHG WKH LPSHWXV IRU IXUWKHU VWXG\ RI IOXRULQHnV HIIHFW RQ WKHUPDO SURFHVVHV LQYROYLQJ GLVURWDWRU\ DQG FRQURWDWRU\ WUDQVLWLRQ VWDWHV 2XW RI WKLV LQWHUHVW D VWUDWHJ\ GHVLJQHG WR SURYLGH PRUH LQVLJKW WR WKLV VHHPLQJ VWHULF LQIOXHQFH RI IOXRULQH ZDV GHYHORSHG DQG LWnV VWXG\ LV GHVFULEHG LQ &KDSWHU

PAGE 88

&+$37(5 >@6,*0$7523,& 5($55$1*(0(176 2) 7(50,1$//< )/825,1$7(' ',(1(6 ,QWURGXFWLRQ 7KH REVHUYDWLRQ WKDW Q WKHUPDO GLVURWDWRU\ FORVXUH RI SHUIOXRULQDWHG =f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fWULHQH GLVURWDWRU\ F\FOL]DWLRQ OHDGV WR D WZLVWLQJ LQ DQG FURZGLQJ RI WKH WHUPLQDO FLV VXEVWLWXHQWV ZKLFK LV EHOLHYHG WR EH DW OHDVW SDUWLDOO\ UHVSRQVLEOH IRU WKH REVHUYHG GHYLDWLRQ RI SHUIOXRURFDUERQ FKHPLVWU\ IURP WKDW RI DQDORJRXV K\GURFDUERQV :KLOH SUHFHGHQW IURP WKH K\GURFDUERQ OLWHUDWXUH LQGLFDWHG GHVWDELOL]DWLRQ RI VXFK D WUDQVLWLRQ VWDWH E\ JURXSV VXEVWDQWLDOO\ ODUJHU WKDQ K\GURJHQ DW WKH =fWULHQH WHUPLQDO FLV SRVLWLRQV LW VHHPHG VXUSULVLQJ WKDW XSRQ VXEVWLWXWLRQ RI K\GURJHQ E\ IOXRULQH DW WKHVH SRVLWLRQV UDWKHU WKDQ REVHUYLQJ DQ KLJKHU HQHUJ\ GLVURWDWRU\ SURFHVV DOWHUQDWH UHDUUDQJHPHQWV ZHUH REVHUYHG ,W ZDV WKHQ WKH LQWHQWLRQ WR VWXG\ DQRWKHU V\VWHP ZLWK D OHVVHU GHJUHH RI IOXRULQDWLRQ UHDUUDQJLQJ IURP D VSHFLILF FRQIRUPDWLRQ ZKLFK ZRXOG DOORZ D

PAGE 89

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b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

PAGE 90

GHPRQVWUDWHG WKH H[FOXVLYH QDWXUH RI WKLV SURFHVV DQG HVWLPDWH WKH FKDLU LV IDYRUHG RYHU D ERDW FRQIRUPDWLRQ WUDQVLWLRQ VWDWH E\ DW OHDVW NFDOPRO LQ HQWKDOS\ 6HPLHPSLULFDO DQG PRUH UHFHQW DE LQLWLR OHYHO WKHRUHWLFDO VWXGLHV FRQILUP E\ VLPLODU EDUULHUV WKH H[SHULPHQWDO SUHIHUHQFH IRXQG IRU WKH FKDLU RYHU WKH ERDW WUDQVLWLRQ VWDWH FRQIRUPDWLRQ 7KH HQHUJ\ GLIIHUHQFH DQG KHQFH WKH H[FOXVLYH FKDLU WUDQVLWLRQ VWDWH IRU WKLV SURFHVV LV UDWLRQDOL]HG DV EHLQJ GXH WR D WKURXJK VSDFH GHVWDELOL]LQJ DQWLERQGLQJ LQWHUDFWLRQ EHWZHHQ RUELWDOV RQ & DQG & LQ WKH ERDW FRQIRUPDWLRQf $OWKRXJK WKHUH LV QR TXHVWLRQ DV WR WKH SUHIHUUHG FRQIRUPDWLRQ RI WKH WUDQVLWLRQ VWDWH WKH DVSHFW RI V\QFKURQLFLW\ RU ERQG WLPLQJ LQ WKLV FRQFHUWHG SURFHVV KDV EHHQ XQGHU FRQWLQXRXV GHEDWH 6XFK PHFKDQLVWLF ILQHSRLQWV ZLOO EH DGGUHVVHG ODWHU LQ GLVFXVVLRQ EXW DW WKLV SRLQW RQO\ WKH DVSHFW RI IDYRUHG FRQIRUPDWLRQ ZLOO EH FRQVLGHUHG 7KH &RSH V\VWHP DSSHDUV WR EH LGHDO IRU VWXG\ RI WKH HIIHFW RI WHUPLQDO IOXRULQDWLRQ DV WKH WUDQVLWLRQ VWDWH JHRPHWULHV )LJXUH f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

PAGE 91

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

PAGE 92

GLGHXWHUHRKH[DGLHQH )LJXUH f 7KH SDUWLDOO\ IOXRULQDWHG ( DQG =IOXRURKH[DGLHQH f DQG GLIOXRURKH[DGLHQH f WKHUPDO VWXGLHV KDG DOUHDG\ EHHQ UHSRUWHG LQ WKH OLWHUDWXUH ZLWK UHOLDEOH DFWLYDWLRQ SDUDPHWHUV 7R FRPSOHWH WKH VLPSOH KH[DGLHQH VHULHV UHTXLUHG V\QWKHVLV DQG WKHUPDO VWXG\ RI WHWUDIOXRURKH[DGLHQH f )LJXUH )OXRULQDWHG +H[DGLHQH &RSH 3URFHVVHV RI ,QWHUHVW 7KH H[SHULPHQWDO VWXG\ RI ERDW FRQVWUDLQHG &RSH V\VWHPV KDV UHFHLYHG D YDULHW\ RI LQWHUHVW DQG DJDLQ V\VWHPV ZHUH FKRVHQ IRU PHFKDQLVWLF QRYHOW\ DFWLYDWLRQ SDUDPHWHU UHOLDELOLW\ RI WKH UHSRUWHG K\GURFDUERQV DQG V\QWKHWLF VLPSOLFLW\ 7ZR K\GURFDUERQ V\VWHPV )LJXUH f ZKLFK KDYH EHHQ LQYHVWLJDWHG ZKHUH JHRPHWULFDO FRQVWUDLQWV IRUFH D ERDW FRQIRUPDWLRQ &RSH UHDUUDQJHPHQW DUH GLPHWK\OHQHF\FORKH[DQHVf VXFK DV DQG PHVR PHWK\OLGHQHF\FORSHQW\OfPHWK\OLGHQHF\FORSHQWDQH PHVRf $Q DUWLIDFW RI WKH V\QWKHWLF URXWH LQWR PHVR WKH G PHWK\OLGHQH F\FORSHQW\OfPHWK\OLGHQHF\FORSHQWDQH LVRPHU GO LV DOVR DIIRUGHG 7KLV

PAGE 93

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f KDV EHHQ UHSRUWHG DV KDV D VWXG\ RI WKH K\GURFDUERQ GO DQG

PAGE 94

PHVRELVPHWK\OHQHF\FORSHQWDQHV ^GO PHVRf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

PAGE 95

6\QWKHVLV DQG 7KHUPRO\VLV RI 7HUPLQDOO\ *HPGLIOXRULQDWHG 'LHQH 6\VWHPV 7HWUDIOXRURKH[DGLHQH f r7HWUDIOXRURKH[DFOLHQH f ZDV V\QWKHVL]HG LQ VL[ VWHSV IURP EXWDQHGLRO LQ DQ RYHUDOO LVRODWHG \LHOG RI b 7KH UHDFWLRQ VHTXHQFH LV LOOXVWUDWHG LQ )LJXUH >7HWUDK\GURS\UDQ\OfR[\@EXWDQDO f ZDV SUHSDUHG E\ D OLWHUDWXUH SURFHGXUH IURP EXWDQHGLRO LQ WZR VWHSV DQG VXEMHFWHG WR D :LWWLJW\SH IOXRURROHILQDWLRQ WR \LHOG >WHWUDK\GUR)S\UDQ \OfR[\@GLIOXRURSHQWHQH f 'HSURWHFWLRQ WR GLIOXRURSHQWHQRO f DQG S\ULGLQLXP GLFKURPDWH 3'&f R[LGDWLRQ \LHOGHG GLIOXRUR SHQWHQDO f :LWWLJW\SH IOXRURROHILQDWLRQ WKHQ DIIRUGHG WKH GHVLUHG WHWUDIOXRURKH[DGLHQH f ,QLWLDO DWWHPSWV WR REWDLQ WKURXJK :LWWLJ W\SH IOXRURROHILQDWLRQ RI EXWDQHGLDO GLG QRW DIIRUG DQ\ DPRXQW RI IOXRURROHILQ DQG ZDV QRW IXUWKHU SXUVXHG + 27+3 )LJXUH 6\QWKHVLV RI 7HWUDIOXRURKH[DGLHQH f 'XH WR DSSUHFLDEOH YRODWLOLW\ WKH WKHUPRO\VLV RI ZDV H[DPLQHG LQ WKH JDV SKDVH DV GHVFULEHG LQ $SSHQGL[ $ 4XDQWLWDWLYH FRQYHUVLRQ RI WR

PAGE 96

/Q>b@ r& r& r& r& r& r& 7HPSHUDWXUH rFf N [ VHFnf 5 s s s s s s NA&) A bA&) )LJXUH )LUVW2UGHU 5DWH 3ORWV DQG 5DWH &RQVWDQWV IRU 7KHUPRO\VLV RI 7HWUDIOXRURKH[DGLHQH f

PAGE 97

WHWUDIOXRUROKH[DGLHQH )LJXUH f ZDV REVHUYHG 7KH WKHUPRO\VLV ZDV H[DPLQHG DW VL[ WHPSHUDWXUHV IURP r& WR r& DQG WKH FRQYHUVLRQ ZDV REVHUYHG WR IROORZ ILUVWRUGHU NLQHWLFV ZLWK QR GHJUHH RI UHYHUVLELOLW\ REVHUYHG )LJXUH RIIHUV WKH ILUVWRUGHU SORWV DQG UDWH FRQVWDQWV IRU WKH WHPSHUDWXUHV H[DPLQHG 7KH DFWLYDWLRQ SDUDPHWHUV $+r $6rf IRU WKH F\FOL]DWLRQ ZHUH REWDLQHG N>$+@ >$60 XVLQJ WKH (\ULQJ H[SUHVVLRQ N f§ HA 57 9 5 UHDUUDQJHG WR WKH IRUP K /QN7f $+r57 $6r5 /Q^NKf ZKHUH N UDWH FRQVWDQW DW DEVROXWH WHPSHUDWXUH 7 N %ROW]PDQQ FRQVWDQW [ -.f K 3ODQFNnV FRQVWDQW [ -[Vf DQG 5 LGHDO JDV FRQVWDQW FDOPR,[.f $ OLQHDU OHDVW VTXDUHV UHJUHVVLRQ SORW RI /QN7fYHUVXV 7 DV LOOXVWUDWHG LQ )LJXUH \LHOGHG $+r s NFDOPRO DQG $6r s FDOPRO[GHJ IRU WKH &RSH UHDUUDQJHPHQW RI WR ZLWK WKH HUURUV UHSRUWHG DV RQH VWDQGDUG GHYLDWLRQ )LJXUH (\ULQJ 3ORW IRU 7KHUPRO\VLV RI 7HWUDIOXRURKH[DGLHQH f

PAGE 98

'LIOXRURPHWK\OLGHQHPHWKYOcGHQHFYFORKH[DQH 'LIOXRURPHWK\OLGHQHPHWK\OcGHQHF\FORKH[DQH f ZDV SUHSDUHG LQ WKUHH VWHSV IURP F\FORKH[DQHGLRQH PRQRHWK\OHQH NHWDO f LQ D b LVRODWHG \LHOG 7KH UHDFWLRQ VHTXHQFH LV LOOXVWUDWHG LQ )LJXUH &+f3&+%U Q%X/L 7+) r& mA&; bf b +6 6LOLFD *HO &+&, bf 31&+ff &)%U 7+) r&57 KU bf )LJXUH 6\QWKHVLV RI 'LIOXRURPHWK\OLGHQHPHWK\OLGHQHF\FORKH[DQH f 0HWK\OLGHQHF\FORKH[DQRQH HWK\OHQH NHWDO f ZDV SUHSDUHG IURP F\FORKH[DQHGLRQH PRQRHWK\OHQH NHWDO f E\ D :LWWLJ UHDFWLRQ WKHQ GHSURWHFWHG WR \LHOG PHWK\OLGHQHF\FORKH[DQRQH f 7KLV PDWHULDO ZDV VXEMHFWHG WR :LWWLJW\SH IOXRURROHILQDWLRQ WR \LHOG WKH GHVLUHG 'XH WR DSSUHFLDEOH YRODWLOLW\ WKH WKHUPRO\VLV RI ZDV H[DPLQHG LQ WKH JDV SKDVH DV GHVFULEHG LQ $SSHQGL[ $ 4XDQWLWDWLYH FRQYHUVLRQ RI WR GLIOXRURGLPHWK\OLGHQHF\FORKH[DQH )LJXUH f ZDV REVHUYHG 7KH WKHUPRO\VLV ZDV H[DPLQHG DW VL[ WHPSHUDWXUHV IURP r& WR r& 7KH FRQYHUVLRQ ZDV REVHUYHG WR IROORZ ILUVWRUGHU NLQHWLFV DQG QR GHJUHH RI UHYHUVLELOLW\ ZDV REVHUYHG )LJXUH RIIHUV WKH ILUVWRUGHU SORWV DQG UDWH FRQVWDQWV IRU WKH WHPSHUDWXUHV H[DPLQHG

PAGE 99

7HPSHUDWXUH r&f N [V VHFf 5 s s s s s s FI $ AA&) )LJXUH )LUVW2UGHU 3ORWV DQG 5DWH &RQVWDQWV IRU 7KHUPRO\VLV RI 'LIOXRURPHWK\OLGHQHPHWK\OLGHQHF\FORKH[DQH f r& r& r& r& r& r&

PAGE 100

$ OLQHDU UHJUHVVLRQ SORW RI /QN7fYHUVXV 7 )LJXUH f DV GHVFULEHG LQ WKH FDVH RI \LHOGHG $+r s NFDOPRO DQG $6r s FDOPRO[GHJ IRU WKH &RSH UHDUUDQJHPHQW RI WR )LJXUH (\ULQJ 3ORW IRU 7KHUPRO\VLV RI 'LIOXRURPHWK\OLGHQH PHWK\OLGHQHF\FORKH[DQH f 'LIGLIOXRURPHWKYOLGHQHFYFORKH[DQH 'LGLIOXRURPHWK\OLGHQHfF\FORKH[DQH f ZDV V\QWKHVL]HG LQ RQH VWHS )LJXUH f IURP F\FORKH[DQHGLRQH f E\ D :LWWLJW\SH IOXRURROHILQDWLRQ DQG LVRODWHG LQ DQ b \LHOG 31&+ff &)%U 7+) r&57 KU FS &)R bf )LJXUH 6\QWKHVLV RI 'LGLIOXRURPHWK\OLGHQHfF\FORKH[DQH f

PAGE 101

7HPSHUDWXUH r&f N [,2 VHFf 5 s s s s s s FI FI r& r& r& r& r& r& )LJXUH )LUVW2UGHU 3ORWV DQG 5DWH &RQVWDQWV IRU 7KHUPRO\VLV RI 'LGLIOXRURPHWK\OLGHQHfF\FORKH[DQH f

PAGE 102

'XH WR DSSUHFLDEOH YRODWLOLW\ WKH WKHUPRO\VLV RI ZDV H[DPLQHG LQ WKH JDV SKDVH DV GHVFULEHG LQ $SSHQGL[ $ 4XDQWLWDWLYH FRQYHUVLRQ RI WR WHWUDIOXRURGLPHWK\OLGHQHF\FORKH[DQH )LJXUH f ZDV REVHUYHG 7KH WKHUPRO\VLV ZDV H[DPLQHG DW VL[ WHPSHUDWXUHV IURP r& WR r& 7KH FRQYHUVLRQ ZDV REVHUYHG WR IROORZ ILUVWRUGHU NLQHWLFV DQG QR GHJUHH RI UHYHUVLELOLW\ ZDV REVHUYHG )LJXUH VKRZV WKH ILUVWRUGHU SORWV DQG UDWH FRQVWDQWV IRU WKH WHPSHUDWXUHV H[DPLQHG $ OLQHDU UHJUHVVLRQ SORW RI /QN7fYHUVXV 7 DV GHVFULEHG LQ WKH FDVH RI \LHOGHG $+r s NFDOPRO DQG $6r s FDOPRO[GHJ IRU WKH &RSH UHDUUDQJHPHQW RI WR )LJXUH (\ULQJ 3ORW IRU 7KHUPRO\VLV RI 'LGLIOXRURPHWK\OLGHQHf F\FORKH[DQH f

PAGE 103

PHVR DQG F+'LIOXRURPHWKYOLGHQHF\FORSHQW\KGLIOXRURPHWK\OLGHQH FYFORSHQWDQH URHVR Gf $IHVR DQG FI ZHUH SUHSDUHG LQ IRXU VWHSV DQG LVRODWHG LQ b RYHUDOO \LHOG DV LOOXVWUDWHG LQ )LJXUH &KORURF\FORSHQWDQRQH ZDV DGGHG WR WKH VRGLXP HQRODWH RI HWK\O R[RF\FORSHQWDQHFDUER[\ODWH f DQG WKH UHVXOWDQW PDWHULDO GHFDUER[\ODWHG XQGHU DFLG FDWDO\VLV WR \LHOG R[RF\FORSHQW\OfF\FORSHQWDQRQH f 7KLV PDWHULDO ZDV VXEMHFWHG WR :LWWLJ W\SH IOXRURROHILQDWLRQ WR \LHOG GLIOXRURPHWK\OLGHQHF\FORSHQW\Of GLIOXRURPHWK\OLGHQHF\FORSHQWDQH f LQ D UDWLR RI GM WR PHVR 'XH WR f 1Dr WROXHQH $ f FKORURF\FORSHQWDQRQH f +&, +S2 (W2+ bf 31&+ff f &)%U f 7+) r&57 KU bf G PHVR )LJXUH 6\QWKHVLV RI PHVR DQG G!'LIOXRURPHWK\OLGHQHF\FORSHQW\Of GLIOXRURPHWK\OLGHQHF\FORSHQWDQH PHVR FIf LQVXIILFLHQW YDSRU SUHVVXUH DW WKH RSHUDWLQJ FRQGLWLRQV RI WKH JDV NLQHWLFV OLQH DQG SUREOHPV ZLWK FRQGHQVDWLRQ RI WKH PDWHULDO RQ FRRO OLQH VHFWLRQV DQG MRLQWV LW ZDV QHFHVVDU\ WR VWXG\ WKH WKHUPRO\VLV RI LQ VROXWLRQ $ 0 VROXWLRQ RI ZDV SUHSDUHG LQ QGRGHFDQH DQG WKH H[WHQW RI FRQYHUVLRQ ZDV IROORZHG YHUVXV LQWHUQDO VWDQGDUG E\ ) 105 7KH WHPSHUDWXUHV QHFHVVDU\ WR DIIRUG WKH UHDUUDQJHPHQW RI PHVR ZHUH URXJKO\ r& KLJKHU WKDQ WKRVH UHTXLUHG IRU UHDUUDQJHPHQW RI FI 7KLV DOORZHG WKH PL[WXUH RI GLDVWHUHRPHUV WR EH WKHUPRO\]HG DQG NLQHWLFV REVHUYHG LQGHSHQGHQWO\ 'LVDSSHDUDQFH RI WKH GO PDWHULDO ZDV VWXGLHG ILUVW DW D ORZHU WHPSHUDWXUH IROORZHG E\ KLJKHU WHPSHUDWXUH VWXG\ RI WKH UHDUUDQJHPHQW RI WKH PHVR PDWHULDO WKXV HQDEOLQJ WZR UDWH FRQVWDQWV WR EH REWDLQHG IURP RQH VDPSOH 'XH WR GLIILFXOWLHV ZLWK WKH

PAGE 104

DSSDUDWXV DQG WLPH LQYROYHG IRU WKH TXDQWLWDWLYH 105 REVHUYDWLRQV D OLPLWHG QXPEHU RI WHPSHUDWXUHV ZHUH XWLOL]HG IRU WKHVH V\VWHPV 4XDQWLWDWLYH FRQYHUVLRQ RI GO WR F\FORSHQWHQ\OfWHWUDIOXRURHWK\Of F\FORSHQWHQH )LJXUH f ZDV REVHUYHG 7KH WKHUPRO\VLV RI GO ZDV H[DPLQHG DW IRXU WHPSHUDWXUHV IURP r& WR r& 7UDQVIRUPDWLRQ RI PHVR WR ZDV REVHUYHG DW WKUHH WHPSHUDWXUHV IURP r& WR r& 6PDOO DPRXQWV bf RI XQLGHQWLILHG PDWHULDOV ZHUH REVHUYHG E\ ) 105 DIWHU ORQJHU SHULRGV RI WLPH DW WKHVH HOHYDWHG WHPSHUDWXUHV &RQYHUVLRQV RI ERWK FI DQG PHVR ZHUH REVHUYHG WR IROORZ ILUVWRUGHU NLQHWLFV DQG QR H[WHQW RI UHYHUVLELOLW\ ZDV REVHUYHG )LJXUHV FIf DQG PHVRf VKRZ WKH ILUVWRUGHU SORWV DQG UDWH FRQVWDQWV IRU WKH WHPSHUDWXUHV H[DPLQHG /LQHDU UHJUHVVLRQ SORWV RI /QN7fYHUVXV 7 DV GHVFULEHG LQ WKH FDVH RI \LHOGHG $+r s NFDOPRO DQG $6r s FDOPRO GHJ IRU WKH &RSH UHDUUDQJHPHQW RI FI WR )LJXUH f DQG $+r s NFDOPRO DQG $6r s FDOPRO[GHJ IRU WKH UHDUUDQJHPHQW RI PHVR WR )LJXUH f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

PAGE 105

/Q>b@ r& r& r& r& 7HPSHUDWXUH r&f N [ VHFnf 5 s s s s )LJXUH )LUVW2UGHU 3ORWV DQG 5DWH &RQVWDQWV IRU 7KHUPRO\VLV RI 'LIOXRURPHWK\OLGHQHF\FORSHQW\OfGLIOXRURPHWK\OLGHQHF\FORSHQWDQH ^GOf

PAGE 106

/Q>b7HVR@ r& r& r& 7HPSHUDWXUH rFf N [O V VHFf 5 s s s PHVR )LJXUH )LUVW2UGHU 3ORWV DQG 5DWH &RQVWDQWV IRU 7KHUPRO\VLV RI PHVR 'LIOXRURPHWK\OLGHQHF\FORSHQW\OfGLIOXRURPHWK\OLGHQHF\FORSHQWDQH PHVR f

PAGE 107

7 )LJXUH (\ULQJ 3ORW IRU 7KHUPRO\VLV RI G'LIOXRURPHWK\OLGHQHF\FOR SHQW\OfGLIOXRURPHWK\OLGHQHF\FORSHQWDQH ^GOf 7 )LJXUH (\ULQJ 3ORW IRU 7KHUPRO\VLV RI PHVR'LIOXRURPHWK\OLGHQH F\FORSHQW\OfGLIOXRURPHWK\OLGHQHF\FORSHQWDQH PHVRf

PAGE 108

PRQRIOXRULQDWLRQ LQ WKH FKDLU SURFHVV :LWKLQ WKH HUURU RI WKH PHDVXUHPHQWV WKH DFWLYDWLRQ HQWKDOS\ DQG HQWURS\ UHPDLQ XQFKDQJHG IURP WKH K\GURFDUERQYDOXHV LQ WKH PRQRIOXRULQDWHG FDVHV DQG 7KH JHP GLIOXRUR V\VWHP RFFXUV ZLWK D NFDOPRO GHFUHDVH LQ $+r EXW QR VLJQLILFDQW FKDQJH LQ $6r UHODWLYH WR WKH K\GURFDUERQ 7ZR WHUPLQDO JHP GLIOXRUR JURXSV GHFUHDVH $+r E\ NFDOPRO IURP WR DQG NFDOPRO IURP FI WR G 7KHUH LV DOVR D PDUNHG GLIIHUHQFH LQ WKH DFWLYDWLRQ HQWURS\ IRU WKHVH WZR UHODWHG SURFHVVHV $6r GHFUHDVHV E\ FDOPRO[GHJ IURP WR DQG FDOPRO[GHJ IURP G WR FI )LJXUH LOOXVWUDWHV GDWD IRU K\GURFDUERQ DQG WHUPLQDOO\ IOXRULQDWHG GLHQH V\VWHPV IURP WKLV VWXG\ DQG OLWHUDWXUH FRQVWUDLQHG WR ERDW WUDQVLWLRQ VWDWH &RSH UHDUUDQJHPHQWV 7KH GLPHWK\OHQHF\FORKH[DQH V\VWHP H[KLELWV DQ LQLWLDO NFDOPRO GHFUHDVH LQ $+r DQG FDOPRO[GHJ GHFUHDVH LQ $6r XSRQ LQWURGXFWLRQ RI RQH WHUPLQDO JHPGLIOXRURPHWK\OHQH JURXS YHUVXV f *HPGLIOXRULQDWLRQ DW ERWK WHUPLQL f VKRZV QR FKDQJH LQ $+r IURP WKH KDOI IOXRULQDWHG V\VWHP f EXW $6r GHFUHDVHV E\ FDOPRO[GHJ 7KH IOXRULQDWHG PHVRELVPHWK\OHQHF\FORKH[DQH V\VWHP PHVR H[KLELWV LQFUHDVHV LQ $+r RI NFDOPRO DQG $6r RI NFDOPRO[GHJ YHUVXV WKH K\GURFDUERQ PHVR :KLOH GLVFXVVLQJ WKH NLQHWLF HIIHFWV RI IOXRULQDWLRQ RQ WKHVH V\VWHPV LW LV LPSRUWDQW WR NHHS LQ PLQG WKH IDVKLRQ LQ ZKLFK WHUPLQDO IOXRULQDWLRQ ZLOO LQIOXHQFH WKH WKHUPRG\QDPLFV RI WKHVH &RSH SURFHVVHV 7KH GHJHQHUDF\ RI WKH SURFHVV LQ KH[DGLHQH DQG GLPHWK\OHQHF\FORKH[DQH OHDGV WR QR QHW HQWKDOS\ FKDQJH XSRQ UHDUUDQJHPHQW DOWKRXJK WKH GHXWHUDWHG PDWHULDOV f XVHG WR UHPRYH WKH GHJHQHUDF\ GLG H[KLELW .HTL}Ff DQG .HT r UHVSHFWLYHO\ GXH WR VHFRQGDU\ LVRWRSH HIIHFWV 7KH K\GURFDUERQ ELV PHWK\OHQHF\FORSHQWDQH f ZDV QRW REVHUYHG WR EH UHYHUVLEOH WR DQ\ H[WHQW

PAGE 109

LAFI A&) + +, G AA&) b) [ FU $+r NFDOPROf s 5HIHUHQFHV f G DQG $6r FDOPRO[GHJf s G$ 7KLV VWXG\ )LJXUH $FWLYDWLRQ 3DUDPHWHUV IRU &KDLU 7UDQVLWLRQ 6WDWH &RSH 3URFHVVHV

PAGE 110

$6r FDOPRO[GHJf s s s s s 5HIHUHQFHV PHVR $OO RWKHUV QHVRf IURP WKLV VWXG\ )LJXUH $FWLYDWLRQ 3DUDPHWHUV IRU %RDW 7UDQVLWLRQ 6WDWH &RSH 3URFHVVHV

PAGE 111

LQGLFDWLQJ $+ NFDOPRO IRU } GXH WR WKH IRUPDWLRQ RI PRUH VXEVWLWXWHG ROHILQV )URP WKH HDUOLHU GLVFXVVLRQ &KDSWHU f SHUWDLQLQJ WR IOXRULQHfV WKHUPRG\QDPLF SUHIHUHQFH WR EH ERQGHG WR VDWXUDWHG FDUERQ LW LV H[SHFWHG WKDW VXFK D IDFWRU ZLOO LPSDUW DQ\ZKHUH IURP WR NFDOPRO H[RWKHUPLFLW\ WR WKH FKDLU RU ERDW W\SH F\FOL]DWLRQV IRU HDFK SHPGLIOXRURROHIOQ ,Q IDFW F\FOL]DWLRQ RI f§! ZDV REVHUYHG WR KDYH $+ NFDOPRO $V PLJKW EH H[SHFWHG WKH FRQYHUVLRQV RI } DQG FI! DUH QRW UHYHUVLEOH WR DQ\ H[WHQW LQ OLQH ZLWK VLPSOH DGGLWLYLW\ RI WKH DERYH LQGLFDWHG H[RWKHUPLFLWLHV IRU WZR VXFK JHPGLIOXRUR JURXSV $ VLPLODU VLWXDWLRQ LV REVHUYHG IRU WKH ERDW FRQVWUDLQHG V\VWHPV LQ )LJXUH :LWK WKH SUHFHGHQW VHW IRU LQFUHDVLQJ H[RWKHUPLFLW\ LQ HDFK RI WKHVH &RSH VHULHV DV WKH GHJUHH RI WHUPLQDO JHPGLIOXRULQDWLRQ LV LQFUHDVHG LW LV QRW VXUSULVLQJ WKDW WKH VHULHV RI IOXRULQDWHG FKDLU &RSH SURFHVVHV H[DPLQHG VKRZ D VWHDG\ GHFUHDVH LQ $+r DV WKH QXPEHU RI WHUPLQDO JHPGLIOXRUR JURXSV LQFUHDVHV 6XFK D WUHQG LV LQ OLQH ZLWK WKH +DPPRQG 3RVWXODWHf LQ WKDW DQ LQFUHDVLQJO\ H[RWKHUPLF SURFHVV ZLOO OHDG WR DQ HDUOLHU WUDQVLWLRQ VWDWH RQH EHLQJ PRUH UHDFWDQWOLNH LQ VWUXFWXUH DQG HQHUJ\ $Q\ VWHULF HIIHFW WKDW IOXRULQH LPSDUWV RQ WKH FKDLU WUDQVLWLRQ VWDWH )LJXUH f PXVW WKHQ EH PLQLPDO RU QRQn H[LVWHQW DV LQFUHDVHG IOXRULQDWLRQ VKRZHG RQO\ LQFUHPHQWDO GHFUHDVHV LQ $+r 7KH WUHQG RI GHFUHDVLQJ DFWLYDWLRQ HQWKDOSLHV EDVHG RQ FKDQJLQJ UHODWLYH WKHUPRG\QDPLFV ZLWK LQFUHDVLQJ GHJUHH RI WHUPLQDO JHPGLIOXRULQDWLRQ ZRXOG EH H[SHFWHG WR EH REVHUYHG LQ WKH ERDW FRQVWUDLQHG &RSH V\VWHPV DV LW ZDV LQ WKH FKDLU V\VWHPV LI WKHUH ZDV QR GHWULPHQWDO VWHULF LQIOXHQFH GXH WR IOXRULQH 7KH VHULHV RI WHUPLQDOO\ IOXRULQDWHG GLPHWK\OHQHF\FORKH[DQHV )LJXUH f VHHPV WR EH VKRZLQJ D EDODQFH EHWZHHQ WKHUPRG\QDPLF EDVHG $+I ORZHULQJ DQG D NLQHWLF GHVWDELOL]DWLRQ RI WKH WUDQVLWLRQ VWDWH DV WKH GHJUHH RI WHUPLQDO ROHILQ JHPGLIOXRULQDWLRQ LQFUHDVHV 7KH DFWLYDWLRQ HQWKDOS\ GHFUHDVHV

PAGE 112

IURP WR DQG GRHV QRW FKDQJH IURP WR LPSO\LQJ WKDW WKH WUDQVLWLRQ VWDWH LQYROYLQJ FRSODQDU HFOLSVHG DSSURDFK RI WKH WHUPLQDO FDUERQV )LJXUH f LV HQFRXQWHULQJ VRPH UHVLVWDQFH 3K\VLFDO RYHUODS RI WKH IOXRULQHV LV XQOLNHO\ LQ WKLV FDVH DQG UHVLVWDQFH ZRXOG PRVW OLNHO\ DULVH IURP GLIOXRURROHILQ GLSROH RU ILHOG UHSXOVLRQV ,W LV PRUH OLNHO\ WKRXJK WKDW WKH GHFUHDVH LQ DFWLYDWLRQ HQWURS\ IURP WR PD\ H[SODLQ WKH IDFW WKDW $+r LV FRQVWDQW EHWZHHQ WKHVH WZR V\VWHPV 7KH GHFUHDVH LQ DFWLYDWLRQ HQWURS\ LV FRQVLVWHQW ZLWK D KLJKHU GHJUHH RI ERQG IRUPDWLRQ EHWZHHQ WKH WHUPLQDO GLHQH FDUERQV ZLWK PLQLPDO && D ERQG FOHDYDJH DW WKH WUDQVLWLRQ VWDWH RI ,Q HIIHFW WKLV LV D KLJKHU GHJUHH RI ELF\FOR>@RFWDQHGL\O FKDUDFWHU ZKLFK ZRXOG LPSDUW PRUH VWUDLQ WR WKH WUDQVLWLRQ VWDWH LQ WKH WHWUDIOXRULQDWHG f YHUVXV WKH GLIOXRULQDWHG f FDVH ,I WKLV LQFUHDVH LQ VWUDLQ ZDV LQIOXHQFLQJ WKH WUDQVLWLRQ VWDWH HQHUJ\ LQ D VLPLODU PDJQLWXGH DV WKH VWDELOL]LQJ HIIHFW RI VDWXUDWLRQ RI WKH DGGLWLRQDO GLIOXRURPHWK\OHQH JURXS WKHQ DV REVHUYHG RQH ZRXOG H[SHFW QR QHW FKDQJH LQ WKH YDOXH RI $+r WR RFFXU EHWZHHQ DQG ,Q PHVR GLI,XRURPHWK\OLGHQHF\FORSHQW\OfGLIOXRURPHWK\OLGHQH F\FORSHQWDQH PHVRf WKH WUXH ERDW FRQIRUPDWLRQ )LJXUH f DOORZV IRU VLJQLILFDQW WZLVWLQJ LQ RI WZR WHUPLQDO FnV VXEVWLWXHQWV 7KH NFDOPRO LQFUHDVH LQ $+r EHWZHHQ PHVR DQG PHVR LV EHOLHYHG WR EH GXH WR VWURQJ UHSXOVLRQ EHWZHHQ WKH WZR WHUPLQDO FLV IOXRULQHV GLUHFWHG DW RQH DQRWKHU ,W LV DOVR SRVVLEOH WKDW WKLV LQFUHDVH PD\ EH H[SODLQHG E\ D FRSODQDU DSSURDFK RI WKH WHUPLQDO ROHILQLF FDUERQV FUHDWLQJ UHSXOVLRQ EHWZHHQ K\GURJHQV HQGR RQ WKH WZR F\FORSHQW\O ULQJV ,W LV GLIILFXOW WR SRVWXODWH ZKLFK VLWXDWLRQ ZLOO RFFXU LQ WKH WUDQVLWLRQ VWDWH RI PHVR (LWKHU ZD\ WKH ODUJH LQFUHDVH LQ $+r EHWZHHQ PHVR DQG PHVR LQGLFDWHV WKDW WHUPLQDO FnVIOXRULQDWLRQ FUHDWHV VLJQLILFDQW UHVLVWDQFH WR DSSURDFK RI WHUPLQDO ROHILQLF FDUERQV WKURXJK D ERDW FRQIRUPDWLRQ WUDQVLWLRQ VWDWH 7KH DFWLYDWLRQ HQWKDOS\ DQG HQWURS\ IRU WKLV

PAGE 113

UHDUUDQJHPHQW DUH WKH KLJKHVW RI WKH ERDW &RSH V\VWHPV REVHUYHG 7KHVH HQHUJ\ SDUDPHWHUV DUH FRQVLVWHQW ZLWK D QHDUGLVVRFLDWLYH PHFKDQLVP LQYROYLQJ FOHDYDJH RI WKH GLHQH && ERQG ERQG D LQ PHVR )LJXUH f WR IRUP D SDLU RI DOO\O UDGLFDOV f ZKLFK PD\ UHFRPELQH WR IRUP WKH REVHUYHG SURGXFW RU SRWHQWLDO >@VKLIW DGGXFW 7KH GLVVRFLDWLRQ HQHUJ\ $+rGf IRU ERQG D LQ WKLV V\VWHP PD\ EH HVWLPDWHG E\ VXEWUDFWLQJ $+rI NFDOPRO IRU GLPHWK\OKH[DGLHQH IURP WZLFH WKH KHDW RI IRUPDWLRQ RI EXWHQH\O [ $+rI NFDOPROff 7KLV \LHOGV $+rG r NFDOPRO IRU FOHDYDJH RI WKLV V\VWHP WR D SDLU RI DOO\OLF UDGLFDOV f 6XFK DQ DSSUR[LPDWLRQ LV YDOLG DV HDFK ILYH PHPEHUHG ULQJ LV ERQGHG WR D QRGDO FDUERQ LQ WKH DOO\OLF V\VWHP DQG JHPGLIOXRULQDWLRQ KDV OLWWOH HIIHFW RQ WKH VWDELOLW\ RI DQ DOO\OLF UDGLFDO )LJXUH f )LJXUH 7KHUPDO 5HDUUDQJHPHQW RI PHVR'LIOXRURPHWK\OLGHQH F\FORSHQW\OfGLIOXRURPHWK\OLGHQHF\FORSHQWDQH PHVROf 7KLV H[FHUFLVH LQGLFDWHV WKDW WKH REVHUYHG SURFHVV LV RFFXUULQJ ZLWK DQ DFWLYDWLRQ HQWKDOS\ NFDOPRO EHORZ WKDW QHFHVVDU\ IRU FOHDYDJH RI PHVR WR WKH K\SRWKHWLFDO SDLU RI DOO\O UDGLFDOV f 7KLV GLIIHUHQFH FDQ EH WKRXJKW RI DV WKH HQHUJ\ RI FRQFHUW IRU WKLV ERDW FRQIRUPDWLRQ &RSH SURFHVV

PAGE 114

7KH DFWLYDWLRQ HQWURSLHV IRU ERWK WKH FKDLU DQG ERDW &RSH SURFHVVHV DUH REVHUYHG WR EHFRPH LQFUHDVLQJO\ QHJDWLYH DV WKH QXPEHU RI JHPGLIOXRUR JURXSV LQFUHDVHV )LJXUHV DQG f H[FHSW DV GLVFXVVHG LQ WKH FDVH RI PHVR 7KH KH[DGLHQH V\VWHPV IURP K\GURFDUERQ WR WHUPLQDOO\ JHP GLIOXRULQDWHG FDVHV DQG f VKRZ VLPLODU $6r YDOXHV ZLWKLQ WKH PHDVXUHG HUURUV %HWZHHQ GLIOXRURKH[DGLHQH DQG WHWUDIOXRURKH[DGLHQH DQG f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r NFDOPRO WKH F\FORKH[DQHGL\O WUDQVLWLRQ VWDWH LV HVWLPDWHG WR EH NFDOPRO

PAGE 115

KLJKHU LQ HQHUJ\ WKDQ WKH FRQFHUWHG VWUXFWXUH DQG LQDFFHVVLEOH WR VLPSOH DON\O VXEVWLWXWHG KH[DGLHQHV 7KLV IDFW KDV EHHQ FRXQWHUHG H[WHQVLYHO\ E\ 'HZDUf ZKR WKURXJK WKHRUHWLFDO DE LQLWLR OHYHO VWXG\ KDV DUJXHG WKH PHFKDQLVP RI WKH ERDW DQG FKDLU SURFHVVHV DUH GLIIHUHQW 'HZDU PDNHV FODLP WKDW WKH ERDW SURFHVVHV ZRXOG EH IRUPDOO\ FRQFHUWHG DQG WKH FRQFHUWHG FKDLU SURFHVVHV DUH DFWXDOO\ RFFXUULQJ WKURXJK D F\FORKH[DQHGL\O ZKLFK LQYROYHV VWURQJ WKURXJK ERQG FRXSOLQJ PDNLQJ WKH WUDQVLWLRQ VWDWH EHKDYH OLNH D FORVHG VKHOO VSHFLHV ,Q FRQWUDVW WKHUH DUH WKRVH ZKR DUJXH LQ IDYRU RI WKH KLVWRULFDO FRQFHUWHG SURFHVV VXFK DV +RXN ZKR VWXGLHG WKH V\VWHP DW WKH DE LQLWLR OHYHO DQG FRQFOXGHG FRQFHUWHG ERQG UHRUJDQL]DWLRQ LV RFFXUULQJ LQ WKH WUDQVLWLRQ VWDWH $OWKRXJK GLVDJUHHPHQW LV REVHUYHG HYHQ ZLWK KLJK OHYHOV RI WKHRU\ WKHVH DXWKRUV DUH FRQVLVWHQW LQ DJUHHLQJ WKDW WKH PHFKDQLVP RI WKH &RSH SURFHVV ZLOO YDU\ VWURQJO\ DFURVV WKH SRVVLEOH DOO\O GLUDGLFDOFRQFHUWHG F\FORKH[DQHGL\O VSHFWUXP GHSHQGLQJ RQ WKH HOHFWURQLF QDWXUH RI VXEVWLWXHQWV DQG WKHLU SRVLWLRQ RI SODFHPHQW XSRQ WKH GLHQH V\VWHP 7KH H[WHQW RI ERQG PDNLQJ DQG ERQG EUHDNLQJ LQ WKH &RSH UHDUUDQJHPHQW KDV EHHQ SUREHG E\ REVHUYLQJ VHFRQGDU\ GHXWHULXP LVRWRSH HIIHFWV LQ VXEVWLWXWHG GLHQHVn )URP WKHVH UHVXOWV LW LV JHQHUDOO\ DJUHHG WKDW UDGLFDO VWDELOL]LQJ VXEVWLWXHQWV DW & DQG & OHDG WR LQFUHDVHG ERQG RUGHU EHWZHHQ & DQG & LQ OLQH ZLWK D F\FORKH[DQHGL\O W\SH VWUXFWXUH DQG VXFK VXEVWLWXHQWV DW & DQG & OHDG WR WUDQVLWLRQ VWDWHV ZKLFK PRUH UHVHPEOH D SDLU RI DOO\O UDGLFDOV 7KH QRWLRQ RI WKH F\FORKH[DQHGL\O KDV EHHQ IXUWKHU SUREHG E\ FRPSDULVRQ RI WKH WKHUPDO FKHPLVWU\ RI GLSKHQ\OKHSWDGLHQH f DQG GLSKHQ\OKH[DGLHQH& f +HSWDGLHQH ZDV WHUPHG D IUXVWUDWHG &RSH V\VWHP DV LW FRQWDLQV DQ DGGLWLRQDO PHWK\OHQH XQLW PDNLQJ D FRQFHUWHG SURFHVV LPSRVVLEOH DQG RIIHULQJ D FKDQFH WR SUREH WKH GLUDGLFDO )RU LW ZDV IRXQG WKDW $+r s NFDOPRO DQG

PAGE 116

FK &+ FK FK )LJXUH 7KHUPDO 5HDUUDQJHPHQWV RI 'LSKHQ\OKHSWDGLHQH f DQG 'LSKHQ\OKH[DGLHQH& f $6r s FDOPRO[GHJ DQG IRU LW ZDV IRXQG WKDW $+r s NFDOPRO DQG $6r s FDOPRO[GHJ )URP WKLV GDWD DQG LPSURYHG 00 IRUFH ILHOG FDOFXODWLRQV LW ZDV FRQFOXGHG WKDW E\ LQWURGXFWLRQ RI EHQ]\OOLF UHVRQDQFH LQWR WKH F\FORKH[DQHGL\O WKH GLUDGLFDO SURFHVV RFFXUV ZLWK DQ HQWKDOS\ RI DFWLYDWLRQ NFDOPRO EHORZ WKH FRQFHUWHG WUDQVLWLRQ VWDWH IRU KH[DGLHQH 5HFHQWO\ WKH >@VLJPDWURSLF UHDUUDQJHPHQW RI SHUIOXRURDOO\OYLQ\O HWKHU WR SHUIOXRURSHQWHQDO KDV EHHQ UHSRUWHG ZLWK DFWLYDWLRQ SDUDPHWHUV $+r NFDOPRO DQG $6r FDOPRO[GHJ ZKLFK GLIIHU VLJQLILFDQWO\ IURP WKH DQDORJRXV K\GURFDUERQ DOO\OYLQ\O HWKHU DFWLYDWLRQ SDUDPHWHUV RI $+r NFDOPRO DQG $6r FDOPRO[GHJ $ TXDOLWDWLYH VWXG\ )LJXUH f RI SHUIOXRURKH[DGLHQH f DQG SHUIOXRURFKORURKH[DGLHQH f KDV DOVR EHHQ UHFHQWO\ UHSRUWHG $W r& HTXLOLEUDWHV ZLWK ZLWK .HT } DQG DW WHPSHUDWXUHV JUHDWHU WKDQ r& LV IRUPHG TXDQWLWDWLYHO\

PAGE 117

) ) A )O \? &/ A ) R ) f§)r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f KDV OLPLWHG SUHFHGHQW LQ WKH SHUIOXRUR &ODLVHQ UHDUUDQJHPHQW RI SHUIOXRURDOO\OYLQ\O HWKHU DQG LV VLPLODU LQ WUHQG WR WKH & DQG & VXEVWLWXWHG K\GURFDUERQ &RSH V\VWHPV ZKLFK DUH DUJXHG WR SURFHHG WKURXJK F\FORKH[DQHGL\O W\SH LQWHUPHGLDWHV $ PHFKDQLVP LQYROYLQJ D SDLU RI DOO\OLF UDGLFDOV LV QRW FRQVLVWHQW ZLWK WKH REVHUYHG DFWLYDWLRQ SDUDPHWHUV DV DFWLYDWLRQ HQWURSLHV DQG HQWKDOSLHV ZRXOG EH H[SHFWHG WR EH ODUJHU WKDQ WKRVH

PAGE 118

RI FRUUHVSRQGLQJ K\GURFDUERQV XSRQ LQFUHDVLQJ IOXRULQDWLRQ DQG WKH VWDELOLW\ RI DQ DOO\O UDGLFDO LV NQRZQ WR EH LQVHQVLWLYH WR SDUWLDO IOXRULQDWLRQ )LJXUH f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

PAGE 119

WHUPLQDO FLV IOXRULQHV LQ WKLV FRQIRUPDWLRQ OHDGV WR KLJKO\ UHSXOVLYH LQWHUDFWLRQV ZKLFK JLYH ULVH WR DFWLYDWLRQ SDUDPHWHUV FRQVLVWHQW ZLWK D WUDQVLWLRQ VWDWH PRUH UHVHPEOLQJ D SDLU RI DOO\O UDGLFDOV LQYROYLQJ D KLJK GHJUHH RI && ERQG FOHDYDJH ZLWKRXW D VLPLODU GHJUHH RI && ERQG IRUPDWLRQ

PAGE 120

&+$37(5 (;3(5,0(17$/ *HQHUDO 0HWKRGV 1XFOHDU PDJQHWLF UHVRQDQFH 105f FKHPLFDO VKLIWV DUH UHSRUWHG LQ SDUWV SHU PLOOLRQ SSPf GRZQILHOG f IURP LQWHUQDO UHIHUHQFH 706 IRU + DQG & VSHFWUD DQG LQ SSP XSILHOG FSf IURP LQWHUQDO VWDQGDUG &)&, IRU ) VSHFWUD $OO 105 VSHFWUD ZHUH REWDLQHG RQ 9DUDQ 9;5 RU 9DUDQ ;/ LQVWUXPHQWV 7KH IRUPDW ILHOG VWUHQJWK VROYHQW UHIHUHQFHf LV LQFOXGHG IRU DOO 105 VSHFWUD UHSRUWHG *DV FKURPDWRJUDSKLF VHSDUDWLRQV ZHUH SHUIRUPHG E\ *DV/LTXLG 3KDVH &KURPDWRJUDSK\ */3&f RQ SDFNHG FROXPQV 4XDQWLWDWLYH */3& ZDV SHUIRUPHG RQ D +HZOHWW 3DFNDUG 6HULHV ,, JDV FKURPDWRJUDSK ZLWK D IODPH LRQL]DWLRQ GHWHFWRU DQG D +HZOHWW 3DFNDUG $ LQWHJUDWRU 3UHSDUDWLYH */3& ZDV SHUIRUPHG RQ D 9DUDQ $HURJUDSK $ JDV FKURPDWRJUDSK HTXLSSHG ZLWK D WKHUPDO FRQGXFWLYLW\ GHWHFWRU &RQGLWLRQV DQG FROXPQV XVHG DUH GLVFXVVHG LQ UHOHYDQW H[SHULPHQWDO VHFWLRQV 0DVV VSHFWUD DQG H[DFW PDVVHV ZHUH GHWHUPLQHG RQ D .UD\WRV$(, VSHFWURPHWHU DW HY 8OWUDYLROHW 89f VSHFWUD ZHUH REWDLQHG RQ DQ 3HUNLQ(OPHU /DPEGD 89$,61,5 VSHFWURSKRWRPHWHU 0HOWLQJ SRLQWV ZHUH REWDLQHG RQ D 7KRPDV +RRYHU 8QL0HOW FDSLOODU\ PHOWLQJ SRLQW DSSDUDWXV DQG DUH XQFRUUHFWHG

PAGE 121

([SHULPHQWDO WH[W GLVFXVVLQJ D GU\ VROYHQW LQGLFDWHV VXFK PDWHULDO ZDV SXULILHG GLVWLOOHGf RII RI WKH DSSURSULDWH GU\LQJ DJHQW DQG VWRUHG XQGHU DQ LQHUW DWPRVSKHUH 7KH IROORZLQJ VROYHQWV DQG GU\LQJ DJHQWV ZHUH XVHG GLPHWK\OIRUPDPLGH &D+ RU 32 r& PP +Jf WULJO\PH &D+ RU VRGLXP EHQ]RSKHQRQH NHW\O PP +Jf WHWUDK\GURIXUDQ VRGLXP EHQ]RSKHQRQH NHW\Of GLHWK\O HWKHU VRGLXP EHQ]RSKHQRQH NHW\Of QDONDQHV &D+f $OO RWKHU VSHFLDO SUHSDUDWLRQV DUH GLVFXVVHG LQ WKH DSSURSULDWH H[SHULPHQWDO VHFWLRQ ([SHULPHQWDO 3URFHGXUHV 3UHSDUDWLRQ RI %URPRQLWURSKHQDQWKUHQH f %URPRQLWURSKHQDQWKUHQH f ZDV SUHSDUHG E\ DGDSWDWLRQ RI D SURFHGXUH DV GHVFULEHG E\ &DOORZ DQG *XOODQG %URPRSKHQDQWKUHQH J [ 2n PROf ZDV GLVVROYHG LQ PO RI JODFLDO DFHWLF DFLG LQ D PO WKUHH QHFN URXQG ERWWRP IODVN HTXLSSHG ZLWK D PDJQHWLF VWLUUHU VWRSSHU DQG D FRQGHQVHU ZLWK D SLHFH RI SRO\HWK\OHQH WXELQJ IRU GLUHFWLQJ QLWURJHQ R[LGHV HYROYHG XS LQWR WKH KRRG PO RI DFHWLF DQK\GULGH ZDV DGGHG DQG WKH PL[WXUH ZDV ZDUPHG WR r& &RQFHQWUDWHG b POf QLWULF DFLG ZDV SODFHG LQ WKH DGGLWLRQ IXQQHO DQG DGGHG GURSZLVH ZLWK YLJRURXV VWLUULQJ RYHU PLQXWHV 8SRQ FRPSOHWLRQ RI DGGLWLRQ WKH PL[WXUH ZDV KHDWHG DW D JHQWOH UHIOX[ IRU KRXU $QDO\VLV RI WKH PL[WXUH E\ 7/& 0HUFN .LHVHOJHO ) JODVV EDFNHG SODWHVf LQ KH[DQHV &+&, VKRZHG HLJKW VSRWV 5I YDOXHV Z EURPRSKHQDQWKUHQHf Zf Vf Zf Pf Pf Zf Zf $IWHU WKH UHIOX[ SHULRG WKH UHDFWLRQ PL[WXUH ZDV DOORZHG WR FRRO WR URRP WHPSHUDWXUH DQG DQ DPRUSKRXV GHHS EULFNUHG VROLG IHOO RXW RI D VROXWLRQ RI WKH VDPH FRORU 7KLV PDWHULDO ZDV UHFU\VWDOOL]HG IURP DFHWRQH &&8 WKHQ WZLFH IURP PHWK\O HWK\O NHWRQH &U\VWDOOLQH LV DIIRUGHG SXUH IURP WKH ODVW UHFU\VWDOOL]DWLRQ LQ PHWK\O HWK\O NHWRQH DV J bf OLJKW \HOORZ QHHGOHV

PAGE 122

PHOWLQJ r& /LW r&f ZLWK 5I LQ WKH DERYH VROYHQW V\VWHP $ ILQH \HOORZ SUHFLSLWDWH ZDV REWDLQHG RXW RI WKH &&8 DQG ILUVW PHWK\O HWK\O NHWRQH ILOWUDWHV 5I ZHDNf DQG VWURQJf 2QH IXUWKHU UHFU\VWDOOL]DWLRQ IURP PHWK\O HWK\O NHWRQH \LHOGV J bf SDOH \HOORZ FU\VWDOV RI EURPR QLWURSKHQDQWKUHQH PHOWLQJ r& ZLWK 5I LQ WKH DERYH VROYHQW V\VWHP %URPRQLWURSKHQDQWKUHQH f + 105 0+] &'&, 706f P +f G ZLWK ILQH VSOLWWLQJ + -+K +] -+K +]f G + -++ +]f G + -++ +]f & 105 0+] &'&, 706f /RZ 5HVROXWLRQ 0DVV 6SHFWUXP P] b UHODWLYH LQWHQVLW\f f f f f f f f f f f f %URPRQLWURSKHQDQWKUHQH + 105 0+] &'&, 706f P +f G + -KK +]f V +f G + -+K +]f G + -KK +]f G + -++ +]f G + -++ +]f & 105 0+] &'&, 706f /RZ 5HVROXWLRQ 0DVV 6SHFWUXP P] b UHODWLYH LQWHQVLW\f f f f f f f f f f f f f 3UHSDUDWLRQ RI ORGRQLWUR'KHQDQWKUHQH %URPRQLWURSKHQDQWKUHQH J [f PROf GU\ 1DO J [ 2f PROf DQG PO RI '0) ZHUH FRPELQHG LQ D PO WKUHH QHFN URXQG ERWWRP IODVN HTXLSSHG ZLWK D PDJQHWLF VWLUUHU FRQGHQVHU DQG WZR VWRSFRFNV 7KH UHDFWLRQ PL[WXUH ZDV EURXJKW WR D JHQWOH UHIOX[ IRU KRXUV ZKLOH IROORZLQJ WKH UHDFWLRQ E\ 7/& 0HUFN .LHVHOJHO ) JODVV EDFNHG SODWHVf LQ

PAGE 123

KH[DQHV &+&, $IWHU KRXUV 7/& VKRZV RQH PDMRU DQG WZR PLQRU SURGXFWV 5I Vf Zf Pf EURPRQLWURSKHQDQWKUHQH KDV 5I LQ WKH VDPH V\VWHPf 7KH UHDFWLRQ PL[WXUH ZDV FRROHG DQG DGGHG WR D VHSDUDWRU\ IXQQHO FRQWDLQLQJ PO RI ZDWHU 7KH DTXHRXV PL[WXUH ZDV H[WUDFWHG ZLWK GLHWK\O HWKHU [ POf 7KH HWKHU H[WUDFWV ZHUH FRPELQHG DQG ZDVKHG ZLWK [ PO RI ZDWHU 7KH HWKHU VROXWLRQ ZDV GULHG RYHU DQK\GURXV 0J6 DQG GLVWLOOHG E\ URWDU\ HYDSRUDWRU WR \LHOG J bf EXUQWRUDQJH FU\VWDOV RI PHOWLQJ r& /LWr&f ORGRQLWURSKHQDQWKUHQH f + 105 0+] &'&, 706f P +f G ZLWK ILQH VSOLWWLQJ + -+K +] -+K +]f G + -+K +] -++ +]f G + -++ +]f & 105 0+] &'&, 706f /RZ 5HVROXWLRQ 0DVV 6SHFWUXP P] b UHODWLYH LQWHQVLW\f f f f f f f f f f f f (OHPHQWDO $QDO\VLV RQ &L+,1 &DOFXODWHG b & + 1 0HDVXUHG b & + 1 3UHSDUDWLRQ RI ORGRWULIOXRURHWKYOHQH ORGRWULIOXRURHWK\OHQH ZDV HLWKHU SXUFKDVHG IURP 3HQLQVXODU &KHPLFDOV 5HVHDUFK *DLQHVYLOOH )ORULGD RU SUHSDUHG E\ WKH PHWKRG RI +DQVHQ )ODPH GULHG DSSDUDWXV ZDV DVVHPEOHG XQGHU 1 SXUJH DV IROORZV OLWHU WKUHH QHFN URXQG ERWWRP IODVN ILWWHG ZLWK FROG ILQJHU FRQGHQVHU MDFNHWHG DGGLWLRQ IXQQHO VWRSSHU DQG PDJQHWLF VWLUUHU $FLG DFWLYDWHG ]LQF SRZGHU J PROf ZDV DGGHG WR WKH UHDFWLRQ YHVVHO IROORZHG E\ PO RI GU\ '0) %U)& &) J PROf ZDV FRQGHQVHG LQWR WKH GU\LFHLVRSURS\O DOFRKRO FRROHG MDFNHWHG DGGLWLRQ IXQQHO IURP D WDUHG 5RWDIORZ WXEH 7KH %U)& &) ZDV DGGHG

PAGE 124

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f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ƒ VLHYHV /RZ ERLOLQJ UHSRUWHG ERLOLQJ SRLQW RI r&f FOHDU OLTXLG J bf JUDGXDOO\ WXUQLQJ SLQN ZDV REWDLQHG ) 105 RI WKLV PDWHULDO LV FRQVLVWHQW ZLWK VDPSOHV REWDLQHG IURP 3HQLQVXODU &KHPLFDOV 5HVHDUFK *DLQHVYLOOH )ORULGD ORGRWULIOXRURHWKYOHQH ) 105 0+] &'&, &)&,f GG ) -II +] -FLV)) +]f GG ) -WUDQV)) +] -)I +]f GG ) -WUDQV)) +] -II +]f

PAGE 125

3UHSDUDWLRQ RI =QO)& &) DQG =Q&) &) =QO)& &) DQG =Q&) &)f VROXWLRQV ZHUH SUHSDUHG E\ WKH PHWKRG RI +HLQ]H DQG %XUWRQ $Q PO QHFN URXQG ERWWRP IODVN ZLWK D PDJQHWLF VWLUUHU VWRSSHU DQG VHSWXP ZDV IODPH GULHG XQGHU $U SXUJH $FLG DFWLYDWHG =Q SRZGHU J PROf ZDV DGGHG IROORZHG E\ PO RI GU\ WULJO\PH 7KH PL[WXUH ZDV VWLUUHG UDSLGO\ DQG FRROHG WR r& ,)& &) J [ 2n PROf ZDV DGGHG E\ FDQQXOD IURP D WDUHG ERWWOH $IWHU KRXUV VWLUULQJ DW URRP WHPSHUDWXUH WKH VROXWLRQ KDG WXUQHG D PDSOH V\UXS EURZQ IURP LQLWLDOO\ FOHDU DQG FRORUOHVV 7KH \LHOG EDVHG RQ VWDUWLQJ ,)& &) E\ ) 105 YHUVXV LQWHUQDO VWDQGDUGf LV b DQG WKH UDWLR RI PRQR WR EVWULIOXRURHWKHQ\OVXEVWLWXWHG =Q UHDJHQW LV =QO)& &)e DQG =Q&) &)f ) 105 0+] WULJO\PH &)&,f PRQR GG ) -II +] -FVII +]f GG ) -UDQV)) +] -II +]f GG ) -UDQV)) +] -)) +]f ELV GG ) -FcV)) +] -II +]f GG ) -UDQ6)) +] -)) +]f GG ) -UDQV)) +] -)I +]f 3UHSDUDWLRQ RI %LVWULIOXRURHWKHQYKRKHQDQWKUHQH ELVWULIOXRURHWKHQ\OfSKHQDQWKUHQH f ZDV SUHSDUHG E\ DGDSWDWLRQ RI D SURFHGXUH DV GHVFULEHG E\ +HLQ]H DQG %XUWRQ $SSDUDWXV DV IROORZV ZDV IODPH GULHG XQGHU 1 SXUJH PO WKUHH QHFN URXQG ERWWRP IODVN ILWWHG ZLWK D VHSWXP JODVV VWRSSHU FRQGHQVHU ZLWK 1 SXUJH DQG D PDJQHWLF VWLUUHU 'U\ WULJO\PH POf ZDV DGGHG E\ V\ULQJH IROORZHG E\ J [ 2n PROf LRGRQLWURSKHQDQWKUHQH f J [f PROf 3G3&+ff ZHLJKHG LQ GU\ER[ DQG WUDQVIHUUHG E\ VROLG DGGLWLRQ WXEHf DQG PO RI SHUIOXRURHWKHQ\O ]LQF LRGLGH VROXWLRQ &) &) FRQFHQWUDWLRQ LV 0 E\ LQWHUQDO VWDQGDUG ) 105 PO LV [f PROf E\ V\ULQJH 7KH PL[WXUH ZDV

PAGE 126

VWLUUHG DQG KHDWHG WR r& $IWHU KRXUV LRGRQLWURSKHQDQWKUHQH LV FRQVXPHG DV LQGLFDWHG E\ 7/& 0HUFN .LHVHOJHO ) JODVV EDFNHG SODWHVf LQ KH[DQH 7+) 6HYHQ VSRWV DUH HYLGHQW 5I Vf Zf Zf Zf Zf Vf Pf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bf ZDV REWDLQHG DV ZKLWH IODNHV PHOWLQJ r& 5I LQ WKH DERYH VROYHQW V\VWHP 2WKHU IUDFWLRQV ZHUH QRW SXUH DQG DFFRXQWHG IRU J PDWHULDO ZKLFK ZHUH QRW IXUWKHU DQDO\]HG 3XULILFDWLRQ RI %LVWQIOXRURHWKHQYOfSKHQDQWKUHQH f EY 3UHSDUDWLYH */3& 7KH FRXSOLQJ UHDFWLRQ ZDV FDUULHG RXW XVLQJ VLPLODU FRQGLWLRQV DV GHVFULEHG SUHYLRXVO\ XVLQJ J LRGRQLWURSKHQDQWKUHQH f ([WUDFWLRQV ZHUH FDUULHG RXW DV LQ WKH SUHYLRXV SUHSDUDWLRQ DQG WKH UHVXOWDQW J EURZQ RLO ZDV GLVVROYHG LQ PO RI GLHWK\O HWKHU DQG VHSDUDWHG E\ SUHSDUDWLYH */3& LQ M[O DOLTXRWV &ROXPQ LQFK [ IHHW b 4) RQ &KURPDVRUE :+3 2YHQ FRQVWDQW DW r& ,QMHFWRU r& 7&' EORFN r& +H IORZ POPLQXWH UHWHQWLRQ WLPH PLQXWHVf :KLWH IODNHV RI

PAGE 127

J bf ZHUH REWDLQHG PHOWLQJ DW r& 7KH SXULW\ RI WKLV PDWHULDO LV b E\ DQDO\WLFDO */3& 4%LVWULIOXRURHWKHQ\OfSKHQDQWKUHQH + 105 0+] &'&, 706f W + -++ +]f W + -++ +]f G + -++ +]f G + -++ +]f ) 105 0+] &'&, &)&, r&f V\Q GLDVWHURPHU ORZ ILHOG f VLJQDO RYHUODSSHG ZLWK DQWL GLDVWHUHRPHU GG ) -WUDQV)) +] -)) +]f GG ) -)) +] -FLV)) +]f DQWL GLDVWHURPHU GG ) MII +] -FLV)) +]f GG ) -WUDQV)) +] M)) +]f GG ) -)) +] -FLV)) +]f 105 0+] &'&, 706f EPf 89 6SHFWUXP LQ QSHQWDQH ;QPf (FPPRLff f f f f f /RZ 5HVROXWLRQ 0DVV 6SHFWUXP P] b UHODWLYH LQWHQVLW\f f f f f f f f f +LJK 5HVROXWLRQ 0DVV 6SHFWUXP &DOFXODWHG IRU &LV+) 0HDVXUHG 7KHUPRO\VLV RI %LVWULIOXRURHWKHQYQSKHQDQWKUHQH f ,VRODWLRQ RI 3URGXFWV +H[DIOXRURGLKYGURWUL'KHQYOHQH f +H[DIOXRURSKHQDQWKURfELFYFORI 2OKH[HQH f 'LIOXRUR PHWKYOLGHQHWHWUDIOXRURSKHQDQWKURfF\FORSHQWHQH f DQG 3KHQDQWKURfWULIOXRURWULIOXRURPHWKYO FYFORSHQWDGLHQH $ VROXWLRQ RI J [ 2n PROf LQ J &H+ZDV SUHSDUHG DQG IODPH VHDOHG LQ D &DULXV WXEH XQGHU 1 7KH VDPSOH ZDV WKHQ SODFHG LQ D 6WDWLP WKHUPRVWDWHG RLO EDWK DW r& DQG KHDWHG IRU KRXUV 7KH WXEH ZDV RSHQHG DQG */3& DQDO\VLV VKRZHG VWDUWLQJ PDWHULDO DQG IRXU QHZ SURGXFWV &ROXPQ LQFK [ IHHW b 4) RQ &KURPDVRUE :+3 2YHQ FRQVWDQW DW r& ,QMHFWRU r&f SHUFHQWDJHV RI WRWDO PDVV EDODQFH EHLQJ b b b b DQG b 7KH VROYHQW ZDV HYDSRUDWHG XQGHU D VWUHDP RI 1 WKHQ WKH VDPSOH ZDV VXEMHFW WR YDFXXP PP+J IRU

PAGE 128

KRXUf WR \LHOG J RI \HOORZLVKWDQ SRZGHU FRUUHVSRQGLQJ WR DQ b \LHOG RI &LV+V)H LVRPHUV 7KLV PL[WXUH ZDV WDNHQ XS LQ PO GLHWK\O HWKHU DQG VHSDUDWHG LQWR ILYH IUDFWLRQV E\ SUHSDUDWLYH */3& IRU D b \LHOG RI &L+) LVRPHUV LVRODWHG &ROXPQ LQFK [ IHHW b 4) RQ &KURPDVRUE :+3 2YHQ FRQVWDQW DW r& ,QMHFWRU r& 7&' EORFN r& +H IORZ POPLQXWH 5HWHQWLRQ WLPHV &RPSRXQG PLQXWHVf f f f f ff )UDFWLRQ %\ FRPSDULVRQ RI + DQG ) 105 VSHFWUD DQG PHOWLQJ SRLQW ZLWK HDUOLHU REWDLQHG VDPSOH WKH PDWHULDO LV IRXQG WR EH :KLWH IODNHV PJ b LVRODWHGf ZHUH REWDLQHG PHOWLQJ r& DQG b SXUH E\ DQDO\WLFDO */3& )UDFWLRQ +H[DIOXRURSKHQDQWKURELFYFOR> KH[HQH f :KLWH SRZGHU PJ b LVRODWHGf ZDV REWDLQHG DFWXDOO\ D PL[WXUH RI DQG $ VHFRQG FDUHIXO VHSDUDWLRQ RI VXFK D PL[WXUH E\ WKH DIRUHPHQWLRQHG SUHSDUDWLYH */3& FRQGLWLRQV ZRXOG \LHOG UDWLRV DURXQG UHVSHFWLYHO\ +H[DIOXRURSKHQDQWKURfELF\FOR>@KH[ HQH f + 105 0+] &'&, 706f P +f P +f G + -KK +]f G + M++ +]f ) 105 0+] &'&, &)&,f GGGP ) -)) +] -)) +] -)) +]f GP ) -)) +]f GGGP ) -)) +] -)) +] -II +]f GWG ) -)) +] -)) +] -)) +]f WR P )f GGGGG ) -)) +] MII +] -)) +] -II +] -)) +]f /RZ 5HVROXWLRQ 0DVV 6SHFWUXP P] b UHODWLYH LQWHQVLW\f f f f f f f f f +LJK 5HVROXWLRQ 0DVV 6SHFWUXP &DOFXODWHG IRU &LV+H)H 0HDVXUHG

PAGE 129

)UDFWLRQ 'LILXRURPHWKYOLGHQHWHWUDIOXRURSKHQ DQWKURfF\FORSHQWHQH f $ OLJKW \HOORZ SRZGHU PJ b LVRODWHGf EHLQJ D PL[WXUH RI DQG ZDV REWDLQHG 'LIOXRURPHWKYOLGHQH WHWUDIOXRURSKHQDQWKURfFYFORSHQWHQH f + 105 0+] &'&, 706f W ZLWK ILQH VSOLWWLQJ + -+K +] -+K +]f W ZLWK ILQH VSOLWWLQJ + -+K +] -+K +]f G + -+K +]f G ZLWK ILQH VSOLWWLQJ + -++ +] -++ +]f ) 105 0+] &'&, &)&,f WR P )f GGP ) -)I +] -)I +]f /RZ 5HVROXWLRQ 0DVV 6SHFWUXP P] b UHODWLYH LQWHQVLW\f f f f f f f +LJK 5HVROXWLRQ 0DVV 6SHFWUXP &DOFXODWHG IRU &L+) 0HDVXUHG )UDFWLRQ +H[DIOXRURGLKYGURWULSKHQYOHQH $ OLJKW \HOORZ VROLG PJ b LVRODWHGf b SXUH ZLWK FRQWDPLQDWLRQ E\ b DQG b ZDV REWDLQHG +H[DIOXRURGLK\GURWULSKHQ\OHQH f + 105 0+] &'&, 706f W + -++ +]f W + -+K +]f G + -+K +]f G + -++ +]f ) 105 0+] &'&, &)&,f GP ) -)) +]f WP ) -)) +]f /RZ 5HVROXWLRQ 0DVV 6SHFWUXP P] b UHODWLYH LQWHQVLW\f f f f f f f f f +LJK 5HVROXWLRQ 0DVV 6SHFWUXP &DOFXODWHG IRU &+) 0HDVXUHG )UDFWLRQ 3KHQDQWKURfWULIOXRURWULIOXRURPHWK\O F\FORSHQWDGLHQH f /LJKW \HOORZ QHHGOHV PJ b LVRODWHGf ZHUH REWDLQHG $ VHFRQG VHSHUDWLRQ RI VXFK PDWHULDO E\ WKH SUHYLRXV SUHSDUDWLYH */3& FRQGLWLRQV FRXOG \LHOG PDWHULDO b SXUH E\ DQDO\WLFDO */3& PHOWLQJ r& 3KHQDQWKURfWULIOXRURWULIOXRURPHWK\OF\FOR SHQWDGLHQH f + 105 0+] &'&, 706f W + -+K +]f W + -KK +]f G + -++ +]f G + -++

PAGE 130

+]f G + -+K +]f G + M++ +]f ) 105 0+] &'&, &)&,f GW ) -)I +] -)) +]f P)f GP ) -II +]f /RZ 5HVROXWLRQ 0DVV 6SHFWUXP P] b UHODWLYH LQWHQVLW\f f f f f f f +LJK 5HVROXWLRQ 0DVV 6SHFWUXP &DOFXODWHG IRU &+) )RXQG 6ROXWLRQ 3KDVH 7KHUPRO\VLV RI %LVWULIOXRURHWKHQYQSKHQDQWKUHQH $ 4XDQWLWDWLYH 6WXG\ )ROORZHG EY ,e 105 $ VWRFN VROXWLRQ RI LQ &' ZDV SUHSDUHG DV IROORZV J [ 2n PROf SUHSDUDWLYH */3& SXULILHG */3& FRQGLWLRQV DV LQ SUHYLRXV V\QWKHWLF VHFWLRQf ZDV GLVVROYHG LQ PO RI &' DQG PJ &+) ZDV DGGHG DV DQ ) 105 LQWHUQDO VWDQGDUG $Q DOLTXRW RI WKH VROXWLRQ ZDV V\ULQJHG LQWR HDFK RI WKUHH WKLFN ZDOOHG 105 WXEHV EDVH ULQVHG GHLRQL]HG ZDWHU ULQVHG DFHWRQH ULQVHG IODPH GULHGf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f 6ROXWLRQ 3KDVH 7KHUPRO\VLV RI +H[DIOXRURL'KHQDQWKUR ELF\FOR>@KH[HQH f $ 4XDQWLWDWLYH 6WXG\ )ROORZHG EYLA) 105 $ VWRFN VROXWLRQ RI LQ &' ZDV SUHSDUHG DV IROORZV J [ PROf SUHSDUDWLYH */3& SXULILHG SUHSDUDWLYH */3& DV LQ V\QWKHWLF GLVFXVVLRQ VHFWLRQ FRQWDLQLQJ WUDFHV RI DQG f ZDV GLVVROYHG LQ J

PAGE 131

7DEOH 5HODWLYH 3HUFHQW &RPSRVLWLRQ 'DWD IRU 7KHUPRO\VLV RI DW r& 6HFRQGV b b b b b b0% B 7DEOH 5HODWLYH 3HUFHQW &RPSRVLWLRQ 'DWD IRU 7KHUPRO\VLV RI r& 6HFRQGV b b b b b b0% B

PAGE 132

7DEOH &RQWLQXHG 6HFRQGV b b b b b b0% f 7DEOH 5HODWLYH 3HUFHQW &RPSRVLWLRQ 'DWD IRU 7KHUPRO\VLV RI r& 6HFRQGV b b b b b b0% &' DQG PJ RI &) ZDV DGGHG DV DQ ) 105 LQWHUQDO VWDQGDUG $Q DOLTXRW RI WKH VROXWLRQ ZDV V\ULQJHG LQWR HDFK RI WKUHH WKLFN ZDOOHG 105 WXEHV EDVH ULQVHG GHLRQL]HG ZDWHU ULQVHG DFHWRQH ULQVHG IODPH GULHGf DQG WKHQ WKH WXEHV ZHUH IODPH VHDOHG XQGHU 1 7KHUPRO\VLV ZDV FDUULHG RXW E\ VXEPHUJLQJ D VDPSOH LQ D 6WDWLP WKHUPRVWDWHG RLO EDWK IRU D WLPH SHULRG WKHQ UDSLGO\ UHPRYLQJ DQG FRROLQJ WKH VDPSOH LQ DQ LFH EDWK 7KH VDPSOH ZDV WKHQ REVHUYHG E\ ) 105 XVLQJ D 7L GHOD\ RI VHFRQGV DQG FROOHFWLQJ D PLQLPXP RI WUDQVLHQWV EHIRUH )RXULHU WUDQVIRUPLQJ WKH VSHFWUXP 7KH UHODWLYH FRQFHQWUDWLRQV RI DOO IOXRULQDWHG SURGXFWV ZDV DUULYHG DW E\ LQWHJUDWLRQ RI WKH

PAGE 133

VDPSOH VLJQDOV DQG FRPSDULVRQ YHUVXV WKH LQWHUQDO VWDQGDUG &) 6HH 7DEOHV DQG IRU GDWDf 7DEOH 5HODWLYH 3HUFHQW &RPSRVLWLRQ 'DWD IRU 7KHUPRO\VLV RI DW r& 6HFRQGV b b b b0% B B B B 7DEOH 5HODWLYH 3HUFHQW &RPSRVLWLRQ 'DWD IRU 7KHUPRO\VLV RI DW r& 6HFRQGV b b b b0% B B

PAGE 134

7DEOH 5HODWLYH 3HUFHQW &RPSRVLWLRQ 'DWD IRU 7KHUPRO\VLV RI DW r& 6HFRQGV b b b b0% f 5HDFWLRQ RI %LVWULIOXRURHWKHQ\OfSKHQDQWKUHQH f ZLWK &V) %LVWULIOXRURHWKHQ\OfSKHQDQWKUHQH J [n PROf ZDV GLVVROYHG LQ PO RI GU\ '0) WR ZKLFK ZDV DGGHG J [f PROf GU\ &V) 7KH UHDFWLRQ PL[WXUH ZDV VWLUUHG UDSLGO\ IRU KRXUV DW URRP WHPSHUDWXUH DQG D VPDOO DOLTXRW RI WKH UHDFWLRQ PL[WXUH ZDV WDNHQ GLOXWHG ZLWK ZDWHU H[WUDFWHG ZLWK GLHWK\O HWKHU FRQFHQWUDWHG XQGHU D VWUHDP RI 1 WKHQ DQDO\]HG E\ DQDO\WLFDO */3& &ROXPQ LQFK [ IHHW b 4) RQ &KURPDVRUE :+3 2YHQ FRQVWDQW DW r& ,QMHFWRU r&f VKRZLQJ QR UHDFWLRQ KDG RFFXUUHG 7KH VDPSOH ZDV WKHQ KHDWHG DW r& $IWHU KRXUV DQ DOLTXRW ZDV WDNHQ DV HDUOLHU DQG */3& DQDO\VLV VKRZV WKUHH SURGXFWV ZLWK DSSUR[LPDWHO\ b FRQVXPHG &RPSDULVRQ ZLWK D WKHUPRO\VLV UHDFWLRQ PL[WXUH VDPSOH FRQWDLQLQJ PDWHULDOV DQG f VKRZV WKDW WKH &V) UHDFWLRQ KDV QR SURGXFWV LQ FRPPRQ ZLWK WKH WKHUPDO UHDFWLRQ $IWHU KRXUV IXUWKHU KHDWLQJ */3& DQDO\VLV VKRZV KDV EHHQ FRQVXPHG DQG RQH PDMRU DQG WZR PLQRU SURGXFWV DUH REVHUYHG 7KH UHDFWLRQ PL[WXUH ZDV WUDQVIHUUHG WR D VHSDUDWRU\ IXQQHO ZLWK PO RI ZDWHU DQG H[WUDFWHG ZLWK GLHWK\O HWKHU 7KH HWKHU ZDV WKHQ GULHG RYHU DQK\GURXV 0J6&! DQG HYDSRUDWHG WR

PAGE 135

\LHOG D VPDOO DPRXQW RI EURZQ RLO 7KH RLO ZDV WDNHQ XS LQ &'&, DQG LWnV ) 105 VSHFWUXP REVHUYHG 7KH VSHFWUXP VKRZV WZR FOXVWHUV RI VLJQDOV WR SSP VLJQDOV RI YDULRXV LQWHQVLWLHVf DQG WR SSP VLJQDOVf &RPSDULVRQ RI WKLV VSHFWUXP ZLWK NQRZQ VSHFWUD RI WKHUPRO\VLV SURGXFWV DQG VKRZV WKHVH WZR UHDFWLRQV KDYH QR SURGXFWV LQ FRPPRQ 1R IXUWKHU FKDUDFWHUL]DWLRQ RU VHSDUDWLRQ ZDV SHUIRUPHG RQ WKH &V) UHDFWLRQ PL[WXUH 5HDFWLRQ RI 'LIOXRURPHWKYOLGHQHWHWUDIOXRURSKHQDQWKURf FYFORSHQWHQH f ZLWK &DWDO\WLF &V) 7R DQ 105 VDPSOH LQ &' ZLWK &) LQWHUQDO VWDQGDUG FRQWDLQLQJ b b DQG b ZDV DGGHG SL RI &H' FRQWDLQLQJ WUDFHV RI &V) 7KLV IOXRULGH VSLNHG &' VROXWLRQ ZDV SUHSDUHG E\ DGGLQJ PO RI GU\ &' WR PJ RI GU\ &V) WKHQ KHDWLQJ WR UHIOX[ IRU PLQXWHV 9LVXDOO\ QR &V) GLVVROYHG 7KH 105 VDPSOH ZDV WKHQ IODPH VHDOHG DQG SODFHG LQ D 6WDWLP WKHUPRVWDWHG RLO EDWK DW r& IRU PLQXWHV $IWHU WKLV WLPH WKH VDPSOH ZDV FRROHG DQG IRXQG WR FRQWDLQ b b DQG b E\ LQWHJUDWLRQ RI WKH ) 105 VLJQDOV YHUVXV WKH &) LQWHUQDO VWDQGDUG 7KH RYHUDOO PDVV EDODQFH RI DQG YHUVXV WKH VWDUWLQJ PL[WXUH LV b 7KHUPRO\VLV RI KH[DIOXRURGLKYGURWULSKHQYOHQH )ROORZHG EY */3& 7ZR PLOOLJUDPV RI D PL[WXUH EHLQJ b DQG b ZDV GLVVROYHG LQ J RI EHQ]HQH DQG D VPDOO DPRXQW D IHZ PJf RI SKHQDQWKUHQH ZDV DGGHG DV DQ LQWHUQDO VWDQGDUG 7KH VROXWLRQ ZDV V\ULQJHG LQWR FDSLOODU\ WXEHV ZKLFK ZHUH WKHQ IODPH VHDOHG 7KH VDPSOHV ZHUH SODFHG LQ D 6WDWLP WKHUPRVWDWHG RLO EDWK DW r& 7KH SURJUHVV RI WKH UHDFWLRQ ZDV IROORZHG E\ UHPRYLQJ VHDOHG VDPSOHV RYHU WLPH DQG REVHUYLQJ WKH UHDFWLRQ VROXWLRQ E\ DQDO\WLFDO */3&

PAGE 136

&ROXPQ LQFK [ IHHW b 4) RQ &KURPDVRUE :+3 2YHQ FRQVWDQW DW r& ,QMHFWRU r&f GHFRPSRVHV DQG DIWHU KRXUV LV b FRQVXPHG 1R QHZ SURGXFWV ZHUH REVHUYHG E\ */3& RI WKH UHDFWLRQ PL[WXUH DQG WKHUH ZDV QR LQFUHDVH LQ WKH UHODWLYH FRQFHQWUDWLRQ RI RYHU WKH WKHUPRO\VLV SHULRG $IWHU KRXUV KDV EHHQ FRPSOHWHO\ FRQVXPHG WKH FRQFHQWUDWLRQ KDV QRW FKDQJHG DQG WKHUH ZHUH QR QHZ SURGXFWV REVHUYHG E\ */3& 7KHUPRO\VLV RI +H[DIOXRURGLKYGURWULSKHQYOHQH f )ROORZHG E\OI!)105 7KUHH PLOOLJUDPV RI D PL[WXUH EHLQJ b DQG b ZDV GLVVROYHG LQ J RI &' FRQWDLQLQJ WUDFHV RI &) DV DQ LQWHUQDO VWDQGDUG $Q DOLTXRW RI WKH VROXWLRQ ZDV WKHQ WUDQVIHUUHG WR DQ WKLFN ZDOOHG 105 WXEH DQG IODPH VHDOHG XQGHU 1 7KH VDPSOH ZDV SODFHG LQ D 6WDWLP WKHUPRVWDWHG RLO EDWK DW r& WDNHQ RXW DW VSHFLILF WLPH LQWHUYDOV DQG FRROHG UDSLGO\ LQ DQ LFHZDWHU EDWK WKHQ REVHUYHG E\ ) 105 7KH VDPSOHnV ) 105 VSHFWUXP ZDV REWDLQHG ILYH WLPHV RYHU PLQXWHV 7KH DPRXQW RI ZDV FOHDUO\ REVHUYHG WR GHFUHDVH DQG DIWHU PLQXWHV b RI WKH KDG EHHQ FRQVXPHG 7KHUH ZHUH PDQ\ QHZ ORZ LQWHQVLW\ VLJQDOV LQ WKH ) 105 VSHFWUXP REVHUYHG LQ WKH UHJLRQ RI WR SSP 7KHUH ZDV QR FKDQJH LQ WKH DPRXQW RI DQG QR QRU ZHUH REVHUYHG WR KDYH IRUPHG 'LVDSSHDUDQFH RI /Qbf YHUVXV WLPHf GLG QRW IROORZ ILUVWRUGHU NLQHWLFV 6ROXWLRQ 3KDVH 3KRWRO\VLV RI +H[DIOXRURGLKYGURWQSKHQYOHQH PL $ J VDPSOH EHLQJ b DQG b ZDV GLVVROYHG LQ J RI QSHQWDQH FRQWDLQLQJ WUDFHV RI &+) 7KH VROXWLRQ ZDV IUHH]HWKDZ GHJDVVHG DQG DQ DOLTXRW ZDV V\ULQJHG LQWR D PP TXDUW] 105 WXEH DQG IODPH

PAGE 137

VHDOHG XQGHU 1 7KH VDPSOH ZDV SKRWRO\]HG XVLQJ D 5D\RQHW UHDFWRU PRGHO 535 IRXU ORZ SUHVVXUH PHUFXU\ EXOEV RI W\SH 58/ ƒ IURP 6RXWKHUQ 1( 8OWUDYLROHW &R 0LGGOHWRQ &RQQHFWLFXWf DQG WKH FRQFHQWUDWLRQV RI DOO PDWHULDOV ZHUH PRQLWRUHG YHUVXV LQWHUQDO VWDQGDUG E\ ) 105 6HH 7DEOH IRU GDWDf $ ILQH ILOP RI LQVROXEOH VROLG ZDV REVHUYHG WR KDYH IRUPHG RQ WKH LQWHULRU RI WKH 105 WXEH +H[DIOXRUR SKHQDQWKURfELF\FOR>@KH[HQH f ZDV REVHUYHG LQ VROXWLRQ E\ ) 105 EXW QRW LVRODWHG GXH WR WKH VPDOO DPRXQW RI PDWHULDO +H[DIOXRURSKHQDQWKURfELFYFOR>@KH[HQH f ) 105 0+] QSHQWDQH &)&,f GP ) -)) +]f GP ) -)) +]f EV )f 7DEOH 5HODWLYH &RPSRVLWLRQ 'DWD IRU 6ROXWLRQ 3KDVH 3KRWRO\VLV RI 0LQXWHV b b b0% 6ROXWLRQ 3KDVH 3KRWRO\VLV RI %LVWULIOXRURHWKHQ\OfSKHQDQWKUHQH f $ VDPSOH FRQVLVWLQJ RI J [f PROf DQG J [f PROf &H+) ZDV GLVVROYHG LQ PO RI GU\ QSHQWDQH DQG WKH VROXWLRQ ZDV IUHH]HWKDZ GHJDVVHG 7KH VROXWLRQ ZDV V\ULQJHG LQWR DQ 105 WXEH DQG IODPH VHDOHG XQGHU 1 7KH VDPSOH ZDV LUUDGLDWHG E\ 5D\RQHW UHDFWRU PRGHO 535 ORZ SUHVVXUH PHUFXU\ EXOEV RI W\SH 58/ ƒ IURP 6RXWKHUQ 1( 8OWUDYLROHW &R 0LGGOHWRQ &RQQHFWLFXWf DQG WKH FRPSRVLWLRQ RI WKH UHDFWLRQ PL[WXUH ZDV PRQLWRUHG E\ ) 105 RYHU D SHULRG RI KRXUV 6HH 7DEOH IRU GDWDf $IWHU WKLV WLPH WKH VROXWLRQ KDG WXUQHG FOHDU OLJKW \HOORZ IURP FOHDU

PAGE 138

FRORUOHVV DQG D WKLQ VROLG ILOP KDG GHYHORSHG RQ WKH LQVLGH RI WKH VDPSOH WXEH 7KUHH PDWHULDOV LGHQWLILHG HDUOLHU ZHUH VHHQ LQ WKH UHDFWLRQ PL[WXUH WKRVH EHLQJ DQG $OVR REVHUYHG LQ VROXWLRQ E\ ) 105 EXW QRW LVRODWHG ZDV KH[DIOXRURSKHQDQWKURfELF\FOR> @KH[HQH f KH[DIOXRURSKHQDQWKURELFYFOR>@KH[HQH f ) 105 0+] QSHQWDQH &)&,f GWW ) -)) +] -)) +] -II +]f GWW ) -)) +] -)) +] -)) +]f S ) -II +]f 7DEOH 5HODWLYH &RPSRVLWLRQ 'DWD IRU 6ROXWLRQ 3KDVH 3KRWRO\VLV RI %LVWULIOXRURHWKHQ\OfSKHQDQWKUHQH f 0LQXWHV b b b b b b0% P 7UDFH 7UDFH 7UDFH B 7UDFH 7UDFH 7UDFH B B B $Q DWWHPSW WR VHSDUDWH WKLV UHVXOWDQW PL[WXUH ZDV SHUIRUPHG E\ SUHSDUDWLYH */3& &ROXPQ LQFK [ IHHW b 4) RQ &KURPDVRUE :+3 2YHQ FRQVWDQW DW r& ,QMHFWRU r& 7&' EORFN r& +H IORZ POPLQXWHf 7ZR IUDFWLRQV ZHUH LVRODWHG )UDFWLRQ PJ OLJKW \HOORZ VROLG

PAGE 139

bf bf bf )UDFWLRQ PJ OLJKW \HOORZ VROLG bf bf bf 3KRWRO\VLV RI %LVWULIOXRURHWKHQYOfSKHQDQWKUHQH f DQG 7KHUPRO\VLV RI 6XEVHTXHQW 5HDFWLRQ 0L[WXUH $ VDPSOH RI J [f PROf ZDV GLVVROYHG LQ PO RI GU\ IUHH]HWKDZ GHJDVVHG QSHQWDQH DQG SKRWRO\]HG ZLWK D 5D\RQHW UHDFWRU PRGHO 535 ORZ SUHVVXUH PHUFXU\ EXOEV RI W\SH 58/ ƒ IURP 6RXWKHUQ 1( 8OWUDYLROHW &R 0LGGOHWRQ &RQQHFWLFXWf WKURXJK D 3\UH[ URWDIORZ WXEH IRU KRXUV DQG PLQXWHV $IWHU WKLV WLPH WKH VROXWLRQ KDG WXUQHG IURP FOHDU FRORUOHVV WR FOHDU \HOORZ ZLWK D ILQH ILOP IRUPLQJ RQ WKH LQVLGH RI WKH WXEH 7KH WXEH ZDV WKHQ RSHQHG DQG WKH VROYHQW UHPRYHG XQGHU D VWUHDP RI 1 7KH UHPDLQLQJ VROLG ZDV GLVVROYHG LQ &' DQG ) 105 VKRZV DW WKLV WLPH bf bf bf 7KH VDPSOH ZDV WKHQ IODPH VHDOHG LQ D WKLFN ZDOOHG 105 WXEH +HDWLQJ WKLV VDPSOH DW r& IRU KRXU HIIHFWHG QR FKDQJH 7KH VDPSOH ZDV WKHQ KHDWHG DW r& IRU PLQXWHV $IWHU WKLV KHDWLQJ SHULRG H[DPLQLQJ WKH UHDFWLRQ PL[WXUH E\ ) 105 VKRZHG bf bf bf bf ZLWK QR RU UHPDLQLQJ DQG QR RWKHU QHZ VLJQDOV LQ WKH ) 105 VSHFWUXP ,QWHUQDO VWDQGDUG ZDV QRW XVHG VR WKH RYHUDOO PDVV EDOODQFH IURP ZDV QRW HVWDEOLVKHG 3UHSDUDWLRQ RI 3HUIOXRUR(=+DQG ((DGLPHWK\ORFWDWULHQH = (f 3HUIOXRUR(=((((fGLPHWK\ORFWDWULHQH =(f ZDV SUHSDUHG E\ WKH PHWKRG RI +DQVHQ $ PO WKUHH QHFNHG URXQG ERWWRP IODVN ZDV DVVHPEOHG ZLWK WZR VHSWD D VWRSSHU DQG D PDJQHWLF VWLUUHU WKHQ IODPH GULHG XQGHU $U SXUJH 'U\ GHJDVVHG '0) POf ZDV V\ULQJHG LQWR WKH UHDFWLRQ YHVVHO &Gr SRZGHU J [ 2n PROf ZDV ZHLJKHG RXW LQWR D

PAGE 140

VROLG DGGLWLRQ WXEH LQ D GU\ER[ WKHQ DGGHG WR WKH UHDFWLRQ YHVVHO 7KH PL[WXUH ZDV FRROHG WR r& WKHQ J PO [n PROf SHUIOXRUR= LRGRSURSHQH ZDV DGGHG GURSZLVH 7KH PL[WXUH ZDV DOORZHG WR ZDUP WR 57 DQG VWLUULQJ ZDV FRQWLQXHG IRU KRXUV ,QWHUQDO VWDQGDUG ) 105 DW WKLV WLPH VKRZV D b \LHOG RI =;&Gf)& &)&)f ZKHUH ; DQG =&) &)&)f DV D GHHS EURZQUHG VROXWLRQ ([FHVV &Gr ZDV UHPRYHG E\ 6FKOHQN ILOWHULQJ WKH VROXWLRQ LQWR DQRWKHU WKUHH QHFNHG URXQG ERWWRP IODVN XQGHU $U 5HFU\VWDOOL]HG &X%U J [f PROf ZDV ZHLJKHG RXW LQWR D VROLG DGGLWLRQ WXEH LQ D GU\ER[ WKHQ DGGHG WR WKH VROXWLRQ DW 57 7KLV PL[WXUH ZDV VWLUUHG YLJDURXVO\ IRU KRXU DW 57 WKHQ WKH VROLGV ZHUH UHPRYHG E\ 6FKOHQN ILOWHULQJ WKH VROXWLRQ LQWR DQRWKHU WKUHH QHFNHG URXQG ERWWRP IODVN XQGHU $U $ FROG ILQJHU WUDS ZLWK D JDV LQOHW SRUW ZDV DGGHG WR WKH DSSDUDWXV DQG J [ 2f PROf KH[DIOXRUR EXW\QH ZDV VORZO\ DGGHG IURP D WDUHG 5RWDIORZ WXEH RYHU PLQXWHV ZKLOH PDLQWDLQLQJ WKH WHPSHUDWXUH RI WKH V\VWHP DW 57 E\ XVH RI D ZDWHU EDWK 7KLV PL[WXUH ZDV VWLUUHG YLJDURXVO\ DW 57 IRU KRXU WR \LHOG D FORXG\ RUDQJHEURZQ VXVSHQVLRQ 7KH FRQGHQVHU ZDV UHPRYHG DQG UHSODFHG ZLWK D YDFXXP WDNHRII 7KH UHDFWLRQ PL[WXUH ZDV HYDFXDWHG DW PP +J DQG 57 IRU PLQXWHV DQG H[FHVV KH[DIOXRUREXW\QH ZDV WUDSSHG 3HUIOXRUR=LRGRSURSHQH J [ PROf ZDV WKHQ VORZO\ DGGHG E\ V\ULQJH DQG WKH PL[WXUH VWLUUHG YLJDURXVO\ IRU KRXUV :KHQ VWLUULQJ ZDV VWRSSHG WKH PL[WXUH VHSDUDWHG LQWR DQ XSSHU GDUN EURZQ OD\HU RI '0) PDMRULW\ RI YROXPHf DQG D FOHDU FRORUOHVV OD\HU RI SHUIOXRURROHILQ RQ WKH ERWWRP ZLWK WDQ VROLG VHWWOLQJ RQ WKH VLGHV RI WKH YHVVHO 7KH PL[WXUH ZDV WKHQ IODVK GLVWLOOHG XVLQJ D EDWK WHPSHUDWXUH XS WR r& DQG YDFXXP RI PP +J $SSUR[LPDWHO\ PO RI FOHDU OLJKW \HOORZ OLTXLG ZDV REWDLQHG ZLWK PO RI D GDUN \HOORZ '0) OD\HU RQ WRS 7KH ERWWRP SHUIOXRURROHILQ f OD\HU ZDV GUDZQ RXW E\ V\ULQJH DQG WUDQVIHUUHG WR D ODUJH VHSWXP FDSSHG YLDO 7KH PDWHULDO ZDV ZDVKHG ZLWK [ PO RI FROG ZDWHU

PAGE 141

WUDQVIHUUHG WR D QHZ YLDO DQG GULHG RYHU 0J6f WKHQ V\ULQJHG WKURXJK D MLP V\ULQJH ILOWHU LQWR D YLDO FRQWDLQLQJ DFWLYDWHG ƒ VLHYHV $ J bf VDPSOH RI FOHDU IDLQW \HOORZ ZDV REWDLQHG EHLQJ b SXUH E\ */3& =;&Gf)& &)&)Jf ; DQG =&) &)&)f 105 0+] '0) &)&,f GG RU ) -)) +] -)) +]f P RU )f GP RU ) -)) +]f 3HUIOXRUR(=((((fGLPHWK\ORFWDWULHQH =(f ) 105 0+] QSHQWDQH &)&,f (=( EV )f GG RYHUODSSHG ZLWK ((( WULHQH VLJQDO ) -)) +] -)) m +]f GT ) -)) +] -II +]f GP RYHUODSSHG ZLWK ((( WULHQH VLJQDO ) -II p +]f ((( SXUH VDPSOH REWDLQHG E\ SUHSDUDWLYH */3& DIWHU HQULFKPHQW YLD SKRWRO\VLV RI WULHQH PL[WXUH WKURXJK 3\UH[f EV )f GG ) -II +] -)) +]f GT ) -)) +] -)) +]f GP ) -)) +]f 89 LQ QSHQWDQH !rPD[ QP (PD[ FPPRO /RZ 5HVROXWLRQ 0DVV 6SHFWUXP P] b UHODWLYH LQWHQVLW\f f f f f f f +LJK 5HVROXWLRQ 0DVV 6SHFWUXP &DOFXODWHG IRU &) 0HDVXUHG 6ROXWLRQ 3KDVH 7KHUPRO\VLV RI 3HUIOXRUR(=(I(((OGLPHWKYO RFWDWULHQH =(ff $ J [f PROf VDPSOH RI (DQG =ZDV GLVVROYHG LQ PO RI GU\ QSHQWDQH DQG SL &H+) DGGHG 7KH VROXWLRQ ZDV IUHH]HWKDZ GHJDVVHG DQG D PO DOLTXRW WDNHQ DQG WUDQVIHUUHG WR D PP WKLFN ZDOOHG 105 WXEH EDVH ULQVHG GHLRQL]HG ZDWHU ULQVHG DFHWRQH ULQVHG IODPH GULHGf DQG IODPH VHDOHG XQGHU 1 7KH VDPSOH ZDV WKHQ KHDWHG IRU D JLYHQ WLPH LQ D 6WDWLP WKHUPRVWDWHG RLO EDWK DQG FRQFHQWUDWLRQV RI DOO PDWHULDOV IROORZHG E\ LQWHJUDWLRQ RI ) 105 VLJQDOV YHUVXV LQWHUQDO VWDQGDUG &+) 6HH 7DEOH IRU GDWDf

PAGE 142

7DEOH 5HODWLYH &RPSRVLWLRQ 'DWD IRU 7KHUPRO\VLV RI DW r& WKHQ r& 0LQXWHV b= b( b b0% B B B B 7UDFH 7HPSHUDWXUH ZDV UDLVHG WR r& DQG WKHUPRO\VLV FRQWLQXHG B 3HUIOXRURFnVDQG IUDQVfWULPHWK\O(SURSHQ\OfF\FOREXWHQH f ZHUH REVHUYHG LQ WKH UHDFWLRQ VROXWLRQ E\ ) 105 DQG */3& &ROXPQ LQFK [ IHHW b 6( RQ &KURPDVRUE :+3 2YHQ FRQVWDQW DW r& ,QMHFWRU r& 1 IORZ POPLQXWH 5HWHQWLRQ WLPHV PLQXWHV PLQXWHVf 3HUIOXRURFVIDQG WUDQVfA WULPHWKYO(SUR'HQYQFYFOREXWHQH f ) 105 0+] QSHQWDQH &+) ff EV )f EV )f EV )f EV )f GT ) -)) +] -)) +]f EV )f GEV ) -)) +]f

PAGE 143

3KRWRO\VLV RI 3HUIOXRUR(=(((DGLPHWK\ORFWDWULHQH =(f $ VDPSOH EHLQJ J [ 2n PROf ZDV GLVVROYHG LQ PO RI GU\ QSHQWDQH DQG SL &+) ZDV DGGHG 7KH VROXWLRQ ZDV IUHH]H WKDZ GHJDVVHG WKHQ D PO DOLTXRW ZDV GUDZQ DQG V\ULQJHG LQWR DQ PP 3\UH[ 105 WXEH EDVH ULQVHG GHLRQL]HG ZDWHU ULQVHG DFHWRQH ULQVHG IODPH GULHGf DQG WKH VDPSOH IODPH VHDOHG XQGHU 1 7KH SKRWRO\VLV ZDV FDUULHG RXW E\ VXVSHQGLQJ WKH VDPSOH LQ D 5D\RQHW UHDFWRU PRGHO 535 IRXU ORZ SUHVVXUH PHUFXU\ EXOEV RI W\SH 58/ ƒ IURP 6RXWKHUQ 1( 8OWUDYLROHW &R 0LGGOHWRQ &RQQHFWLFXWf IRU D SHULRG RI WLPH WKHQ REVHUYLQJ WKH UHDFWLRQ PL[WXUH E\ ) 105 5HODWLYH FRQFHQWUDWLRQV RI DOO VSHFLHV ZHUH REWDLQHG E\ LQWHJUDWLRQ YHUVXV LQWHUQDO VWDQGDUG &+) 6HH 7DEOH IRU GDWDf 7DEOH 5HODWLYH &RPSRVLWLRQ 'DWD IRU 3KRWRO\VLV RI 3HUIOXRUR(=(((ef GLPHWK\ORFWDWULHQH =(f 0LQXWHV b= b( b b b0% B B )RU LVRODWLRQ RI SHUIOXRURIUDQVWHWUDPHWK\OF\FORKH[DGLHQH f D UHDFWLRQ VROXWLRQ DIWHU D VXLWDEOH SHULRG RI SKRWRO\VLV FRPSRVLWLRQ EHLQJ b ( ( ( (=(f b b SHUIOXRURIDQV WHWUDPHWK\OELF\FOR>@KH[HQH ff ZDV IUR]HQ LQ OLTXLG QLWURJHQ DQG FDUHIXOO\ WKDZHG 7KLV IUHH]HWKDZ F\FOH ZDV UHSHDWHG WZLFH DQG UHVXOWHG LQ SKDVH VHSHUDWLRQ EHWZHHQ WKH SHUIOXRURRUJDQLFV DQG QSHQWDQH :KLOH VWLOO FRRO r&f WKH XSSHU QSHQWDQH OD\HU FRXOG EH V\ULQJHG DZD\ FRQWDLQLQJ

PAGE 144

OHVV WKDQ b SHUIOXRURRUJDQLFV E\ */3& 7KH UHPDLQLQJ SHUIOXRURRUJDQLFV FRQWDLQLQJ RQ DYHUDJH b RU OHVV QSHQWDQHf ZHUH VHSHUDWHG E\ SUHSDUDWLYH */3& &ROXPQ LQFK [ IHHW b 6( RQ &KURPDVRUE 3 2YHQ FRQVWDQW DW r& ,QMHFWRU r& 7&' EORFN r& +H IORZ POPLQXWH 5HWHQWLRQ WLPHV e PLQXWHV ) 105 GDWD IRU WKLV PDWHULDO LV JLYHQ LQ SHUIOXRURWULHQH SUHSDUDWLRQ H[SHULPHQWDO GLVFXVVLRQf PLQXWHVf 3HUIOXRURIUDQVWHWUDPHWKYOF\FORKH[DGLHQH f ) 105 0+] QSHQWDQH &+) ff P )f P )f P )f P )f 89 LQ QSHQWDQH ;PD[ QP (PD[ FPPRO /RZ 5HVROXWLRQ 0DVV 6SHFWUXP P] b UHODWLYH LQWHQVLW\f f f f f +LJK 5HVROXWLRQ 0DVV 6SHFWUXP &DOFXODWHG IRU &LR) 0HDVXUHG 3KRWRO\VLV RI 3HUIOXRURIUDQVWHWUDPHWKYOFYFORKH[DGLHQH f $ VROXWLRQ EHLQJ b DQG b &+) ZDV SUHSDUHG LQ GU\ QSHQWDQH DQG IUHH]HWKDZ GHJDVVHG $Q PO DOLTXRW ZDV V\ULQJHG LQWR D PP TXDUW] 105 WXEH ZKLFK KDG EHHQ ULQVHG ZLWK EDVH GHLRQL]HG ZDWHU DFHWRQH WKHQ IODPH GULHG XQGHU 1 SXUJH 7KH VROXWLRQ ZDV WKHQ IODPH VHDOHG XQGHU 1 7KH VDPSOH ZDV SKRWRO\]HG XVLQJ D 5D\RQHW UHDFWRU PRGHO 535 IRXU ORZ SUHVVXUH PHUFXU\ EXOEV RI W\SH 58/ ƒ IURP 6RXWKHUQ 1( 8OWUDYLROHW &R 0LGGOHWRQ &RQQHFWLFXWf DQG FRQFHQWUDWLRQV RI DOO PDWHULDOV IROORZHG E\ LQWHJUDWLRQ RI ) 105 VLJQDOV YHUVXV LQWHUQDO VWDQGDUG &+) 6HH 7DEOH IRU GDWDf

PAGE 145

7DEOH 5HODWLYH &RPSRVLWLRQ 'DWD IRU 3KRWRO\VLV RI 3HUIOXRURIUDQV WHWUDPHWK\OF\FORKH[DGLHQH f 0LQXWHV b b b0% 3HUIOXRURIUDQVWHWUDPHWK\OELF\FOR>@KH[HQH f ZDV LVRODWHG RXW RI WKH UHDFWLRQ VROXWLRQ DIWHU D VXLWDEOH SKRWRO\VLV SHULRG 7KH VROXWLRQ ZDV IUR]HQ LQ OLTXLG QLWURJHQ DQG FDUHIXOO\ WKDZHG 7KLV IUHH]HWKDZ F\FOH ZDV UHSHDWHG WZLFH DQG UHVXOWHG LQ SKDVH VHSHUDWLRQ EHWZHHQ WKH SHUIOXRURRUJDQLFV DQG QSHQWDQH :KLOH VWLOO FRRO r&f WKH XSSHU QSHQWDQH OD\HU ZDV FDUHIXOO\ V\ULQJHG DZD\ FRQWDLQLQJ OHVV WKDQ b SHUIOXRURRUJDQLFV E\ */3& 7KH UHPDLQLQJ SHUIOXRURRUJDQLFV FRQWDLQLQJ RQ DYHUDJH b RU OHVV Q SHQWDQHf ZHUH VHSDUDWHG E\ SUHSDUDWLYH */3& &ROXPQ LQFK [ IHHW b 6( RQ &KURPDVRUE 3 2YHQ FRQVWDQW DW r& ,QMHFWRU r& 7&' EORFN r& +H IORZ POPLQXWH 5HWHQWLRQ WLPHV PLQXWHV PLQXWHV QSHQWDQH PLQXWHVf 3HUIOXRURDQVWHWUDPHWK\OELFYFOR>KH[HQH f ) 105 0+] &+&, &)&,f EV )f P )f P )f P )f P )f P )f P )f GP ) -)) +]f /RZ 5HVROXWLRQ 0DVV 6SHFWUXP P] b UHODWLYH LQWHQVLW\f f f f f f f f +LJK 5HVROXWLRQ 0DVV 6SHFWUXP &DOFXODWHG IRU <) 0HDVXUHG

PAGE 146

3UHSDUDWLRQ RI I7HWUDK\GUR+SYUDQYQR[Y EXWDQRO >7HWUDK\GURS\UDQ\OfR[\@EXWDQRO ZDV SUHSDUHG E\ WKH PHWKRG RI +RIIPDQQ DQG 5DEH %XWDQHGLRO PO PROf ZDV SODFHG LQ D URXQG ERWWRP IODVN HTXLSSHG ZLWK D VWURQJ PDJQHWLF VWLUUHU 'LHWK\O HWKHU POf DQG GURSV RI FRQFHQWUDWHG +&, ZHUH WKHQ DGGHG 'LK\GUR+S\UDQ '+3 PO J PROf ZDV GLVVROYHG LQ PO GLHWK\O HWKHU DQG DGGHG GURSZLVH DW 57 ZLWK UDSLG VWLUULQJ WR WKH KHWHURJHQRXV GLROHWKHU PL[WXUH 7KH UHDFWLRQ PL[WXUH EHFDPH KRPRJHQRXV DIWHU DGGLWLRQ RI DSSUR[LPDWHO\ PO RI WKH '+3HWKHU VROXWLRQ 8SRQ FRPSOHWLRQ RI DGGLWLRQ RI WKH '+3 VROXWLRQ WKH UHDFWLRQ PL[WXUH ZDV VWLUUHG IRU KRXUV DW 57 WKHQ H[WUDFWHG ZLWK [ PO b DTXHRXV .2+ 7KH DTXHRXV VROXWLRQ ZDV EDFN H[WUDFWHG ZLWK PO GLHWK\O HWKHU WKHQ WKH HWKHU H[WUDFWV ZHUH FRPELQHG DQG GULHG RYHU 0J6 7KH HWKHU ZDV WKHQ UHPRYHG E\ URWDU\ HYDSRUDWRU DQG WKH UHPDLQLQJ FOHDU FRORUOHVV OLTXLG ZDV IUDFWLRQDOO\ GLVWLOOHG WKURXJK DQ FP YLJHUDX[ FROXPQ >7HWUDK\GUR+S\UDQ\OfR[\@EXWDQRO J bf ZDV REWDLQHG DV DQ HDUO\ IUDFWLRQ ERLOLQJ r& DW PP +J DV D FRORUOHVV YLVFRXV OLTXLG >7HWUDKYGUR$SYUDQYR[Y EXWDQRO + 0+] &'&, 706f P +f V +f P +f W + -++ r +]f & 0+] &'&, &+&,f 3UHSDUDWLRQ RI U7HWUDKYGUR+S\UDQYOfR[YEXWDQDO f >7HWUDK\GUR+S\UDQ\OfR[\@EXWDQDO f ZDV SUHSDUHG E\ DGDSWDWLRQ RI D SURFHGXUH DV GHVFULEHG E\ &RUH\ DQG 6FKPLGW $ / URXQG ERWWRP IODVN ZDV IODPH GULHG XQGHU $U SXUJH DQG HTXLSSHG ZLWK D VWURQJ PDJQHWLF VWLUUHU DQG VHSWXP >7HWUDK\GUR+S\UDQ\OfR[\@EXWDQRO J [ 2n PROf ZDV V\ULQJHG LQWR WKH IODVN IROORZHG E\ PO RI GU\ &+&, 3\ULGLQLXP GLFKURPDWH 3'& J [B PROf ZDV TXLFNO\ DGGHG DQG

PAGE 147

UDSLG VWLUULQJ EHJXQ 7KH VROXWLRQ WXUQHG GDUN EURZQEODFN ZLWKLQ PLQXWHV RI DGGLWLRQ RI WKH 3'& 6WLUULQJ ZDV FRQWLQXHG IRU KRXUV DW 57 WKHQ WKH UHDFWLRQ PL[WXUH ZDV GLOXWHG ZLWK PO GLHWK\O HWKHU 7KH EODFN VROLG UHVLGXH ZDV JUDYLW\ ILOWHUHG DQG WKH UHVXOWDQW EURZQEODFN VROXWLRQ ILOWHUHG WKURXJK D EHG RI PHVK EDVLF DFWLYDWHG %URFNPDQQ ,f DOXPLQXP R[LGH 7KH UHVXOWDQW VROXWLRQ ZDV FRQFHQWUDWHG E\ URWDU\ HYDSRUDWRU WR \LHOG D FOHDU FRORUOHVV VOLJKWO\ YLVFRXV OLTXLG 7KLV PDWHULDO ZDV IUDFWLRQDOO\ GLVWLOOHG WKURXJK D FP YLJHUDX[ FROXPQ DQG J bf FOHDU FRORUOHVV SOHDVDQW VPHOOLQJ ZDV REWDLQHG LQ DQ HDUO\ IUDFWLRQ ERLOLQJ r& DW PP +J >7HWUDK\GURS\UDQ\OfR[\EXWDQDO f + 0+] &'&, 706f P +f S + -++ +]f GW + -++ +] M++ +]f P +f P +f W + M++ +]f W + -KK +]f & 0+] &'&, &+&,f 3UHSDUDWLRQ RI L7HWUDKYGUR)S\UDQYOfR[YGLIOXRURSHQWHQH f >7HWUDK\GUR+S\UDQ\OfR[\@ GLIOXRURSHQW HQH f ZDV SUHSDUHG E\ DGDSWDWLRQ RI D SURFHGXUH DV GHVFULEHG E\ 1DDH DQG %XUWRQ $ WKUHH QHFN / IODVN ZDV DVVHPEOHG XQGHU $U SXUJH ZLWK D PHFKDQLFDO VWLUUHU VHSWXP DQG WZR DGGLWLRQ IXQQHOV 7KH V\VWHP ZDV WKHQ IODPH GULHG XQGHU $U SXUJH 'LEURPRGLIOXRURPHWKDQH J [n PROf ZDV WUDQVIHUUHG WR D 5RWDIORZ WXEH GLVVROYHG LQ PO RI GU\ 7+) WKHQ V\ULQJHG LQWR WKH UHDFWLRQ YHVVHO IROORZHG E\ DQ DGGLWLRQDO PO RI GU\ 7+) 7KLV VROXWLRQ ZDV FRROHG WR r& E\ DQ LFHVDOW EDWK 'U\ 7+) POf ZDV SODFHG LQ DQ DGGLWLRQ IXQQHO IROORZHG E\ PO J [f PROf 31&+ff 5DSLG VWLUULQJ ZDV EHJXQ DQG WKH 31&+ff ZDV DGGHG GURSZLVH RYHU KRXU WR WKH &)%U VROXWLRQ ZLWK FRROLQJ $ ILQH ZKLWH SUHFLSLWDWH IRUPHG DV DGGLWLRQ FRQWLQXHG

PAGE 148

8SRQ FRPSOHWLQJ DGGLWLRQ RI WKH 31&+ff WKH PL[WXUH ZDV VWLUUHG DW r& IRU KRXU WKHQ EURXJKW WR 57 >7HWUDK\GUR+S\UDQ\OfR[\@EXWDQDO J [f PROf ZDV GLVVROYHG LQ PO RI GU\ 7+) DQG SODFHG LQ WKH VHFRQG DGGLWLRQ IXQQHO 7KH VROXWLRQ ZDV WKHQ DGGHG WR WKH \OLGH VROXWLRQ RYHU PLQXWHV DW 57 WKHQ VWLUUHG IRU KRXUV DW 57 $W WKLV WLPH WKH UHDFWLRQ PL[WXUH LV D \HOORZEURZQ VROXWLRQ ZLWK D ILQH \HOORZ SUHFLSLWDWH VHWWOLQJ RQ WKH ERWWRP RI WKH UHDFWLRQ YHVHO 7KH VROLGV ZHUH JUDYLW\ ILOWHUHG DQG ULQVHG ZLWK PO RI GLHWK\O HWKHU 7KLV VROXWLRQ ZDV FRQFHQWUDWHG RQ D URWDU\ HYDSRUDWRU WR m PO YROXPH ZKLFK ZDV WDNHQ XS LQ PO RI IUHVK GLHWK\O HWKHU DQG H[KDXVWLYHO\ H[WUDFWHG ZLWK ZDWHU 7KH HWKHU VROXWLRQ ZDV WKHQ GULHG RYHU 0J6&8 DQG WKH HWKHU UHPRYHG E\ GLVWLOODWLRQ XS WR r& DW PP +J >7HWUDK\GUR+S\UDQ\OfR[\@GLIOXRURSHQWHQH J b E\ LQWHUQDO VWDQGDUG ) 105 mb SXUH WKH UHPDLQGHU EHLQJ HWKHU DQG WUDFH 7+)f ZDV REWDLQHG DV D FOHDU OLJKW EURZQ OLTXLG IQaHWUDK\GUR+SYUDQ\R[YGLIOXRURSHQWHQH + 0+] &'&, 706f P +f P +f P +f P +f GWG + -WUDQV+) +] M++ +] -FVKI +]f W + -++ } +]f & 0+] &'&, &+&,f G & -&I +]f W & -&I +]f W & -&I +]f W & -&) +]f ) 0+] &'&,f &)&,f G ) -II +]f GG ) -)) +] -+) +]f 3UHSDUDWLRQ RI 'LIOXRURSHQWHQRO >7HWUDK\GUR:S\UDQ\OfR[\@GLIOXRURSHQWHQH f ZDV GHSURWHFWHG WR GLIOXRURSHQWHQRO f E\ DGDSWDWLRQ RI D SURFHGXUH DV GHVFULEHG E\ %HLHU DQG 0XQG\ >7HWUDK\GURS\UDQ\OfR[\@ GLIOXRURSHQWHQH J [nPRO GHOLYHUHG b SXUH LPSXULWLHV

PAGE 149

EHLQJ HWKHU DQG WUDFH 7+)ff ZDV GLVVROYHG LQ PO EXWDQHGLRO $FLG DFWLYDWHG 'RZH[ [ LRQ H[FKDQJH UHVLQ Jf ZDV DGGHG DQG WKH PL[WXUH VWLUUHG UDSLGO\ IRU KRXUV 7KH UHDFWLRQ ZDV WKHQ IODVK GLVWLOOHG GRZQ WR D SUHVVXUH RI PP +J $SSUR[LPDWHO\ PO RI 7+) DQG HWKHU ZDV FROOHFWHG XSRQ SXPS GRZQ RI WKH V\VWHP 7KH IUDFWLRQ ERLOLQJ EHWZHHQ DQG r& DSSOLHG EDWK WHPSHUDWXUHf ZDV FROOHFWHG WR \LHOG m PO FOHDU FRORUOHVV OLTXLG %HLQJ VOLJKWO\ DFLGLF WKLV PDWHULDO ZDV GLVWLOOHG RII RI J RI GU\ 1D+& WR \LHOG J bf FOHDU FRORUOHVV GLVWLOOLQJ IURP r& DW PP +J 'LIOXRURSHQWHQ RO f + 0+] &'&, 706f WW + -KK +] -+K +]f P +f EV +f W + -++ +]f GWG + -WUDQV+) +] -++ +] -FLV+) +]f & 0+] &'&, &+&,f G & -&) +]f W & -&I +]f W & -&I +]f GG & -&I +] -&) +]f ) 0+] &'&, &)&,f G ) -)) +]f GG ) -II +] -WUDQV+) +]f /RZ 5HVROXWLRQ 0DVV 6SHFWUXP P] b UHODWLYH LQWHQVLW\f f f f 3UHSDUDWLRQ RI 'LIOXRURSHQWHQDO 'LIOXRURSHQWHQDO f ZDV SUHSDUHG E\ DGDSWDWLRQ RI D SURFHGXUH DV GHVFULEHG E\ &RUH\ DQG 6FKPLGW $ URXQG ERWWRP IODVN ZDV IODPH GULHG XQGHU $U SXUJH DQG PO RI GU\ &+&, DGGHG 'LIOXRUR SHQWHQRO J [n PROf ZDV WKHQ DGGHG IROORZHG E\ J [f PROf S\ULGLQLXP GLFKURPDWH 7KH UHDFWLRQ PL[WXUH ZDV VWLUUHG DW 57 IRU KRXUV WKHQ GLOOXWHG ZLWK PO GLHWK\O HWKHU 7KH PL[WXUH ZDV WKHQ JUDYLW\ ILOWHUHG WR UHPRYH WKH EODFN VROLGV ZKLFK ZHUH ULQVHG ZLWK GLHWK\O HWKHU WKHQ WKH UHVXOWDQW EURZQEODFN VROXWLRQ ZDV ILOWHUHG WKURXJK D EHG RI PHVK EDVH DFWLYDWHG %URFNPDQQ ,f DOXPLQXP R[LGH &RQWDPLQDWLRQ E\ S\ULGLQH ZDV

PAGE 150

GHWHFWHG E\ */3& VR WKH UHDFWLRQ VROXWLRQ ZDV H[WUDFWHG ZLWK [ PO KDOI VDWXUDWHG &862 WKHQ [ PO ZDWHU %\ */3& WKH S\ULGLQH KDG EHHQ UHPRYHG VR WKH VROXWLRQ ZDV GULHG RYHU 0J6&! 7KH HWKHU DQG &+&, ZHUH FDUHIXOO\ GLVWLOOHG WKURXJK D FP YLJHUDX[ FROXPQ DQG WKH UHPDLQGHU WUDQVIHUUHG WR D PLFUR GLVWLOODWLRQ DSSDUDWXV $V WKH KHDWLQJ EDWK WHPSHUDWXUH ZDV UDLVHG WR r& ZLWK DQ DSSOLHG SUHVVXUH RI PP +J WKH UHPDLQGHU RI PDWHULDO EXPSHG RYHU 'XH WR WKH VPDOO DPRXQW RI PDWHULDO GLVWLOODWLRQ ZDV QRW DWWHPSWHG DJDLQ $ FOHDU OLJKW \HOORZ OLTXLG ZDV REWDLQHG EHLQJ b SXUH J bf FRQWDPLQDWHG ZLWK GLHWK\O HWKHU DQG &+&, 'LIOXRURSHQWHQDO f + 0+] &'&, 706f P +f WP + -++ +]f GWG + -WUDQV+) +] -++ +] -FLV+) +]f W + -++ +]f & 0+] &'&, &+&,f G & -&I +]f W & -&I +]f W & -&I +]f GG & -&I +] -&I +]f ) 0+] &'&, &)&,f G ) -II +] GG ) -)I +] -WUDQV+) +]f /RZ 5HVROXWLRQ 0DVV 6SHFWUXP P] b UHODWLYH LQWHQVLW\f f f f f f f +LJK 5HVROXWLRQ 0DVV 6SHFWUXP &DOFXODWHG IRU &+)2 0HDVXUHG 3UHSDUDWLRQ RI 7HWUDIOXRURKH[DGLHQH f 7HWUDIOXRURKH[DGLHQH f ZDV SUHSDUHG E\ DGDSWDWLRQ RI D SURFHGXUH DV GHVFULEHG E\ 1DDH DQG %XUWRQ $ WKUHH QHFNHG URXQG ERWWRP IODVN ZDV DVVHPEOHG ZLWK WZR VHSWD D SUHVVXUH HTXDOL]LQJ DGGLWLRQ IXQQHO PDJQHWLF VWLUUHU DQG IODPH GULHG XQGHU $U SXUJH 'LEURPRGLIOXRURPHWKDQH J [ 2n PROf ZDV WUDQVIHUUHG WR D 5RWDIORZ WXEH WKHQ GLVVROYHG LQ PO RI GU\ WULJO\PH DQG DGGHG WR WKH UHDFWLRQ YHVVHO E\ V\ULQJH 7KLV VROXWLRQ ZDV FRROHG WR r& ZLWK DQ LFHVDOW EDWK 31&+ff PO J [

PAGE 151

PROf ZDV GLVVROYHG LQ PO RI GU\ WULJO\PH LQ WKH DGGLWLRQ IXQQHO WKHQ DGGHG WR WKH &)%U VROXWLRQ RYHU PLQXWHV ZLWK JRRG VWLUULQJ DQG FRROLQJ DW r& 7KH UHVXOWDQW FORXG\ VROXWLRQ WKLFN ZLWK ZKLWH SUHFLSLWDWH ZDV VWLUUHG IRU KRXU DW r& WKHQ EURXJKW WR 57 'LIOXRURSHQWHQDO J [ 2f PROf ZDV GLVVROYHG LQ PO GU\ WULJO\PH DQG DGGHG WR WKH \OLGH VROXWLRQ DW 57 RYHU PLQXWHV 7KLV PL[WXUH ZDV DOORZHG WR VWLU IRU KRXUV DW 57 7KH UHDFWLRQ PL[WXUH ZDV WKHQ IODVK GLVWLOOHG LQWR D WZR QHFNHG 5RWDIORZ WUDS XS WR D EDWK WHPSHUDWXUH RI r& DW PP +J 7HWUDIOXRURKH[DGLHQH J bf ZDV REWDLQHG EHLQJ D FOHDU FRORUOHVV OLTXLG FRQWDLQLQJ WUDFHV RI GLHWK\O HWKHU &+&, DQG 231&+ff 7HWUDIOXRURKH[DGLHQH f + 0+] &'&, 706f P +f GP + -UDQ6+) +]f & 0+] &'&, &+&,f P &f W & -&I +=f GG & -&) +] -&I +]f ) 0+] &'&, &)&,f G ) -)) +] GG ) -II +] -WUDQV+) +]f /RZ 5HVROXWLRQ 0DVV 6SHFWUXP P] b UHODWLYH LQWHQVLW\f f f f f f f f +LJK 5HVROXWLRQ 0DVV 6SHFWUXP &DOFXODWHG IRU &+) 0HDVXUHG *DV 3KDVH 7KHUPRO\VLV RI 7HWUDIOXRURKH[DGLHQH $Q PJ VDPSOH RI ZDV REWDLQHG b SXUH E\ SUHSDUDWLYH */3& VHSHUDWLRQ IURP DQ 105 VROXWLRQ LQ &' &ROXPQ LQFK [ IHHW b 6( RQ &KURPRVRUE 3 2YHQ FRQVWDQW DW r& ,QMHFWRU r& 7&' EORFN r& +H IORZ UDWH POPLQXWHf (LJKW PLOOLPHWHU +J VDPSOHV RI ZHUH H[SDQGHG LQWR WKH JDV NLQHWLFV YHVVHO DV GHVFULEHG LQ $SSHQGL[ $ DQG FRQYHUVLRQ WR WHWUDIOXRURKH[DGLHQH f IROORZHG E\ */3& 6HH 7DEOH IRU GDWD &ROXPQ LQFK [ IHHW $J1&+&+&1

PAGE 152

b RQ &KURPRVRUE = 2YHQ FRQVWDQW DW r& 1 IORZ UDWH POPLQXWH 5HWHQWLRQ WLPHV PLQXWHV PLQXWHVf )ROORZLQJ WKH JDV SKDVH UHDFWLRQ YHUVXV LQWHUQDO VWDQGDUG QRFWDQH VKRZHG WKH \LHOG RI WKLV WUDQVIRUPDWLRQ WR EH b 5HYHUVLELOLW\ RI EDFN WR ZDV QRW REVHUYHG ,VRODWLRQ RI $ b VROXWLRQ RI LQ &H+ ZDV VHDOHG LQ D &DULXV WXEH DQG WKHUPRO\]HG DW r& IRU KRXUV ) 105 DW WKLV WLPH VKRZV RQO\ 3XUH ZDV LVRODWHG E\ SUHSDUDWLYH VFDOH */3& IURP WKLV VROXWLRQ &ROXPQ LQFK [ IHHW b 7ULWRQ ; RQ &KURPRVRUE : 2YHQ r& FRQVWDQW ,QMHFWRU r& 7&' EORFN r& +H IORZ UDWH POPLQXWHf 7HWUDIOXRURKH[DGLHQH f + 0+] &'&, 706f P +f P +f & 0+] &'&, &+&,f WW & -&) +] -&) +]f P &f W & -&I +]f ) 105 0+] &'&, &)&,f GP ) -+) +]f /RZ 5HVROXWLRQ 0DVV 6SHFWUXP P] b UHODWLYH LQWHQVLW\f f f f f f f f f f +LJK 5HVROXWLRQ 0DVV 6SHFWUXP &DOFXODWHG IRU &+) 0HDVXUHG 3UHSDUDWLRQ RI 0HWKYOLGHQHF\FORKH[DQRQH HWKYOHQH NHWDO 0HWK\OLGHQHF\FORKH[DQRQH HWK\OHQH NHWDO f ZDV SUHSDUHG E\ DGDSWDWLRQ RI D JHQHUDO SURFHGXUH $ PO WKUHH QHFNHG URXQG ERWWRP IODVN ZDV DVVHPEOHG ZLWK D PDJQHWLF VWLUUHU WZR SUHVVXUH HTXDOL]LQJ DGGLWLRQ IXQQHOV DQG D VHSWXP 7KH V\VWHP ZDV WKHQ IODPH GULHG XQGHU $U SXUJH &H+f3&+%U J [ 2n PROf ZDV DGGHG DQG D VOXUU\ FUHDWHG E\ WKH DGGLWLRQ RI PO RI GU\ 7+) 7KLV VOXUU\ ZDV FRROHG WR r& E\ DQ LFHZDWHU EDWK Q%XW\O OLWKLXP Q%X/Lf LQ QSHQWDQH PO RI D 0 VROXWLRQ [ 2n PROf

PAGE 153

7DEOH $YHUDJHG 3HUFHQW &RPSRVLWLRQ 'DWD IRU 7KHUPRO\VLV RI r& 6HFRQGV b r& 6HFRQGV b r& 6HFRQGV b r& 6HFRQGV b r& 6HFRQGV b r& 6HFRQGV b ZDV DGGHG WR DQ DGGLWLRQ IXQQHO ZLWK D 7HIORQ VWRSFRFN :KLOH YLJDURXVO\ VWLUULQJ WKH VOXUU\ WKH Q%X/L VROXWLRQ ZDV DGGHG RYHU PLQXWHV 7KH VROXWLRQ WXUQHG FDQDU\ \HOORZ XSRQ DGGLWLRQ RI Q%X/L $W PLQXWHV LQWR WKH DGGLWLRQ WKH PL[WXUH KDG EHFRPH D FOHDU GHHS \HOORZUHG KRPRJHQRXV VROXWLRQ 8SRQ FRPSOHWLRQ RI DGGLWLRQ RI WKH Q%X/L WKH VROXWLRQ ZDV ZDUPHG WR 57 DQG VWLUUHG IRU KRXU 7KH \OLGH VROXWLRQ ZDV WKHQ FRROHG WR r& DQG J [ 2n PROf

PAGE 154

F\FORKH[DQHGLRQH PRQRHWK\OHQH NHWDO LQ PO GU\ 7+) ZDV DGGHG GURSZLVH IURP WKH VHFRQG DGGLWLRQ IXQQHO RYHU PLQXWHV 7KH UHDFWLRQ PL[WXUH ZDV WKHQ VWLUUHG DW 57 IRU KRXUV WR \LHOG D FOHDU OLJKW \HOORZ VROXWLRQ FRQWDLQLQJ PXFK ILQH ZKLWH SUHFLSLWDWH :DWHU POf ZDV WKHQ DGGHG WR GHFRPSRVH DQ\ SRVVLEOH UHPDLQLQJ \OLGH 7KH VROLGV ZHUH JUDYLW\ ILOWHUHG DQG ULQVHG ZLWK PO 7+) DQG PO KH[DQHV 7KH VROXWLRQ ZDV WKHQ FRQFHQWUDWHG E\ URWDU\ HYDSRUDWRU WR \LHOG DQ RLO ZLWK VRPH ZKLWH VROLG 7KLV PDWHULDO ZDV WKHQ GLVVROYHG LQ PO PHWKDQRO DQG H[WUDFWHG ZLWK [ PO KH[DQHV 7KH FRPELQHG KH[DQHV ZKHUH WKHQ H[WUDFWHG ZLWK [ PO VDWXUDWHG DTXHRXV 1D&, 7KH KH[DQH VROXWLRQ ZDV WKHQ GULHG RYHU 0J6 DQG FRQFHQWUDWHG E\ URWDU\ HYDSRUDWRU WR \LHOG PO RI FOHDU RLO FRQWDLQLQJ VRPH ZKLWH FU\VWDOV 7KLV PDWHULDO ZDV GLVVROYHG LQ PO KH[DQHV DQG VHW DVLGH LQ D IUHH]HU DW r& IRU KRXUV 7KH VROXWLRQ ZDV YDFXXP ILOWHUHG ZKLOH FROGf WKURXJK D IULWWHG ILOWHU WR UHPRYH WKH ZKLWH FU\VWDOOLQH 23&H+f 7KH UHVXOWDQW FOHDU FRORUOHVV VROXWLRQ ZDV FRQFHQWUDWHG E\ URWDU\ HYDSRUDWRU WR \LHOG J bf FOHDU FRORUOHVV 0HWK\OLGHQHF\FORKH[DQRQH HWKYOHQH NHWDO + 0+] &'&, 706f W + -+K +]f W + -++ +]f V +f V +f 0+] &'&, &+&,f 3UHSDUDWLRQ RI 0HWKYOLGHQHFYFORKH[DQRQH 0HWK\OLGHQHF\FORKH[DQRQH f ZDV SUHSDUHG E\ DGDSWDWLRQ RI D SURFHGXUH DV GHVFULEHG E\ +XHW HW D 6LOLFD JHO Jf ZDV VXVSHQGHG LQ PO RI &+&, E\ UDSLG VWLUULQJ LQ D URXQG ERWWRP IODVN 6XOIXULF DFLG b Jf ZDV DGGHG WR WKH VLOLFD JHO VOXUU\ GURSZLVH $IWHU PLQXWHV WKH EHDGV RI DTXHRXV DFLG KDG EHHQ DGVRUEHG RQWR WKH VLOLFD JHO 0HWK\OLGHQH F\FORKH[DQRQH HWK\OHQH NHWDO J [ 2f PROf ZDV WKHQ DGGHG DQG UDSLG VWLUULQJ FRQWLQXHG $IWHU KRXUV */3& DQDO\VLV VKRZV D UDWLR RI

PAGE 155

GHSURWHFWHG WR SURWHFWHG NHWRQH 7KH VROXWLRQ ZDV ILOWHUHG WKHQ VXEMHFWHG WR D VHFRQG WUHDWPHQW DV DERYH J VLOLFD JHO J RI b +62f $IWHU KRXUV VWLUULQJ */3& DQDO\VLV VKRZV UDWLR RI 7KH VROXWLRQ ZDV WKHQ ILOWHUHG DQG WKH VLOLFD JHO ULQVHG ZLWK [ PO &+&, DQG WKHQ FRQFHQWUDWHG E\ URWDU\ HYDSRUDWRU WR \LHOG J RI OLJKW \HOORZ RLO 7KLV PDWHULDO ZDV GLVWLOOHG \LHOGLQJ DQG LQLWDO IUDFWLRQ RI &+&, IROORZHG E\ J bf FOHDU FRORUOHVV ERLOLQJ IURP r& DW PP +J 0HWK\OLGHQHFYFORKH[DQRQH + 0+] &'&, 706f P +f V +f m& 0+] &'&, &+&,f 3UHSDUDWLRQ RI 'LIOXRURPHWKYOLGHQHPHWKYOLGHQHFYFORKH[DQH 'LIOXRURPHWK\OLGHQHPHWK\OLGHQHF\FORKH[DQH f ZDV SUHSDUHG E\ DGDSWDWLRQ RI D SURFHGXUH DV GHVFULEHG E\ 1DDH DQG %XUWRQ $ PO WKUHH QHFNHG URXQG ERWWRP IODVN ZDV HTXLSSHG ZLWK D VHSWXP SUHVVXUH HTXDOL]LQJ DGGLWLRQ IXQQHO DQG VWURQJ PDJQHWLF VWLUUHU 7KH V\VWHP ZDV WKHQ IODPH GULHG XQGHU $U SXUJH 'LEURPRGLIOXRURPHWKDQH J [ 2n PROf ZDV ZHLJKHG RXW LQWR D 5RWDIORZ WXEH GLVVROYHG LQ PO GU\ 7+) WKHQ WUDQVIHUUHG WR WKH UHDFWLRQ YHVVHO E\ V\ULQJH 7KLV VROXWLRQ ZDV FRROHG WR r& 31&+ff PO J [n PROf ZDV WUDQVIHUUHG WR WKH DGGLWLRQ IXQQHO DQG GLVVROYHG LQ PO RI GU\ 7+) WKHQ DGGHG WR WKH &)%U VROXWLRQ GURSZLVH RYHU PLQXWHV ZLWK FRROLQJ 7KH UHVXOWDQW VOXUU\ RI ZKLWH SUHFLSLWDWH ZDV VWLUUHG KRXU WKHQ EURXJKW WR 57 0HWK\OLGHQHF\FORKH[DQRQH J [f PROf ZDV GLVVROYHG LQ PO GU\ 7+) DQG DGGHG GURSZLVH WR WKH \OLGH VROXWLRQ 7KLV PL[WXUH ZDV VWLUUHG IRU KRXUV DW 57 7KH \HOORZ VROLG ZDV JUDYLW\ ILOWHUHG DQG WKH VROXWLRQ FRQFHQWUDWHG WR PO YROXPH E\ VLPSOH GLVWLOODWLRQ 7KH OLTXLG ZDV WKHQ GLVVROYHG LQ PO GLHWK\O HWKHU DQG H[KDXVWLYHO\ H[WUDFWHG

PAGE 156

ZLWK ZDWHU 7KLV HWKHU VROXWLRQ ZDV WKHQ GULHG RYHU 0J6&! ILOWHUHG DQG GLVWLOOHG RII WKURXJK D FP YLJHUDX[ FROXPQ 7KH UHPDLQGHU RI WKH PDWHULDO ZDV WUDQVIHUUHG WR D PLFUR GLVWLOODWLRQ DSSDUDWXV DQG GLVWLOOHG XQGHU YDFXXP WR \LHOG J bf DV DQ HQG IUDFWLRQ ERLOLQJ r& DW PP +J 'LIOXRURPHWK\OLGHQHPHWKYOLGHQHFYFORKH[DQH + 0+] &'&O 706f P +f V +f & 0+] &'&, &+&,f W & -FI +]f W & -&I +]f W & -&I +]f ) 0+] &'&, &)&,f P )f /RZ 5HVROXWLRQ 0DVV 6SHFWUXP P] b UHODWLYH LQWHQVLW\f f f f f f f f f +LJK 5HVROXWLRQ 0DVV 6SHFWUXP &DOFXODWHG IRU &+) 0HDVXUHG *DV 3KDVH 7KHUPRO\VLV RI 'LIOXRURPHWKYOLGHQHPHWKYOLGHQHFYFORKH[DQH DP $Q m PJ VDPSOH RI ZDV REWDLQHG b SXUH E\ SUHSDUDWLYH */3& &ROXPQ LQFK [ IHHW b 6( RQ &KURPRVRUE 3 2YHQ FRQVWDQW DW r& ,QMHFWRU r& 7&' EORFN r& +H IORZ UDWH POPLQXWHf (LJKW PLOOLPHWHU +J VDPSOHV RI ZHUH H[SDQGHG LQWR WKH JDV NLQHWLFV YHVVHO DV GHVFULEHG LQ $SSHQGL[ $ DQG FRQYHUVLRQ WR GLIOXRUR GLPHWK\OLGHQHF\FORKH[DQH f IROORZHG E\ */3& 6HH 7DEOH IRU GDWD &ROXPQ LQFK [ IHHW b '13 RQ &KURPRVRUE :+3 2YHQ FRQVWDQW DW r& 1 IORZ UDWH POPLQXWH 5HWHQWLRQ WLPHV PLQXWHV PLQXWHVf )ROORZLQJ WKH JDV SKDVH UHDFWLRQ YHUVXV LQWHUQDO VWDQGDUG Q RFWDQH VKRZHG WKH \LHOG RI WKLV WUDQVIRUPDWLRQ WR EH b 5HYHUVLELOLW\ RI EDFN WR ZDV QRW REVHUYHG 'LIOXRUFGLPHWK\OLGHQHF\FORKH[DQH f ZDV LVRODWHG E\ WZLFH WKHUPRO\]LQJ PP +J VDPSOHV RI LQ ERWK

PAGE 157

WKHUPRO\VLV YHVVHOV IRU PLQXWHV DW r& DQG FROOHFWLQJ WKH SURGXFW LQ D 5RWDIORZ WXEH IRU DQDO\VLV 'LIOXRURGLPHWK\OLGHQHF\FORKH[DQH + 0+] &'&, 706f P +f P +f WW + -+) +] m-KK +]f P +f P +f P +f P +f ) 0+] &'&, &)&,f W ) -KI +]f /RZ 5HVROXWLRQ 0DVV 6SHFWUXP P] b UHODWLYH LQWHQVLW\f f f f f f +LJK 5HVROXWLRQ 0DVV 6SHFWUXP &DOFXODWHG IRU &+L) 0HDVXUHG 7DEOH $YHUDJHG 3HUFHQW &RPSRVLWLRQ 'DWD IRU 7KHUPRO\VLV RI r& 6HFRQGV r& 6HFRQGV r& 6HFRQGV

PAGE 158

7DEOH &RQWLQXHG r& 6HFRQGV r& 6HFRQGV r& 6HFRQGV 3UHSDUDWLRQ RI 'LGLIOXRURPHWKYOLGHQHfFYFORKH[DQH f 'LGLIOXRURPHWK\OLGHQHfF\FORKH[DQH f ZDV SUHSDUHG E\ DGDSWDWLRQ RI D SURFHGXUH DV GHVFULEHG E\ 1DDH DQG %XUWRQ $ PO WKUHH QHFNHG URXQG ERWWRP IODVN ZDV HTXLSSHG ZLWK D PHFKDQLFDO VWLUUHU VHSWXP DQG SUHVVXUH HTXDOL]LQJ DGGLWLRQ IXQQHO DQG IODPH GULHG XQGHU $U SXUJH 'LEURPRGLIOXRURPHWKDQH J [ PROf ZDV WUDQVIHUUHG WR D 5RWDIORZ WXEH WKHQ GLVVROYHG LQ PO RI GU\ 7+) 7KLV VROXWLRQ ZDV WUDQVIHUUHG WR WKH UHDFWLRQ YHVVHO E\ V\ULQJH IROORZHG E\ DQ DGGLWLRQDO PO GU\ 7+) 31&+ff PO J [n PROf ZDV GLVVROYHG LQ PO GU\ 7+) LQ WKH DGGLWLRQ IXQQHO 7KH &)%U VROXWLRQ ZDV FRROHG WR r& ZLWK DQ LFHVDOW EDWK WKHQ WKH 31&+ff VROXWLRQ ZDV DGGHG GURSZLVH RYHU KRXU 7KLV PL[WXUH ZDV VWLUUHG DW r& IRU KRXUV WKHQ EURXJKW WR 57 &\FORKH[DQHGLRQH J [nPROf ZDV GLVVROYHG LQ PO GU\ 7+) DQG DGGHG WR WKH \OLGH VROXWLRQ RYHU PLQXWHV 7KH UHDFWLRQ PL[WXUH ZDV WKHQ VWLUUHG IRU KRXUV DW 57 7KH SDOH \HOORZ VROLGV ZHUH WKHQ ILOWHUHG DZD\ IURP

PAGE 159

WKH \HOORZEURZQ VROXWLRQ 7KH VROXWLRQ ZDV WKHQ FRQFHQWUDWHG E\ URWDU\ HYDSRUDWRU GRZQ WR D YROXPH RI r PO ZKLFK ZDV WDNHQ XS LQ PO GLHWK\O HWKHU 7KH HWKHU VROXWLRQ ZDV H[KDXVWLYHO\ H[WUDFWHG ZLWK ZDWHU WKHQ GULHG RYHU 0J6&8 7KH HWKHU ZDV GLVWLOOHG RII WKURXJK D FP YLJHUDX[ FROXPQ WR OHDYH r PO RI FOHDU EURZQ OLTXLG 7KLV PDWHULDO ZDV WUDQVIHUUHG WR D PLFUR GLVWLOODWLRQ DSSDUDWXV DQG YDFXXP DSSOLHG GRZQ WR PP +J DQG r PO RI HWKHU IURWKHG RYHU $V D ODWHU IUDFWLRQ J bf FOHDU OLJKW \HOORZ ZDV REWDLQHG ERLOLQJ r& DW D SUHVVXUH RI PP +J 'LGLIOXRURPHWK\OLGHQHfFYFORKH[DQH + 0+] &'&, 706f S + -+I +]f & 0+] &'&, &+&,f P &f W & -FI +]f W & -&I +]f ) 0+] &'&, &)&,f VHSWHW ) -KI +]f /RZ 5HVROXWLRQ 0DVV 6SHFWUXP P] b UHODWLYH LQWHQVLW\f f f f f f f f f +LJK 5HVROXWLRQ 0DVV 6SHFWUXP &DOFXODWHG IRU &+) 0HDVXUHG *DV 3KDVH 7KHUPRO\VLV RI 'LGLIOXRURPHWKYOLGHQHFYFORKH[DQH f $Q r PJ VDPSOH RI ZDV REWDLQHG b SXUH E\ SUHSDUDWLYH */3& VHSHUDWLRQ IURP D VROXWLRQ LQ 7+) &ROXPQ LQFK [ IHHW b 6( RQ &KURPRVRUE 3 2YHQ FRQVWDQW DW r& ,QMHFWRU r& 7&' EORFN r& +H IORZ UDWH POPLQXWHf (LJKW PLOOLPHWHU +J VDPSOHV RI ZHUH H[SDQGHG LQWR WKH JDV NLQHWLFV YHVVHO DV GHVFULEHG LQ $SSHQGL[ $ DQG FRQYHUVLRQ WR WHWUDIOXRURGLPHWK\OLGHQHF\FORKH[DQH f IROORZHG E\ */3& 6HH 7DEOH IRU GDWD &ROXPQ LQFK [ IHHW b 4) RQ &KURPRVRUE :+3 2YHQ FRQVWDQW DW r& 1 IORZ UDWH POPLQXWH 5HWHQWLRQ WLPHV PLQXWHV PLQXWHVf )ROORZLQJ WKH UHDFWLRQ YHUVXV LQWHUQDO VWDQGDUG QRFWDQHf VKRZHG WKH \LHOG RI WKLV

PAGE 160

7DEOH $YHUDJHG 3HUFHQW &RPSRVLWLRQ 'DWD IRU 7KHUPRO\VLV RI r& 6HFRQGV r& 6HFRQGV r& 6HFRQGV r& 6HFRQGV r& 6HFRQGV r& 6HFRQGV WUDQVIRUPDWLRQ WR EH b 5HYHUVLELOLW\ RI EDFN WR ZDV QRW REVHUYHG 7KH SURGXFW ZDV LVRODWHG E\ WZLFH WKHUPRO\]LQJ PP +J VDPSOHV RI LQ ERWK WKHUPRO\VLV YHVVHOV IRU PLQXWHV DW r& DQG FROOHFWLQJ WKH SURGXFW LQ D 5RWDIORZ WXEH IRU DQDO\VLV 7HWUDIOXRURGLPHWKYOLGHQHFYFORKH[DQH + 0+] &'&, 706f EV +f V +f V +f 0+] &'&, &)&,f V )f /RZ 5HVROXWLRQ 0DVV 6SHFWUXP P] b UHODWLYH LQWHQVLW\f

PAGE 161

f f f f f +LJK 5HVROXWLRQ 0DVV 6SHFWUXP &DOFXODWHG IRU &+) 0HDVXUHG 3UHSDUDWLRQ RI 2[RFYFORSHQWYOfFYFORSHQWDQRQH f 2[RF\FORSHQW\OfF\FORSHQWDQRQH f ZDV SUHSDUHG E\ WKH PHWKRG RI 3DXO $ WKUHH QHFNHG URXQG ERWWRP IODVN ZDV HTXLSSHG ZLWK D FRQGHQVHU PDJQHWLF VWLUUHU DQG SUHVVXUH HTXDOL]LQJ DGGLWLRQ IXQQHO WKHQ IODPH GULHG XQGHU $U SXUJH )UHVKO\ FXW VRGLXP PHWDO J [ 2n PROf ZDV SODFHG LQ WKH IODVN IROORZHG E\ PO RI GU\ WROXHQH 7KH V\VWHP ZDV KHDWHG WR UHIOX[ DQG VWLUUHG UDSLGO\ EUHDNLQJ WKH 1Dr LQWR VPDOO VSKHUHV (WK\OR[RF\FORSHQWDQH FDUER[\ODWH J [ 2n PROf ZDV GLVVROYHG LQ PO RI WROXHQH DQG DGGHG GURSZLVH WR WKH 1Dr DW UHIOX[ ZLWK UDSLG VWLUULQJ 8SRQ FRPSOHWLRQ RI DGGLWLRQ WKH PL[WXUH ZDV KHDWHG DW UHIOX[ IRU KRXU DIWHU ZKLFK DOO RI WKH 1Dr PHWDO KDG EHHQ FRQVXPHG &KORURF\FORSHQWDQRQH J [a PROf ZDV GLVVROYHG LQ PO GU\ WROXHQH DQG DGGHG GURSZLVH WR WKH UHIOX[LQJ HQRODWH VROXWLRQ 8SRQ FRPSOHWLRQ RI DGGLWLRQ WKH PL[WXUH ZDV KHOG DW D JHQWOH UHIOX[ IRU KRXUV 7KH UHVXOWDQW VROLGV ZHUH WKHQ JUDYLW\ ILOWHUHG DQG WKH UHDFWLRQ VROXWLRQ H[WUDFWHG ZLWK [ PO RI ZDWHU WKHQ GULHG RYHU 0J6 7KH WROXHQH ZDV WKHQ UHPRYHG E\ URWDU\ HYDSRUDWRU WR \LHOG J bf FUXGH SURGXFW ZKLFK ZDV SXULILHG E\ .XJKHOURKU GLVWLOODWLRQ WR JLYH J bf SXUH ZKLWH VROLG HWK\O nELVPHWK\OHQHF\FORSHQWDQHFDUER[\ODWH 7KLV PDWHULDO ZDV DGGHG WR D URXQG ERWWRP IODVN FRQWDLQLQJ PO RI b +&, DQG DVVHPEOHG ZLWK D FRQGHQVHU 7KH PL[WXUH ZDV EURXJKW WR D JHQWOH UHIOX[ DQG HWKDQRO ZDV DGGHG POf XQWLO WKH PL[WXUH EHFDPH KRPRJHQRXV 7KH VROXWLRQ ZDV KHDWHG DW D JHQWOH UHIOX[ IRU KRXUV DW ZKLFK WLPH */3& DQDO\VLV VKRZHG WKH GHFDUER[\ODWLRQ WR EH b FRPSOHWH 7KH UHDFWLRQ VROXWLRQ ZDV H[WUDFWHG ZLWK [ PO GLHWK\O HWKHU DQG WKH HWKHU VROXWLRQ ZDV H[KDXVWLYHO\ H[WUDFWHG ZLWK

PAGE 162

ZDWHU WKHQ GULHG RYHU 0J6 7KH HWKHU ZDV UHPRYHG E\ URWDU\ HYDSRUDWRU DQG WKH UHVXOWDQW PDWHULDO SXULILHG E\ .XJKHOURKU GLVWLOODWLRQ WR \LHOG J bf VROLG ZKLWH 2[RF\FORSHQW\OfFYFORSHQWDQRQH f + 105 0+] &'&, 706f r P ?a?PHVR DQG GLfL P +PHVRDQG Gf! W +PHVRRU GO -KK r +]f W +PHVUG -KK +]f & 105 0+] &'&, &'&,f PHVR DQG GGLDVWHURPHUV 3UHSDUDWLRQ RI PHVR DQG G'LIOXRURPHWKYOLGHQHFYFORSHQWYOfGLIOXRUR PHWKYOLGHQHFYFORSHQWDQH QHVRFIf PHVR DQG G'LIOXRURPHWK\OLGHQHF\FORSHQW\OfGLIOXRUR PHWK\OLGHQHF\FORSHQWDQH QHVRFIf ZDV SUHSDUHG E\ DGDSWDWLRQ RI D SURFHGXUH DV GHVFULEHG E\ 1DDH DQG %XUWRQ $ PO WKUHH QHFNHG URXQG ERWWRP IODVN ZDV HTXLSSHG ZLWK D PHFKDQLFDO VWLUUHU SUHVVXUH HTXDOL]LQJ DGGLWLRQ IXQQHO VHSWXP DQG IODPH GULHG XQGHU $U SXUJH 'LEURPRGLIOXRURPHWKDQH J [B PROf ZDV WUDQVIHUUHG WR D 5RWDIORZ WXEH GLVVROYHG LQ PO GU\ 7+) WKHQ V\ULQJHG LQWR WKH UHDFWLRQ YHVVHO IROORZHG E\ PO GU\ 7+) 7KH &)%U VROXWLRQ ZDV WKHQ FRROHG WR r& 31&+ff PO J [f PROf ZDV WUDQVIHUUHG WR WKH DGGLWLRQ IXQQHO DQG GLVVROYHG LQ PO GU\ 7+) 7KLV VROXWLRQ ZDV DGGHG GURSZLVH WR WKH &)%U ZLWK FRROLQJ RYHU KRXUV 7KH UHVXOWDQW VOXUU\ RI ZKLWH VROLG ZDV VWLUUHG DW r& IRU KRXUV DIWHU ZKLFK LW ZDV KHDWHG WR r& 2[RF\FORSHQW\OfF\FORSHQWDQRQH J [ 2r PROf ZDV GLVVROYHG LQ PO GU\ 7+) DQG DGGHG GURSZLVH WR WKH \OLGH PL[WXUH DW r& RYHU KRXU ZLWK YLJRURXV VWLUULQJ 7KH PL[WXUH ZDV WKHQ VWLUUHG IRU KRXUV DW r& $W WKLV WLPH WKH \LHOG RI LV b DV FKHFNHG E\ ) 105 YHUVXV DGGHG &H+) 7KH

PAGE 163

UHVXOWDQW UHDFWLRQ PL[WXUH ZDV JUDYLW\ ILOWHUHG WR UHPRYH WKH WDQ VROLGV DQG WKH VROXWLRQ FRQFHQWUDWHG E\ URWDU\ HYDSRUDWRU WR \LHOG PO RI GDUN EURZQ YLVFRXV OLTXLG 'LHWK\O HWKHU POf ZDV DGGHG DQG WKLV VROXWLRQ H[KDXVWLYHO\ H[WUDFWHG ZLWK ZDWHU 7KH HWKHU SKDVH ZDV WKHQ GULHG RYHU 0J6 DQG FRQFHQWUDWHG E\ URWDU\ HYDSRUDWRU WR \LHOG J bf OLJKW EURZQ RLO EHLQJ b b 7+)GLHWK\O HWKHU DQG b 231&+ff PHVR DQG G 'LIOXRURPHWK\OLGHQHF\FORSHQW\KGLIOXRUR PHWKYOLGHQHFYFORSHQWDQH PHVRnL Gf + 105 0+] &'&, 706f P +PHVRDQG Gf! P +PHVRDQG c-f EV +rFK PHVRf EV +r FK GLf? ) 105 0+] &'&, &)&,f G )GL -II +]f G )PHVR -)) +]f G )PHVR -)) +]f G )G MII +]f & 105 0+] &+&, 706f PHVR DQG FGLDVWHURPHUV P &f W & -&) +]f W & -FI +]f /RZ 5HVROXWLRQ 0DVV 6SHFWUXP P] UHODWLYH LQWHQVLW\f PHVR f f f f f f f f GK f f f f f f f f +LJK 5HVROXWLRQ 0DVV 6SHFWUXP &DOFXODWHG IRU &L+) 0HDVXUHG GOf 0HDVXUHG ^PHVRf 6ROXWLRQ 3KDVH 7KHUPRO\VLV RI PHVR DQG G'LIOXRURPHWK\OLGHQH FYFORSHQWYOfGLIOXRURPHWKYOLGHQHFYFORSHQWDQH PHVRFIf $ J VDPSOH RI 'LIOXRURPHWK\OLGHQHF\FORSHQW\OfGLIOXRUR PHWK\OLGHQHF\FORSHQWDQH f ZDV REWDLQHG b SXUH E\ SUHSDUDWLYH */3& EHLQJ b DQG b F\FORSHQWHQ\OfWHWUDIOXRURHWK\Of F\FORSHQWHQH f &ROXPQ LQFK [ IHHW b 4) RQ &KURPRVRUE :+3 2YHQ FRQVWDQW DW r& ,QMHFWRU r& 7&' EORFN r& +H IORZ POPLQXWH 5HWHQWLRQ 7LPHV PLQXWHV PLQXWHVf

PAGE 164

7KLV PDWHULDO ZDV GLVVROYHG LQ J GU\ IUHH]HWKDZ GHJDVVHG QGRGHFDQH b SXUH $OGULFK &KHPLFDO &Rf DQG J &+) ZDV DGGHG DV ) 105 LQWHUQDO VWDQGDUG $V VDPSOHV ZHUH QHHGHG PO DOLTXRWV ZHUH GUDZQ E\ V\ULQJH DQG SODFHG LQ WKLFN ZDOOHG 105 WXEHV EDVH ULQVHG GHLRQL]HG ZDWHU ULQVHG DFHWRQH ULQVHG IODPH GULHGf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r& ,Q WKHUPRO\VLV RI PHVR VPDOO DPRXQWV RI RWKHU PDWHULDOV ZHUH HYLGHQFHG E\ ) 105 $W ORQJHU WLPHV LQ WKH WKHUPRO\VLV WULDOV WKHUH DSSHDUHG WUDFH DPRXQWV RI D VHULHV RI VLJQDOV

PAGE 165

IURP WKURXJK D WRWDO RI WHQ VHWV RI PXOWLSOHWV 7KH ODUJHVW FRXSOLQJV REVHUYHG ZHUH RQ WKH RUGHU RI +] $OVR REVHUYHG DW ORQJHU WLPHV ZDV D VLQJOHW RI ODUJHU LQWHQVLW\ DW %RWK PDWHULDOV ZRXOG DFFRXQW IRU OHVV WKDQ b RI WKH UHDFWLRQ PL[WXUH 7KH SURGXFW ZDV REWDLQHG IRU FKDUDFWHUL]DWLRQ E\ WKHUPRO\]LQJ D FUXGH b b 7+)GLHWK\O HWKHU DQG b KH[DPHWK\OSKRVSKRULF WULDPLGHf VDPSOH RI DW r& IRU KRXUV WKHQ LVRODWLQJ WKH SURGXFW DZD\ IURP WKH XQUHDFWHG PHVR E\ SUHSDUDWLYH */3& &ROXPQ LQFK [ IHHW b 4) RQ &KURPRVRUE :+3 2YHQ FRQVWDQW DW r& ,QMHFWRU r& 7&' EORFN r& +H IORZ POPLQXWHf + &\FORSHQWHQYKWHWUDIOXRURHWKYQF\FORSHQWHQH + 105 0+] &'&, 706f S + -+K +]f P +f EV +f & 105 0+] &'&, 706f P & -&I +]f P & -&I +]f ) 105 0+] &'&, &)&,f V +f /RZ 5HVROXWLRQ 0DVV 6SHFWUXP P] UHODWLYH LQWHQVLW\f f f f f f f f f +LJK 5HVROXWLRQ 0DVV 6SHFWUXP &DOFXODWHG IRU &L+) 0HDVXUHG 7DEOH ) 105 5DWLRV IRU 7KHUPRO\VLV RI GDQG PHVR 'LIOXRURPHWK\OLGHQHF\FORSHQW\OfGLIOXRURPHWK\OLGHQHF\FORSHQWDQH G0 PHVRf DW DQG r& 7KHUPRO\VLV DW r& 6HFRQGV bFI bPHVR b

PAGE 166

7DEOH &RQWLQXHG 7HPSHUDWXUH ZDV WKHQ UDLVHG WR r& 6HFRQGV bG bPHVRn?n? b 7DEOH ) 105 5DWLRV IRU 7KHUPRO\VLV RI GO 'LIOXRUR PHWK\OLGHQHF\FORSHQW\OfGLIOXRURPHWK\OLGHQHF\FORSHQWDQH Gf DW r& 6HFRQGV bGO bPHVR b

PAGE 167

7DEOH ) 105 5DWLRV IRU 7KHUPRO\VLV RI GDQG PHVR 'LIOXRURPHWK\OLGHQHF\FORSHQW\OfGLIOXRURPHWK\OLGHQHF\FORSHQWDQH G PHVRf DW DQG r& 7KHUPRO\VLV DW r& 6HFRQGV bG bPHVR b 7HPSHUDWXUH ZDV WKHQ UDLVHG WR r& 6HFRQGV bG bPHVR? b

PAGE 168

7DEOH ) 105 5DWLRV IRU 7KHUPRO\VLV RI GO DQG PHVR 'LIOXRURPHWK\OLGHQHF\FORSHQW\OfGLIOXRURPHWK\OLGHQHF\FORSHQWDQH FI PHVRf DW DQG r& 7KHUPRO\VLV DW r& 6HFRQGV bFI bPHVR b 7HPSHUDWXUH ZDV WKHQ UDLVHG WR r& 6HFRQGV bG b PHV R b

PAGE 169

$33(1',; $ *$6 3+$6( 7+(502/<6,6 $33$5$786 .H\ 5RWDIORZ MRLQWV $ PROWHQ VDOW EDWK E\ ZHLJKW RI 1D1&! .12 %UHVLVWDQFH FRLO & WKHUPRFRXSOHV VWLUUHU ( PO 3\UH[ NLQHWLF EXOEV ) 5RWDIORZ VDPSOLQJ WXEH VWDUWLQJ PDWHULDO VWRFN LQ 5RWDIORZ WXEH + 3LUDQL 35& JDXJH KHDG +J 8WXEH PDQRPHWHU / EDOODVW DW PP +J RI DUJRQ OLTXLG QLWURJHQ WUDS / YDFXXP SXPS )LJXUH $ 'LDJUDP RI *DV .LQHWLFV $SSDUDWXV $OO WKHUPDO LVRPHUL]DWLRQV ZHUH FDUULHG RXW LQ FRQGLWLRQHG VSKHULFDO 3\UH[ PO EXOEV 7KHVH EXOEV ZHUH VXEPHUJHG LQ D VWLUUHG 'f PROWHQ VDOW EDWK $ HXWHFWLF PL[WXUH E\ ZHLJKW RI 1D1 .12 PS r&f 7KH EDWK ZDV KHDWHG E\ D UHVLVWDQFH FRLO %f DQG WHPSHUDWXUH VHW DQG PDLQWDLQHG E\ DQ 2PHJD 0RGHO 3URSRUWLRQLQJ &RQWUROOHU ZLWK SODWLQXP UHVLVWDQFH WKHUPRFRXSOH 7KH WHPSHUDWXUH IRU D UXQ ZDV PHDVXUHG ZLWK DQ 2PHJD 0RGHO

PAGE 170

++ 0LFURSURFHVVRU 7KHUPRPHWHU ZLWK D W\SH )H&X1Lf WKHUPRFRXSOH 7KH WKHUPRFRXSOHV ZHUH LPPHUVHG LQ WKH VDOW EDWK GLUHFWO\ EHWZHHQ WKH S\URO\VLV YHVVHOV 4f 7KH WHPSHUDWXUHV ZHUH IRXQG WR EH FRQVWDQW WR ZLWKLQ r& RYHU D UXQ $ W\SLFDO UXQ LQYROYHV WKH IROORZLQJ JHQHUDO SURFHGXUH 7KH OLQH DQG S\URO\VLV YHVVHOV DUH SXPSHG GRZQ ZLWK D KLJK FDSDFLW\ :HOFK 'XR6HDO URWDU\ YDQH YDFXXP SXPS /f DQG WKH XOWLPDWH YDFXXP f PP +Jf PRQLWRUHG ZLWK DQ (GZDUGV 3LUDQL 0RGHO GLVSOD\ DQG 3LUDQL PRGHO 35& JDXJH KHDG +f 7KH SXPS DQG OLTXLG QLWURJHQ WUDS .f DUH VHDOHG RII f DQG DQ LQLWLDO SUHVVXUH RI s PP +J RI VWDUWLQJ PDWHULDO PHDVXUHG ZLWK D +J 8 WXEH PDQRPHWHU ,f LV LQWURGXFHG LQWR WKH YDFXXP OLQH E\ H[SDQVLRQ IURP D FRROHG 5RWDIORZ WXEH ef $ VDPSOH LV WKHQ H[SDQGHG LQWR WKH NLQHWLFV YHVVHOV ( DQG f DQG WLPLQJ VWDUWHG IRU WKH UXQ 7KH H[FHVV VWDUWLQJ PDWHULDO UHPDLQLQJ LQ WKH OLQH DW WKLV WLPH LV FRQGHQVHG LQWR WKH VWRUDJH YHVVHO f DQG WKH OLQH LV SXPSHG GRZQ $W D GHVLUHG WLPH WKH SXPS LV FXW RXW f DQG D VDPSOH H[SDQGHG LQWR WKH VDPSOLQJ 5RWDIORZ WXEH (f 7KH SXPS LV WKHQ FXW RXW DQG WKH VDPSOH GLOOXWHG ZLWK DUJRQ IURP D ILYH OLWHU EXOE f WR FUHDWH D VDPSOH ZLWK D WRWDO SUHVVXUH RI DSSUR[LPDWHO\ PP +J DQG UHPRYHG WR PDNH PXOWLSOH */3& LQMHFWLRQV YLD D JDV VDPSOLQJ YDOYH 7KH SXPS LV WKHQ FXW LQ f DQG WKH OLQH SXPSHG GRZQ ZLWK D IUHVK VDPSOLQJ WXEH (f LQ SUHSDUDWLRQ IRU WKH QH[W VDPSOH (DFK NLQHWLF WKHUPRO\VLV UXQ ZDV VDPSOHG DW OHDVW ILYH WLPHV $ +HZOHWW 3DFNDUG 6HULHV ,, JDV FKURPDWRJUDSK ZLWK D IODPH LRQL]DWLRQ GHWHFWRU DQG D +HZOHWW 3DFNDUG $ LQWHJUDWRU ZDV XVHG WR DQDO\]H WKH VDPSOHV GUDZQ %DVHOLQH UHVROXWLRQ RI SHDNV ZDV REVHUYHG IRU DOO TXDQWLWDWLYH */3& VWXGLHV (DFK SRLQW LQ D UDWH FRQVWDQW LV DQ DYHUDJH RI DW OHDVW WKUHH */3& LQMHFWLRQV

PAGE 171

7KH JDV VDPSOLQJ WHFKQLTXH XWLOL]HG LQ DOO RI WKH DERYHGHVFULEHG VWXGLHV LQWURGXFHG PXOWLSOH SUHVVXUH YDULDWLRQV SHU UXQ 7KH IDFW WKDW JRRG XQL PROHFXODU EHKDYLRU ZDV DOZD\V REVHUYHG LQGLFDWHV FOHDUO\ WKH ODFN RI VLJQLILFDQW VXUIDFH HIIHFW SUREOHPV 7KH NLQHWLF DSSDUDWXV LV PRGHOHG DIWHU WKH DSSDUDWXV DQG WHFKQLTXH RI 'U + 0 )UH\ 8QLYHUVLW\ RI 5HDGLQJ (QJODQG

PAGE 172

$33(1',; % 6(/(&7(' 105 63(&75$ 7KH ) 105 VSHFWUD RI QHZ FRPSRXQGV DUH JUDSKLFDOO\ LOOXVWUDWHG LQ WKLV DSSHQGL[ 7KH VSHFWUD DUH SUHVHQWHG QXPHULFDOO\ LQ WKHLU UHVSHFWLYH DUHDV LQ &KDSWHU 7KH FRPSRXQGV ( DQG = KDYH EHHQ SUHYLRXVO\ UHSRUWHG DV GLVFXVVHG LQ &KDSWHU 7KH VSHFWUD DUH VKRZQ LQ RUGHU RI WKHLU GLVVHUWDWLRQ LGHQWLILFDWLRQ QXPEHU DQG WKH FRPSRXQGV ZKLFK KDYH EHHQ LQFOXGHG LQ WKLV DSSHQGL[ DUH DW r r& DQG r&f e = PHVR GO DQG

PAGE 173

)LJXUH % %LVWULIOXRURHWKHQ\OfSKHQDQWKUHQH f DW r& LQ &'&,

PAGE 174

.*n22W Lf§Lf§_f§Lf§Lf§Lf§Lf§Ua!f§}f§ff§ff§_f§rf§rf§ff§f§U ORR QR D )LJXUH % %LVWULIOXRURHWKHQ\OfSKHQDQWKUHQH f DW r& LQ &'&,

PAGE 175

)LJXUH % %LVWULIOXRURHWKHQ\OfSKHQDQWKUHQH f DW r& LQ &'&,

PAGE 176

77 W D  V // Q L Lf§> L L L L L L L Lf§L Lf§Lf§Lf§Lf§Lf§_f§Lf§Lf§Lf§Lf§Lf§Pf§U L nf§Lf§U DR QR 330 )LJXUH % +H[DIOXRURGLK\GURWULSKHQ\OHQH f LQ &'&,

PAGE 177

L UL L L L L L L L L U > LM 0 L L L L L L L QQaSL L L QUUQ L L L L L L P L L L L L L L L L L L Q L UL Q L L UL L L L L L L L L L L 330 )LJXUH % +H[DIOXRURSKHQDQWKURfELF\FOR>@KH[HQH f LQ &'&,

PAGE 178

)LJXUH % ([SDQVLRQ RI IRU WKH SSP 5HJLRQ RI +H[DIOXRURSKHQDQWKURfELF\FOR>@KH[HQH f LQ &'&,

PAGE 179

)LJXUH % ([SDQVLRQ RI IRU WKH SSP 5HJLRQ RI ,06HH+H[DIOXRURA6A,2SKHQDQWKUR-ELF\FOR,6,2MKH[AHQH f LQ &'&,

PAGE 180

UM7777777 WWMW L0LL LL Uc P L L L L L L W UUUL L L L L L L L P L L L } UUL UPUMUP WW L L L L } L L LL L L L L L L LW L L } P P7UQ L} L 330 )LJXUH % ([SDQVLRQ RI IRU WKH SSP 5HJLRQ RI +H[DIOXRURffSKHQDQWKURfELF\FOR>@KH[HQH f LQ &'&,

PAGE 181

)LJXUH % ([SDQVLRQ RI IRU WKH SSP 5HJLRQ RI 0$6HH+H[DIOXRURA;JO2SKHQDQWKUR-ELF\FORW6,2OKH[AHQH f LQ &'&,

PAGE 182

)LJXUH % ([SDQVLRQ RI IRU WKH SSP 5HJLRQ RI +H[DIOXRURSKHQDQWKURfELF\FOR>@KH[HQH f LQ &'&,

PAGE 183

-c W M L L L L L L L L L @ U f§ n L 330 )LJXUH % ([SDQVLRQ RI IRU WKH SSP 5HJLRQ RI ,AA6HH+H[DIOXRURA6L2-2SKHQDQWKUR-ELF\FORA,2OKH[AHQH f LQ &'&,

PAGE 184

)LJXUH % 'LIOXRURPHWK\OLGHQHWHWUDIOXRURfOSKHQDQWKURfF\FORSHQWHQH f LQ &'&,

PAGE 185

, -rra L ,f§U n U 77 L M Ua7f§U_f§Lf§Ua Lf§Lf§>f§Lf§Lf§Lf§Lf§_f§Lf§Lf§Lf§? U Lf§Lf§Lf§Uf§Lf§Lf§Lf§Lf§Lf§Af§Wf§UaLf§Lf§_f§Lf§UaUf§}f§Lf§Uf§Uf§U f§U WaUaW W L W W aLa Ua nR WR R ORR QR r"R SSP )LJXUH % 3KHQDQWKURfWULIOXRURWULIOXRURPHWK\OF\FORSHQWDGLHQH f LQ &'&,

PAGE 186

) 0 0 ,, , , ,, f , , @ W ,W , , c , 0 , , @ W ,W _ 0 , , , , , 7 0 f 0 ,, @ 0 , 0 a , \ , , 7 % 330 )LJXUH % 3HUIOXRUR(((A6GLPHWK\OAAHRFWDWULHQH (f LQ Q3HQWDQH

PAGE 187

)LJXUH % 3HUIOXRUR(=( DQG (((GLPHWK\ORFWDWULHQH =(ff LQ Q3HQWDQH

PAGE 188

)LJXUH % 3HUIOXRURUDQVWHWUDPHWK\OF\FORKH[DGLHQH f LQ Q3HQWDQH

PAGE 189

3HUIOXRURIUDQVWHWUDPHWK\OF\FORKH[DGLHQH f LQ Q3HQWDQH

PAGE 190

L U_ UUU LMQ Q\QQL UUU UUUUUU_77U7S7UU_L7U7 @ P U MrUU UU\Q U ULaUUUU SUQ UM Q UUSUUU _aU UU U_ LW )LJXUH % 3HUIOXRURIUDQVA66HWHWUDPHWK\OELF\FORA2OKH[AHQH f LQ Q3HQWDQH

PAGE 191

L W UUUUM WWL UMUPM UUUUMUP L } LWMWW U W M M L U7S LWL > L L L L L L L L L L L L KWWL \UQ L Q Q _UUU L S fr 330 )LJXUH % ([SDQVLRQ RI IRU WKH WR SSP 5HJLRQ RI 3HUIOXRURIUDQVWHWUDPHWK\OELF\FOR>@KH[HQH f LQ Q3HQWDQH

PAGE 192

W U U W Uf§Mf§Lf§Wf§Lf§Lf§_f§f§f§Lf§Lf§_f§Uf§Lf§Lf§Lf§Mf§"f§Lf§U 330 )LJXUH % ([SDQVLRQ RI IRU WKH WR SSP 5HJLRQ RI 3HUIOXRURInDQVWHWUDPHWK\OELF\FOR>@KH[HQH f LQ Q3HQWDQH

PAGE 193

3HUIOXRURIUDQVWHWUDPHWK\OELF\FOR>@KH[HQH f LQ Q3HQWDQH

PAGE 194

U3 U! 77UU773 UQMPL @ W L U IWW UL7M U UL\Q LLSLQMLQU@LLLLQLL +777aA3aUUUUIa07777L77cWWYLWW UUUS Q7_LP_P7>UPSLLU_PQQ p frr f 330 )LJXUH % 7HWUDIOXRURKH[DGLHQH f LQ &'&,

PAGE 195

QVH]IO )LJXUH % 7HWUDIOXRURKH[DGLHQH f LQ &'&,

PAGE 196

YL 9 $ L ,f§Lf§L ,7@f§,f§,f§Lf§,f§@f§U f§,f§,f§,f§,f§,f§,f§,f§,f§,f§, 330 YM 77777 ,77777777777-7777777777777777 79_ , , )77O I7777777Q _7, U777777-77O O_OO Q I777 U77777-7O R )LJXUH % GO DQG PHVR'LIOXRURPHWK\OLGHQHF\FORSHQW\Of GLIOXRURPHWK\OLGHQHF\FORSHQWDQH GO HVRf LQ &'&,

PAGE 197

5 PHVD f UULP 77,77S777 77, 7W /; UUUUSUUUL UUUUUSUQ L L PUUUQM UU7U7UUU7S7U7UUUUM QU77UUU@ LUUUL7777_Q _UQ UM L )LJXUH % 7KHUPRO\VLV RI PHVR'LIOXRURPHWK\OLGHQHF\FORSHQW\Of GLIOXRURPHWK\OLGHQHF\FORSHQWDQH PHVRf 6DPSOH &RQWDLQLQJ &\FORSHQW\Of WHWUDIOXRURHWK\OfF\FORSHQWHQH f DQG &H+) SSPf LQ Q'RGHFDQH

PAGE 198

5()(5(1&(6 )OXRULQH 7KH )LUVW +XQGUHG f

PAGE 199

%HQQHWW *0 %URRNV */ DQG *ODVVWRQH 6 &KHP 6RF 'DOWRQ 7UDQV 3DUW ,, f 6WUHLWZLHVHU -U $ DQG 0DUHV ) $P &KHP 6RF f %HUQDUGL ) 0DQJLQL $ (SLRWLV 1' /DUVRQ -5 DQG 6KDLN 6 $P &KHP 6RF ^f 6LOYHUVWHLQ 50 %DVVOHU *& DQG 0RUULOO 7& 6SHFWURPHWULF ,GHQWLILFDWLRQ RI 2UJDQLF &RPSRXQGV -RKQ :LOH\ DQG 6RQV 1HZ
PAGE 200

&XUU\ 0DQG 6WHYHQV ,'5 &KHP 6RF 3HUNLQ 7UDQV ,, f 5XGROI 6SHOOPH\HU '& DQG +RXN .1 2UJ &KHP f +RXN .1 6SHOOPH\HU '& -HIIRUG &: 5OPEDXOW &* :DQJ < DQG 0LOOHU 5' 2UJ &KHP f 3LUNOH :+ DQG 0F.HQGU\ /+ $P &KHP 6RF f 'ROEOHU -U :5 .RURQODN + %XUWRQ '+HOQ]H 3/ %DLOH\ $5 6KDZ *6 DQG +DQVHQ 6: $P &KHP 6RF f 'ROELHU -U :5 *UD\ 7$ &HOHZLF] / DQG .RURQLDN + $P &KHP 6RF f 6FKODJ (: DQG 3HDWPDQ :% $P &KHP 6RF f 5 : &DUU DQG :DOWHUV :' 3K\V &KHP f %HQVRQ 6: DQG 2n1HDO +( .LQHWLF 'DWD RQ *DV 3KDVH 8QLPROHFXODU 5HDFWLRQV 1DWLRQDO %XUHDX RI 6WDQGDUGV 1DWLRQDO 6WDQGDUG 5HIHUHQFH 'DWD 6HULHV :DVKLQJWRQ '& f *UHHQEXUJ $ DQG /LHEPDQ -) 6WUDLQHG 2UJDQLF 0ROHFXOHV (GLWRU :DVVHUPDQ ++ $FDGHPLF 3UHVV 1HZ
PAGE 201

9RQ (JJHUV 'RHULQJ : 5RWK :5 %RHQNH 0 %UHXFNPDQQ 5 5XKNDPS DQG :RUWPDQQ 2 &KHP %HU ^f %HQVRQ 6: 7KHUPRFKHPLFDO .LQHWLFV -RKQ :LOH\ DQG 6RQV 1HZ
PAGE 202

*DDVEHHN &+RJHYHHQ + DQG 9ROJHU +& 5HF 7UDY &KLP f -DFREV +-& DQG +DYLQJD ( LQ $GYDQFHV LQ 3KRWRFKHPLVWU\ -RKQ :LOH\ DQG 6RQV 1HZ f %HODQJHU DQG 6DQGRUI\ & &KHP 3K\V /HWW f 3RWWLHU 5+ 6HPHOXN *3 DQG 6WHYHQV 5'6 6SHFWURVFRS\ /HWW f 0RGHOHG RQ D 6LOLFRQ *UDSKLFV ,5,6' 6HULHV :RUNVWDWLRQ UXQQLQJ 0DFUR 0RGHO YHUVLRQ ; 1RYHPEHU IURP &ROXPELD 8QLYHUVLW\ 'HSDUWPHQW RI &KHPLVWU\ 1HZ
PAGE 203

0HLQZDOG DQG 0D]]RFFKL 3+ $P &KHP 6RF ^f 6XNXPDUDQ .% DQG +DUYH\ 5* 2UJ &KHP f 3DGZD $ DQG &ORXJK 6 $P &KHP 6RF f 3DGZD $ %URGVN\ / DQG &ORXJK 6 $P &KHP 6RF f &RXUWRW 3 6DODQ DQG 5XPOQ 5 7HWUDKHGURQ /HWW f 7DQDND DQG )XNXL %XOO &KHP 6RF -SQ f 'DXEHQ :* DQG .HOORJJ 06 $P &KHP 6RF f 6DOHP / $FF &KHP 5HV ^f %RQDFLF.RXWHFN\ 9 $P &KHP 6RF ^f :RQLQJ /LWMHQ )$7 DQG /DDUKRYHQ :+ 2UJ &KHP f 6FKODJ (: DQG .DLVHU -U (: $P &KHP 6RF ^f +HLPJDUWQHU + +DQVHQ +DQG 6FKPLG + +HOY &KLP $FWD f %HOODV 0 %U\FH6PLWK % &ODUNH 07 *LOEHUW $ .OXQNLQ .UHVWRQRVLFK 6 0DQQLQJ & DQG :LOVRQ 6 &KHP 6RF 3HUNLQ 7UDQV f /DPEHUWV --0 DQG /DDUKRYHQ :+ 2UJ &KHP f .DUSRY 90 3ODWDQRY 9( 6WRO\DURYD 7$ DQG
PAGE 204

3LFKNR 9$ 6LPNLQ %< DQG 0LQNLQ 9, 2UJ &KHP f 0DUYHOO (1 7HWUDKHGURQ ^f .RPRUQLFNL $ DQG 0FOYHU -U -: $P &KHP 6RF ^f %DOGZLQ -( 5HGG\ 93 6FKDDG /DQG +HVV -U %$ $P &KHP 6RF ^f +RXN .1 *XVWDIVRQ 60 DQG %ODFN .$ $P &KHP 6RF f +XUG &' DQG 3ROODFN 0$ 2UJ &KHP f /HY\ + DQG &RSH $& $P &KHP 6RF f %URZQ $ 'HZDU 0-6 DQG 6FKRHOOHU : $P &KHP 6RF f 0RURNXPD %RUGHQ :7 DQG +URYDW '$ $P &KHP 6RF f 'XSXLV 0 0XUUD\ & DQG 'DYLGVRQ (5 $P &KHP 6RF f 'HZDU 0-6 .LUVFKQHU 6 .ROOPDU +: DQG :DGH /( $P &KHP 6RF ^f 6KDUH 3( .RPSD ./ 3H\HULPKRII 6' DQG YDQ +HPHUW 0& &KHPLFDO 3K\VLFV f 3XUULQJWRQ 67 DQG :HHNV 6& )OXRULQH &KHP f $QGUHHY 9* .RORPLHWV $) DQG )RNLQ $9 )OXRULQH &KHP f 9RQ ( 'RHULQJ : 7RVFDQR 9* DQG %HDVOH\ *+ 7HWUDKHGURQ f 'ROELHU -U :5 $OW\ $& DQG 3KDQVWLHO ,9 2 $P &KHP 6RF f *DMHZVNL -DQG -LPHQH] -/ $P &KHP 6RF f 9RQ ( 'RHULQJ : DQG 7URLVH &$ $P &KHP 6RF f 6KHD .DQG 3KLOOLSV 5% $P &KHP 6RF f +RIIPDQQ +05 DQG 5DEH 2UJ &KHP f 1DDH '* DQG %XUWRQ '6\QWK&RPPXQ f

PAGE 205

)XUQLVV %6 +DQQDIRUG $6PLWK 3:* DQG 7DWFKHOO $5 9RJHOnV 7H[WERRN RI 3UDFWLFDO 2UJDQLF &KHPLVWU\ /RQJPDQ 6FLHQWLILF DQG 7HFKQLFDO (VVH[ (QJODQG (GLWLRQ f +XHW ) /HFKHYDOOLHU $ 3HOOHW 0 DQG &RQLD -0 6\QWKHVLV f 3DXO +f &KHP %HU f +DPPRQG *6 $P &KHP 6RF f )DUFDVLX &KHP (G ^f 'HZDU 0-6 DQG -LH & $FF &KHP 5HV f 'HZDU 0-6 DQG +HDO\ () &KHP 3K\V /HWW f *DMHZVNL -DQG &RQUDG 1' $P &KHP 6RF f 5RWK :5 /HQQDUW] +: YRQ ( 'RHULQJ : %LUODGHDQX / *X\WRQ &$ DQG .LWDJDZD 7 $P &KHP 6RF f 1DNDL 7 $SSOLFDWLRQ RI )(QRODWH &KHPLVWU\ &ODLVHQ 5HDUUDQJHPHQW RI )OXRULQDWHG (QRO (WKHU 6\VWHPV 3UHVHQWDWLRQ DW WKH (OHYHQWK $&6 :LQWHU )OXRULQH &RQIHUHQFH 6W 3HWHUVEXUJ )/ -DQXDU\ /HPDO '0 5HDUUDQJHPHQWV RI )OXRULQDWHG 'LHQHV DQG 7ULHQHV LQ *URXQG DQG ([FLWHG 6WDWHV 3UHVHQWDWLRQ DW WKH (OHYHQWK $&6 :LQWHU )OXRULQH &RQIHUHQFH 6W 3HWHUVEXUJ )/ -DQXDU\ +HLQ]H 3/ 6SDZQ 7' %XUWRQ 'DQG 6KLQ
PAGE 206

%,2*5$3+,&$/ 6.(7&+ .HLWK :LQILHOG 3DOPHU ZDV ERUQ 6HSWHPEHU LQ *DLQHVYLOOH )ORULGD 7KH ILUVW IHZ \HDUV RI KLV OLIH ZHUH VSHQW IHHGLQJ PDUVKPDOORZV WR WKH DOOLJDWRUV UHVLGLQJ LQ /DNH $OLFH )RU IHDU RI ORVV RI OLPE KLV SDUHQWV GHFLGHG D PRYH WR 1HZ
PAGE 207

, FHUWLI\ WKDW KDYH UHDG WKLV VWXG\ DQG WKDW LQ P\ RSLQLRQ LW FRQIRUPV WR DFFHSWDEOH VWDQGDUGV RI VFKRODUO\ SUHVHQWDWLRQ DQG LV IXOO\ DGHTXDWH LQ VFRSH DQG TXDOLW\ DV D GLVVHUWDWLRQ IRU WKH GHJUHH RI 'RFWRU RI 3KLORVRSK\ 8JO L4JtA :LOOLDP 5 'ROELHU -U &KDLUPDQ 3URIHVVRU RI &KHPLVWU\ 9 FHUWLI\ WKDW KDYH UHDG WKLV VWXG\ DQG WKDW LQ P\ RSLQLRQ LW FRQIRUPV WR DFFHSWDEOH VWDQGDUGV RI VFKRODUO\ SUHVHQWDWLRQ DQG LV IXOO\ DGHTXDWH LQ VFRSH DQG TXDOLW\ DV D GLVVHUWDWLRQ IRU WKH GHJUHH RI 'RFWRU RI 3KLORVRSK\ :LOOLDP 0 -RQH 'LVWLQJXLVKHG 3URIHVVRU FHUWLI\ WKDW KDYH UHDG WKLV VWXG\ DQG WKDW LQ P\ RSLQLRQ LW FRQIRUPV WR DFFHSWDEOH VWDQGDUGV RI VFKRODUO\ SUHVHQWDWLRQ DQG LV IXOO\ DGHTXDWH LQ VFRSH DQG TXDOLW\ DV D GLVVHUWDWLRQ IRU WKH GHJUHH RI 'RFWRU RI 3KLORVRSK\ .XN .LUN 6 6FKDQ]H $VVRFLDWH 3URIHVVRU RI &KHPLVWU\ FHUWLI\ WKDW KDYH UHDG WKLV VWXG\ DQG WKDW LQ P\ RSLQLRQ LW FRQIRUPV WR DFFHSWDEOH VWDQGDUGV RI VFKRODUO\ SUHVHQWDWLRQ DQG LV IXOO\ DGHTXDWH LQ VFRSH DQG TXDOLW\ DV D GLVVHUWDWLRQ IRU WKH GHJUHH RI 'RFWRU RI 3KLORVRSK\ FHUWLI\ WKDW KDYH UHDG WKLV VWXG\ DQG WKDW LQ P\ RSLQLRQ LW FRQIRUPV WR DFFHSWDEOH VWDQGDUGV RI VFKRODUO\ SUHVHQWDWLRQ DQG LV IXOO\ DGHTXDWH LQ VFRSH DQG TXDOLW\ DV D GLVVHUWDWLRQ IRU WKH GHJUHH RI 'RFWRU RI 3KLORVRSK\

PAGE 208

7KLV GLVVHUWDWLRQ ZDV VXEPLWWHG WR WKH *UDGXDWH )DFXOW\ RI WKH 'HSDUWPHQW RI &KHPLVWU\ LQ WKH &ROOHJH RI /LEHUDO $UWV DQG 6FLHQFHV DQG WR WKH *UDGXDWH 6FKRRO DQG ZDV DFFHSWHG DV SDUWLDO IXOILOOPHQW RI WKH UHTXLUHPHQWV IRU WKH GHJUHH RI 'RFWRU RI 3KLORVRSK\ 0D\ 'HDQ *UDGXDWH 6FKRRO

PAGE 209

81,9(56,7< 2) )/25,'$

PAGE 210

5()(5(1&( /,67 7ROJ $QDO\VW f -5 'DYLV -U $ 5RKDWJL 5+ +RSNLQV 3' %ODLV 3 5DL&KRXGKXU\ -5 0F&RUPLFN DQG +& 0ROOHQNRSI ,((( 7UDP (OHFWURQ 'HYLFHV (' f 7< .RPHWDQL $QDO &KHP f <+ 3DR 51 =LWWHU DQG -( *ULIILWKV 2SW 6RF $P f <+ 3DR DQG -( *ULIILWKV &KHP 3K\V f &$ 0RUWRQ $SSO 2SW f 0/ )UDQNOLQ +RUOLFN DQG +9 0DOPVWDGW $QDO &KHP f &RPPLVVLRQ ,QWHUQDWLRQDOH GH Of(FODLUDJH ,QWHUQDWLRQDO /LJKWLQJ 9RFDEXODU\ 3XEO 1R &,( 3DULV : +HUVFKHO 3KLO 7UDP 5R\ 6RF f /1RELOL DQG 00HOORQL $QQ &KLP 3K\V f 63 /DQJOH\ 1DWXUH f :1 +DUWOH\ 3KLO 7UDP f + +HUW] $QQ 3K\V f + +HUW] $QQ 3K\V f + +HUW] $QQ 3K\V f $ 5LJKL 3KLO 0DJ f (OVWHU DQG + *HLWHO $QQ 3K\V f /5 5ROOHU 2SW 6RF $P f /5 5ROOHU 3K\V 5HY f -$ 5DMFKPDQ DQG 5/ 6Q\GHU (OHFWURQLFV f

PAGE 211

9. =ZRU\NLQ DQG (* 5DPEHUJ 3KRWRHOHFWULFLW\ DQG ,WV $SSOLFDWLRQV :LOH\ DQG 6RQV 1HZ
PAGE 212

0DWYHHY 1% =RURY DQG
PAGE 213

' 7RQ7KDW 05 )ODQQHU\ 9L\V 5HY $ f DQG UHIHUHQFHV WKHUHLQ (: 0F'DQLHO &ROOLVLRQ SKHQRPHQD LQ LRQL]HG JDVHV :LOH\ 1HZ
PAGE 214

.& 6P\WK 3. 6FKHQFN &KHP 3K\V /HWW f *6 +XUVW 0* 3D\QH 6' .UDPHU DQG -3
PAGE 215

( 9RLJWPDQ $SSO 6SHF )HE f LQ SUHVV ( 9RLJWPDQ DQG -' :LQHIRUGQHU 3URJ $QD/ $WRP 6SHFWURVF f -( /DZOHU $, )HUJXVRQ -(0 *ROGVPLWK '+ -DFNVRQ DQG $/ 6FKDZORZ 3K\V 5HY /HWW f

PAGE 216

%,2*5$3+,&$/ 6.(7&+ *LXVHSSH $QWRQLR 3HWUXFFL ZDV ERUQ LQ )DLFFKLR %1f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

PAGE 217

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
PAGE 218

7KLV GLVVHUWDWLRQ ZDV VXEPLWWHG WR WKH *UDGXDWH )DFXOW\ LQ WKH &ROOHJH RI /LEHUDO $UWV DQG 6FLHQFHV DQG WR WKH *UDGXDWH 6FKRRO DQG ZDV DFFHSWHG DV SDUWLDO IXOILOOPHQW RI WKH UHTXLUHPHQWV IRU WKH GHJUHH RI 'RFWRU RI 3KLORVRSK\ 'HFHPEHU 'HDQ *UDGXDWH 6FKRRO

PAGE 219

) IORULGD $ - / B fr}


THERMAL AND PHOTOCHEMICAL STUDIES OF
9,10-BIS(TRIFLUOROETHENYL)PHENANTHRENE AND
PERFLUORO-E,Z,E- AND E.E.EAS-DIMETHYL^AS-OCTATRIENE AND
THERMAL STUDIES OF TERMINALLY FLUORINATED 1,5-DIENES
By
KEITH W. PALMER
A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
1993
UNIVERSITY OF FLORIDA LIBRARIES

TO DAD, MOM, JACQUELINE, HELEN AND KARYN

ACKNOWLEDGEMENTS
A complete list of all of the friends I am indebted to for assisting me to this
point would require a dissertation in itself. Hopefully in this short space I can
give justice to a few, with the many not mentioned being assured that they will
always be in my thoughts.
I wish to express my gratitude for the excellent guidance and friendship
of my advisor, Professor William R. Dolbier, Jr. Besides attempting to attain a
fraction of his vast knowledge of chemistry, and perhaps more important, I leave
with an appreciation for his understanding, and his methods of motivating those
around him in a positive fashion. With Professor Dolbier, the chemistry is
always surmountable and one comes away with a positive feeling towards
oneself and the tasks ahead. Such an attitude is refreshing in times of stress
and leads to an enjoyable and rewarding experience.
The love and support of my parents and sisters was and will always be
essential. No matter where they live, it is always "home" when I make it away to
see them and the time spent together is cherished. The valuable lessons
learned at a younger age--from Dad's "Pick up the tools!" to Mom’s "Stop
procrastinating, and get to your homework!"--echo in my head from time to time
and raise my level of productivity.
The friends and colleagues I have met since at the University of Florida
Department of Chemistry are numerous. Greatly appreciated are the
exceptional faculty members I have had the opportunity to interact with and
whose courses helped to form the core of my chemical intuition. Due to my
extended stay in the Dolbier group, thanks are required to a number of

labmates: Sarah Weaver for her help in learning the ropes around the lab and
roller-blading companionship; Conrad Burkholder for numerous stimulating
discussions; Jeff Keaffaber, Laurent Wedlinger, Hania Wotowicz, Lech
Celewicz, Mohammed Alii Asghar, Hua Qi Zhang, He Qi Pan, Wen Juan Cao,
Xiao Xin Rong, and more recently Martin McClinton, Mike Bartberger and
Michelle Fletcher, all for providing valuable friendships. Last and certainly not
least, special thanks go to Dr. Henryk Koroniak. A true friend, Henryk is greatly
appreciated for teaching me a variety of technical skills and returning more than
once at just the right time to give me a fresh charge of enthusiasm.
Outside the Dolbier group, I will always remember my pistachio addicted
roommates and true friends Kevin Kinter and Brent Kleintop. The
companionship and good times we had together helped maintain proper
perspective and kept me from spending too much time in the lab.
IV

TABLE OF CONTENTS
ACKNOWLEDGEMENTS iii
ABSTRACT vii
CHAPTER
1 AN OVERVIEW OF FLUORINE SUBSTITUENT EFFECTS IN
ORGANIC SYSTEMS 1
Introduction 1
Fluoroalkanes 2
Fluoroalkenes 5
Fluorine Non-bonded Electron Interactions 8
Fluorine Steric Effects : 11
The Thermal Cyclobutene/1,3-Diene Electrocyclic Process 13
Conclusions 22
2 THERMAL AND PHOTOCHEMICAL REARRANGEMENTS OF
9,10-BIS(TRIFLUOROETHENYL)PHENANTHRENE AND
PERFLUORO-E,E,E-(AND E,Z,E-)4,5-DIMETHYL-2,4,6-OCTATRIENE 23
Introduction 23
Development of a Suitable 1,3(Z),5-Triene/1,3-Cyclohexadiene
System 27
Thermal Study of 9,10-Bis(trifluoroethenyl)phenanthrene 31
Thermal Study of Perfluoro-E,Z,E(E,E,E)-4,5-dimethyl-2,4,6-
octatriene 33
Photochemical Rearrangements of 9,10 Bis(trifluoroethenyl)phenan-
threne and Perfluoro-E,Z,E(E,E,E)-4,5-dimethyl-2,4,6-octatriene 40
Discussion 45
Conclusions 77
3 [3,3]-SIGMATROPIC REARRANGEMENTS OF TERMINALLY
FLUORINATED 1,5-DIENES 79
Introduction 79
The [3,3]-Sigmatropic Shift of 1,5-Dienes: The Cope Rearrangement 80
Fluorinated Cope Systems 82
Synthesis and Thermolysis of Terminally Fluorinated Cope Systems 86
1,1,6,6-Tetrafluoro-1,5-hexadiene 86
1-Difluoromethylidene-4-methylidenecyclohexane 89
v

1,4-D¡(d¡fluoromethyl¡dene)cyclohexane 91
meso- and c/,/-1-(2-Difluorcmethylidenecyclopentyl)-2-
difluoromethylidenecyclopentane 94
Discussion 95
Conclusions 109
4 EXPERIMENTAL 111
General Methods 111
Experimental Procedures 112
APPENDIX A: GAS PHASE THERMOLYSIS APPARATUS 160
APPENDIX B: SELECTED 19F NMR SPECTRA 163
REFERENCES 189
BIOGRAPHICAL SKETCH 197
VI

Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy
THERMAL AND PHOTOCHEMICAL STUDIES OF
9,10-BIS(TRIFLUOROETHENYL)PHENANTHRENE AND
PERFLUORO-E,Z,E- AND E,E,E-4,5-DIMETHYL-2,4,6-OCTATRIENE AND
THERMAL STUDIES OF TERMINALLY FLUORINATED 1,5-DIENES
By
Keith W. Palmer
August 1993
Chairman: William R. Dolbier, Jr.
Major Department: Chemistry
Thermolysis of 9,10-bis(trifluoroethenyl)phenanthrene was examined in
solution between 140°C and 193°C, and led to formation of 1,2,2,3,3,4-
hexafluoro-2,3-dihydrotriphenylene and 1,4,4,5,6,6-hexafluoro-2,3-(9,10-
phenanthro)bicyclo[3.1.0]hex-2-ene by irreversible, competitive first-order
processes. The competitive formation of 1,4,4,5,6,6-hexafluoro-2,3-(9,10-
phenanthro)bicyclo[3.1.0]hex-2-ene is virtually unprecedented in 1,3,5-triene
thermal chemistry with only one similar cyclization found in the hydrocarbon
literature. Thermolysis of 1,4,4,5,6,6-hexafluoro-2,3-(9,10-phenanthro)-
bicyclo[3.1.0]hex-2-ene led to further rearrangement and was examined in
solution between 180°C and 193°C. This material was found to rearrange to 4-
difluoromethylidene-3,3,5,5-tetrafluoro-1,2-(9,10-phenanthro)cyclopent-1 -ene
vii

and 1,2-(9,10-phenanthro)-3,5,5-trifluoro-4-trifluoromethyl-1,3-cyclopentadiene
through irreversible, competitive first-order processes.
Photolysis of 9,10-bis(trifluoroethenyl)phenanthrene in solution led to
1.4.4.5.6.6-hexafluoro-2,3-(9,10-phenanthro)bicyclo[3.1.0]hex-2-ene as the
major product with 1,2,2,3,3,4-hexafluoro-2,3-dihydrotriphenylene and [2n+2n]
cycloaddition products 1,4,5,5,6,6,-hexafluoro-2,3-(9,10-phenanthro)-
bicyclo[2.1,1]hex-2-ene and 1,4,5,5,6,6-hexafluoro-2,3-(9,1O-phenanthro)-
bicyclo[2.2.0]hex-2-ene being observed in minor amounts.
Thermolysis of perfluoro-E,Z,E- and E,E,E-4,5-dimethyl-2,4,6-octatriene
was studied in solution between 154°C and 202°C and initially found to
undergo C4-C5 double bond isomerization. At higher temperatures, an
equilibrium between the perfluorooctatriene and perfluoro-c/'s- and frar7s-1,3,4-
trimethyl-4-(E-1-propenyl)cyclobutene is established requiring an 4rc electron,
conrotatory electrocyclic process.
Photolysis of perfluoro-E,Z,E- and E,E,E-4,5-dimethyl-2,4,6-octatriene in
solution leads to formation of perfluoro-frans-2,3,5,6-tetramethyl-1,3-
cyclohexadiene by a 6tt electron, conrotatory electrocyclic process. This
material was found to undergo further photo-cyclization to perfluoro-frans-
2.3.5.6-tetramethylbicyclo[2.2.0]hex-2-ene through a 47c electron, disrotatory
electrocyclic process.
Reluctance of these perfluorinated-1,3(Z),5-trienes to undergo the
thermal, 6n electron, disrotatory electrocyclization via the required boat
transition state was evident, as was the facility of the photoprocess to occur
through the photo-allowed 6n electron, conrotatory electrocyclization via a chair
transition state. This disparity was believed to arise from a detrimental
interaction between terminal cis fluorines as the 1,3(Z),5-triene approaches the
boat-like disrotatory transition state and required further study.
VIII

The system chosen to probe this effect was the thermal [3,3]-sigmatropic
rearrangement of terminally gem-difluorinated 1,5-dienes. Synthesis and gas
phase thermal study of 1,1,6,6-tetrafluoro-1,5-hexadiene, 1-difluoro-
methylidene-4-methylidenecyclohexane, 1,4-di(difluoromethylidene)cyclo-
hexane, and solution phase thermal study of meso- and af,/-1-(2-
difluoromethylidenecyclopentyl)-2-difluoromethylidenecyclopentane, were
carried out and the transformations found to occur by well-behaved, irreversible,
first-order processes to the respective [3,3]-shift products. Comparison of the
measured activation parameters for these processes and values for the
corresponding hydrocarbon and partially fluorinated 1,5-dienes from the
literature indicates that terminal gem-difluorination accelerates thermal
processes occurring through chair transition states while inhibiting processes
occurring through boat transition states.
IX

CHAPTER 1
AN OVERVIEW OF FLUORINE SUBSTITUENT EFFECTS
IN ORGANIC SYSTEMS
Introduction
The isolation of fluorine by Henri Moissan on June 26, 1886, created
considerable academic interest, and led to rapid advances in the field of
fluorine chemistry.1 In 1930, Midgely and Henne developed CF2CI2 as a cheap
and safe refrigerant to replace the toxic gas ammonia which elevated fluorine
chemistry out of it's status as an academic novelty and initiated the organo-
fluorine industry. Due to the Manhattan Project and nuclear energy applications
in the early 1940s, large scale production of elemental fluorine became
necessary. The post-World War Two era saw intense interest in organo-fluorine
chemistry develop in industrial and academic sectors. This interest was
primarily due to the fascinating properties exhibited by fluoroorganic materials
developed during the concentrated research directed towards production of the
atomic bomb. Fluorine exhibits remarkable effects when utilized as a
substituent in organic systems and a variety of factors intrinsic to the fluorine
atom are responsible. The purpose of this introduction is to address factors
which will be pertinent within this current study by reviewing fluorine effects in a
series of simple and well characterized organic systems.
The effects exhibited by fluorine as a substituent are due to three intrinsic
characteristics of the fluorine atom; extreme electronegativity, non-bonded
electron pairs, and small relative size. Fluorine is the most electronegative of all
1

2
elements with a Pauling scale value of 4.10 as compared with oxygen (3.50),
chlorine (2.83), bromine (2.74), carbon (2.50), and hydrogen (2.20).2 Strong
polarization of fluorinated molecules through the a bonding framework and
through space (field effects) are results of fluorine's large electronegativity. The
atom is mono-valent and accommodates three non-bonded electron pairs in
orbitals of similar dimension to hybridized orbitals on carbon.3 Because of
these two preceding factors, fluorine exhibits an interesting donor/acceptor
contradiction under certain circumstances in that the strong removal of electron
density from a bound atom can be offset due to back donation of density from
the non-bonded electrons. The van der Waals radius of fluorine is 1.47 Á.4
Compared with the other halogens, carbon, and hydrogen (van der Waals radii:
Cl, 1.73 Á; Br, 1.84 Á; I, 2.01 Á; Caiipha,|C, 1.70 Á; H, 1.20 Á),4 fluorine should
exhibit minimal spatial requirements as a substituent, a fact which has allowed
for complete substitution of hydrogen by fluorine in many hydrocarbon systems.
This has enabled the completely synthetic field of perfluorocarbon chemistry to
be developed and exploited by industry and academics with substantial
financial and scholarly success.
The effects of fluorine as a substituent in organic systems have been the
subject of a number of reviews,1'5'6'7'8 those of Smart5 6 being most insightful.
This introduction will demonstrate the ways in which fluorine substitution
perturbs the structure and reactivity of simple hydrocarbons.
Fluoroalkanes
The series of fluorinated methanes show an interesting trend in C-F
bonding. Table 1-15 illustrates the strengthening and incremental shortening of
the C-F bond in this series. This trend of bond strengthening with increased

3
Table 1-1. C-F Bond Lengths and Dissociation Energies in Fluoromethanes.
Fluoromethane
r (C-F) ¿Al
D°(C-F) (kcal/mol)
ch3f
1.385
109.0
ch2f2
1.358
122
chf3
1.332
128.0
cf4
1.317
129.7
Table 1-2. Bond Lengths and Dissociation Energies in Fluoroethanes.
Fluoroethane
r (C-C)jAl
D°(C-C) (kcal/mol)
D°fC-F) (kcal/mol)
ch3-ch3
1.532
90.4
-
ch3-ch2f
1.502
91.2
107.7
ch3-chf2
1.498
95.6
Unknown
ch3-cf3
1.494
101.2
124.8
fch2-cf3
1.501
94.6
109.4 (CH2F)
cf3-cf3
1.545
98.7
126.8
substitution is unique to fluorine among the halogens. The series of chlorinated
methanes exhibits a similar bond shortening but is accompanied by an
incremental weakening; 83.7 kcal/mol down to 72.9 kcal/mol per first C-CI bond
homolysis in the series from CH3CI to CCI4.5
Table 1-26 illustrates the effect of successive fluorination on the bond
lengths and strengths in the case of ethane. Geminal fluorination leads to
strengthening and shortening of the C-C bond in the series CH3-CH3 to CH3-
CF3. The C-C bond lengths increase upon vicinal fluorination from CH3-CF3 to
CF3-CF3 while the C-C bond strength decreases. The C-F bond strengths in the

4
series of ethanes follows a similar trend of strengthening with increased
geminal fluorination as observed in the series of methanes.
As of this time, the trends in C-C bond strengths and lengths with various
degrees of fluorination has not been fully explained. However, valence bond
arguments have been used to rationalize the observed trends in C-F bonding in
alkanes. As previously mentioned, fluorine contains three non-bonded electron
pairs in orbitals of dimension which can accommodate appreciable overlap with
orbitals of other period two elements. It is rationalized that for carbon
substituted with two or more fluorines, double-bond no-bond resonance
structures, or negative hyperconjugation, as shown in the classical sense by
Figure 1-1, lead to increased bond order between the carbon and fluorine.3’9'10
f F-
Figure 1-1. Fluorine Double-bond, No-bond Resonance.
As the degree of geminal fluorination increases, the number of valence bond
structures involving doubly bound fluorine increases and the C-F bonds are
increasingly shorter and stronger. Theoretical calculations at the ab initio level
have confirmed such a bonding scheme where it is found that the stabilizing
interaction arises from back-donation of a fluorine lone pair into an antibonding
o*c-f orbital.9'10’11 This explanation based on fluorine non-bonded electron
interactions to rationalize the observed bonding and geometry characteristics in
fluoro-organics is complemented by other arguments which inherently do not
involve the non-bonding electrons on fluorine. One such argument suggests
that when carbon is bound to more electronegative elements, atomic p
character concentrates in orbitals directed towards the electronegative species

5
since p electrons are less tightly bound than s electrons.12'13 Carbon
rehybridization then assists in accounting for bonding and geometry trends in
fluoro-organics. Another argument arising from ab initio level theoretical study
attributes bond shortening to Coulombic interactions between oppositely
charged fluorine and carbon.14 In effect, an increase in C-F bond ionic
character is predicted as the degree of fluorination increases. Calculations
indicate the trend arises from negligible change in charge on fluorine but
considerable increase in positive charge on carbon as the degree of
fluorination increases. The variety of rationalizations for C-F bonding in such
simple systems illustrates the complexities in theoretically and certainly
qualitatively explaining bonding trends in fluoroorganic systems.
Fluoroalkenes
Fluorine substitution at a vinylic carbon leads to substantial changes in
alkene geometry and reactivity. The data in Table 1-456 reveal that
fluoroethylenes have shorter C=C bonds than ethylene and the C-F bond
lengths are shorter than similarly geminal or vicinal fluorinated alkanes. The
Table 1-4. Structural Aspects of Fluoroethylenes.
CH2=CH2
ch2=chf
ch2=cf2
CHF=CFo
CFo=CFo
r(C-C) Á
1.339
1.333
1.315
1.309
1.311
r(C-F) Á
-
1.348
1.323
1.32
1.319
H-C-H deg
117.8
120.4
121.8
-
-
H-C-F deg
-
115.4
-
116.2
-
F-C-F deg
-
-
109.3
112.2
112.5
D°n kcal/mol
59.1
Unknown
62.1
Unknown
52.3

6
geminally difluorinated olefins contain FCF bond angles which are much
smaller than ethylene and very close to the tetrahedral value of 109.47°.
Theoretical ab initio level calculations show the C-F bond shortening can be
attributed to fluorine non-bonded electron delocalization into the 7t(c=c)
molecular orbital as depicted in a valence bond fashion by Figure 1-2.915'16 FCF
bond angle contraction in this case may be rationalized by attraction between
the charged and neutral fluorine atoms.16
Figure 1-2. Fluorine Non-bonded Electron Pair Delocalization in Alkenes.
Fluoroalkene Reactivities
Reactivities in fluoroalkene series lead in some cases to clear trends as
the degree of olefin fluorination is changed, but are often found to be specific to
the olefin and transformation in question. Generally, reactions involving
transformation of unsaturated, fluorine substituted carbon to a saturated state
are more exothermic than the process for a similar hydrocarbon. Table 1-56
illustrates the increasing exothermicity for hydrogenations in the series of
fluoroethylenes, CH2=CHF clearly deviating from the trend. Other reactions
involving saturation of CF2=CF2's double bond such as bromination,
chlorination, HX (X = Br, Cl, I) addition, and polymerization are all in excess of
10 kcal/mol more exothermic than the corresponding reaction with ethylene.6
Cyclobutene to butadiene isomerizations (Table 1-66) illustrate a reverse
in thermal stability between the hydrocarbon (1) and perfluorinated (2) case.
Perfluoro-1,3-butadiene (2) is found to be 11.7 kcal/mol less stable than
perfluorocyclobutene, a result which is in line with the increased exothermicity

7
Table 1-5. Fluoroalkene Heats of Hydrogenation.
Alkene
AH°H¿ (kcal/moO
ch2=ch2
-32.6
ch2=chf
-29.7
ch2=cf2
-38.8
chf=cf2
-45.7
Table 1-6. Fluorinated Cyclobutene/1,3-Diene Thermal Isomerizations.
c
A
B
£
D
AH0 (kcal/moh
Keg_(315°C)
1
H
H
H
H
-9.7
9000
2
F
F
F
F
11.7
0.0056
3
H
H
F
F
-
77.5
4
ch3
H
F
F
-
0.50
5
ch2ch3
H
F
F
-
0.24
revealed
by AH°h2 upon transcending the series of fluoroethylenes in Table 1-5.
Although
II
CM
X
o
o
CM
X
o
X
<
=CF2 is 6.2 kcal/mol more exothermic than ethylene,
isomerization in the case of 3,3,4,4-tetrafluorocyclobutene (3) favors the diene,
indicating the fluoroalkene is lower in energy. Simple alkyl substitution at C1 in
3,3,4,4-tetrafluorocyclobutene as seen with 4 and 5, dramatically shift the
equilibrium towards the cyclobutene, creating doubt as to the usefulness of this
system in demonstrating the thermodynamic influence of fluorine on an olefin.
Other systems as illustrated in Figure 1-3,17 indicate gem-difluoroolefins are

8
destabilized relative to the saturated species. Results pertaining to the stability
of monofluorinated alkenes are contradictory but it is generally accepted that
monofluorination stabilizes a double bond relative to the saturated state.5’6
f2c=chch3
A, l2
HCF2CH=CH2
AH° = -2.5 kcal/mol
f^CF2
A
<=^cf2
AH° = -5.1 kcal/mol
Figure 1-3. Equilibria Involving Gem-difluoro Alkenes.
Since the enthalpy of reaction is a relative energy change between
reactant and product, it is not entirely established whether the favorable driving
force for transformation of a trifluoro- of gem-difluoroolefin to a saturated
fluoroalkane is due to n bond destabilization in the fluoroolefin or stability as a
result of rehybridization of the fluorinated carbon from sp2 in the fluoroolefin to
sp3 in the fluoroalkane. Arguments for both factors are offered and it appears
that both are important in these systems with n bond destabilization being the
major contributor.5 6
Fluorine Non-bonded Electron Interactions
As the stabilizing influence of fluorination upon alkanes has been
offered, a discussion on fluorine's non-bonded electron interactions with
adjacent occupied and non-occupied orbital systems is warranted in light of the
aforementioned question of fluoroolefin destabilization.
Destabilization of n systems has related precedent in the case of a-fluoro
carbanions. Such systems are found to be destabilized in situations where the
carbon bearing the negative charge and fluorine are planar.1 Figure 1-4

9
OH OH
F
10.59 10.49
pKa in 30% EtOH at 25.0°C
D 1
F 0.125
Cl 400
Br 700
Figure 1-4. Destabilization in Planar a-Fluorocarbanions.
illustrates the decrease in acidity in 4-fluorophenol (6)18 relative to phenol and
rate inhibition in isotope exchange in 9-fluorofluorene relative to fluorene-9-d2
(7)19and other 9-halogenofluorenes. Conjugative destabilization is invoked in
these cases between the fluorine non-bonded electron pairs and the planar
carbanion.
A variety of experimentally observed situations occur with fluorine bound
to sp2 hybridized carbon for which perturbation of an adjacent neutral n system
is induced by interaction with fluorine non-bonded electrons. Fluorine is found
to be an ortho and para director and frequently a net activator in electrophillic
aromatic substitutions.7 Along the same line of thought, fluorine and oxygen are
found to strongly influence the distribution of n electron charge in aromatic

10
Table 1-3. 13C NMR Shifts (8jms) for Heteroatom Substituted Benzene.
X
Geminal
ortho
meta
para
F
163.8
114.4
129.6
124.3
OH
154.9
115.4
129.7
121.0
Cl
134.3
128.6
129.8
126.5
SH
130.7
129.2
128.9
125.4
13CNMR Shift for C6H6 21: 128.5
systems leading to the development of partial negative charge at the ortho and
para positions. This is revealed by the observed shielding of carbons at these
positions in the 13C NMR spectra of representative substituted benzenes as
illustrated in Table 1-3.20 The larger third period analogies, chlorine and sulfur
respectively, show a minimal effect as might be expected due to poorer overlap
of their non-bonded electrons with the aromatic n system.
Direct evidence for the stabilization of carbocations by geminally
substituted fluorine has been obtained by a gas phase, ion cyclotron resonance
technique. This study has revealed that the ascending order of stability in the
series of fluoromethyl carbocations is +CH3 < +CF3 < +CH2F < +CHF2.2223
Furthermore, the +CF3 cation has been generated by matrix photoionization of
trifluoromethyl halides and exhibits an infrared spectrum which is consistent
with extensive 7t(P.P) bonding.24 Generally, the degree to which carbocations are
stabilized by hydrogen, fluorine, and alkyl will be found to follow the order +CH
< +CF < +CR.5

11
a-Fluorine changes the geometry of methyl radical from planar to
pyramidal which is proposed to be due to repulsion between the radical and
fluorine non-bonded pairs.25'26 Stability of a and (3-fluoro radicals as
established5 from bond dissociation energies is relatively unchanged from
hydrocarbon analogs and thermal rearrangement of 8 to 10 occurs with
activation parameters which are almost identical when X = H or F.27 The overall
effect of fluorination on the stability of free radicals is believed to be minimal.5'6
Figure 1-5. Thermal Rearrangement of 6-Methylidenebicyclo[3.2.0]heptane (8).
Fluorine Steric Effects
It is often assumed that when considered alone, the small differences
between hydrogen and fluorine in size and bond length to carbon will lead to
minimal or no effect on the conformation and reactivity in a hydrocarbon upon
substitution of C-F for C-H. This is often the case and has allowed for synthesis
and study of many poly and perfluorinated hydrocarbons, a situation which is
not available for any other atom to the extent to which it is for fluorine. Although
this is true, there remain a number of situations in which substitution of fluorine
for hydrogen in a hydrocarbon leads to a profound effect on the conformation
and (or) reactivity in a system due solely to the relative size and charge density
of fluorine versus hydrogen.
The potential energy barrier for rotation of the C-C bond in CH3-CH3 is
2.8 kcal/mol whereas in CF3-CF3 it is increased to 3.9 kcal/mol.28 1,3-Repulsion

12
between fluorines in perfluoro-n-alkanes leads to a twisting in the carbon
backbone. Such an effect is said to be evidenced by polytetrafluoroethylene,
which below 19°C contains a 360° twist in the carbon backbone per 26 CF2
units.29 This is in marked contrast to polyethylene, where the carbon backbone
maintains a zig-zag structure with all of the C-C bonds in the same plane and all
of the hydrogen atoms in straight rows.29 Examples of fluorine influencing
conformational processes are offered in Figure 1-6.30 In these systems,
conformational barriers develop upon substitution of fluorine for hydrogen
arising from electrostatic repulsion between fluorine and the group moving past.
Figure 1-7 shows a persistent radical (14) which was able to be formed up to
88% (weight) in solution and could be diluted in the open air and dissolved in
good hydrogen donor solvents like toluene, or heated to 100°C without
11
Ring Flip kH/kp = 1011 at 25°C
S
/(CH^
s
12
Ring Flip AG* = 23.5n=4, 15.3n=5, 10.5n=6 kcal/mol
Figure 1-6. Influence of Fluorine on Conformational Processes.
13
14
15
Figure 1-7. A Persistent Perfluoroalkyl Radical (14).

13
destroying the ESR signals.1 The stability of this species was attributed to the
sheltering of the radical center provided by the perfluoroethyl and
perfluoroisopropyl groups. From Taft Es values, the CF3 group is found to be
larger than CH(CFl3)2 and the CF(CF3)2 group is similar in size to C(CFI3)3.31
Steric effects attributed to fluorine are most occurrent and documented in
the case of perfluorinated systems. For fluorine to exhibit a steric effect in a
mono or partially fluorinated system, the molecule must exist with very small
spatial tolerance, whereby substitution of hydrogen by fluorine leads to
destabilization. This would be the result of attempted direct overlap of nuclei or,
more likely, electrostatic repulsion between a substituent and fluorine's high
negative charge density. As shown, steric effects due to fluorine are most
frequently documented for conformational processes occurring in rigid systems
or in the sheltering of a reaction site by a perfluoroalkyl group.
The Thermal Cvclobutene/1.3-Diene Electrocvclic Process
In the previous discussions, examples of the novelty of fluorine
substituent effects were offered and rationalized based on intrinsic
characteristics of the fluorine atom. With this basic groundwork in mind, the
effect of fluorine on the thermal cyclobutene to 1,3-diene electrocyclic
interconversion will be discussed. Understanding the studies of this system is
imperative since the results lead to a hypothesis which this author's initial
project (Chapter 2) was developed to further address.
An electrocyclic rearrangement is a subset of the pericyclic class of
reactions which involve bonding changes in a concerted fashion through a
closed cycle of atoms.32 The electrocyclic rearrangement involves the formation
of a a bond between the termini of a conjugated linear n system which results in
the formation of a ring containing one fewer n bond.33 The reaction is potentially

14
reversible, a fact which will depend on the relative thermodynamics of the
specific system in question.
Woodward and Hoffmann identified the thermal cyclobutene to butadiene
interconversion as occurring through a concerted, conrotatory pathway.34
Concertedness in a process, a situation where the energetics of bond breaking
assist bond making,33 is evidenced in these systems by low activation energies
relative to the energy of a corresponding homolytic or heterolytic process, low
activation entropies, and stereoselectivity in product formation. The
stereoselectivity in the product butadiene (or cyclobutene for the reverse
reaction) is a result of the conrotatory nature of this process. Woodward and
Hoffmann proposed that conservation of orbital symmetry from reactants to
products is the lowest energy path by which the process may occur.34 To
maintain symmetry for the thermal 4k process, C3 and C4 of cyclobutene (or
terminal carbons in butadiene) must rotate in a similar direction upon breaking
of the a bond; hereby defining a conrotatory process.34 Two equivalent,
stereodistinct, conrotatory processes are allowed by orbital symmetry for the 4k
thermal reaction. As shown in Figure 1-8, each leads to a different conjugated
diene. Theoretical studies show that a concerted transition structure does not
exist for the thermally forbidden disrotatory process and estimates the non-
concerted path involving the allylmethylene diradical to be 9-11 kcal/mol above
the concerted conrotatory transition state.35
Figure 1-8. Conrotatory 4k Electrocyclic Process.

15
Stereochemistry of butadiene products from early thermal studies of C3
and C4 alkylated cyclobutenes were rationalized based on a steric argument.
The C3 and C4 methylated cyclobutenes (Figure 1-9) yielded butadienes in
which the bulkier substituent had stereospecifically rotated outward to form the
References: 1636, 1737
Figure 1-9. Thermal Ring Opening of Methyl Substituted Cyclobutenes.
E-alkenes, away from the breaking C3-C4 a bond in the concerted transition
state. In 1980 Curry and Stevens reported a series of 3,3-disubstituted
cyclobutenes which yielded products contrary to those which would have been
predicted on steric grounds.38 Figure 1-10 illustrates their results in which ethyl,
n-propyl, and /-propyl favor inward rotation over methyl to predominately form Z-
butadienes and, surprisingly, f-butyl yields 32% of the product where this very
bulky group has rotated inward. More intriguing examples have followed as
illustrated in Figure 1-11. In each case, the reaction is 100% stereoselective
and occurs contrary to expectations based on steric interactions.
Thermal Study of the Fluorinated Cyclobutene/1.3-Diene Interconversion
The unquantified nature of the system and an interest in fluorine
substituent effects led Dolbier et al. to investigate the thermodynamics and

16
kinetics of the process for a series of fluorinated materials in the mid-1980s.42'43
Fairly rapidly, studies in the fluorocarbon systems showed drastic deviations
from the corresponding hydrocarbons. One of the major differences is that the
relative thermodynamics of the perfluorocarbon systems are reversed from the
hydrocarbons; at equilibrium, mainly perfluorocyclobutenes exist.42’44 The
Z E
Ratio of Products
R Z E
Ethyl
68
32
n-Propyl
62
38
/-Propyl
66
34
f-Butyl
32
68
Figure 1-10. Thermal Ring Opening of 3,3-Dialkylcyclobutenes.
19
z
och3
â– C(CH3)3 A
20
A
COOH
References: 1839, 1940, 2041
Figure 1-11. Contrasteric Stereoselective Thermal Ring Openings in
Substituted Cyclobutenes.

17
hydrocarbon cyclobutene ring opening is found to occur with AH* = 32.0
kcal/mol,45 AS* = 0.1 cal/molxdeg,45 and is irreversible at reasonable
temperatures due to an exothermicity of 9.7 kcal/mol.46 The exothermicity of the
hydrocarbon process arises roughly from differences in release of cyclobutene
ring strain47 (34.0 kcal/mol) and overall bonding change of a n (=61 kcal/mol)33
for a a (=79 kcal/mol)33 bond. This exothermicity is offset in the case of the
perfluorinated species by the preference of fluorine to be bound to carbon
orbitals hybridized with maximal p character. This factor amounts to 2 - 5
kcal/mol upon conversion of a gem-difluoroalkene to alkane as discussed
earlier (Figure 1-3). Figure 1-12 shows some of the systems reported by
Dolbier et al. In all of the systems, fluorine kinetically prefers outward rotation
and in some cases, outward rotation of fluorine is favored even at the steric
expense of rotating the bulkier CF3 group inward. Formation of the Z-alkenes
(23, 26) from thermolysis of 22 and 25 occur with activation energies 12.9 and
27.1 kcal/mol respectively lower than the alternate processes leading to the E-
alkenes (21, 24). This corresponds to ratios of rates for Z and E-diene
formation (kz/kf) of 7219 and 4.3x106 respectively for these two systems at
200.0°C. With only one possible butadiene available from both conrotatory
processes, 27 undergoes ring opening to stereospecifically yield 28 with
relative normal activation parameters. The partially fluorinated cyclobutenes
29, 31, and 34 were investigated to quantitatively determine the effect of a
single fluoro or trifluoromethyl substituent. 3-Fluorocyclobutene (29) was found
to open stereospecifically to 30 with an activation energy 16.9 kcal/mol lower
than that required for ring opening of 34, the large difference in activation
energies arising from inward rotation of a fluorine in 34 versus 29. To
demonstrate that thermodynamic factors were not contributing to the
stereospecificities in ring opening of 29 and 31, iodine catalyzed thermal

18
F
F
ApF3
"lF
Í*'F
CF3
27
0
38.1(2.0)
32.7(-10.5)
CF3 F
28
5.7
28.1 (-3.5)
36.3(3.9)
F
/-F 45.0(8.1)
34
30
32
97.8% (at 200.0°C)
CF,
33
2.2%
35
‘Format is, Ea in kcal/mol (AS*, cal/molxdeg); Relative AH0 in kcal/mol is shown below
structures for 21-23, 24-26, 27-28. References: (21-28)42, (29-35)43
Figure 1-12. Thermal Fluorocyclobutene/Fluoro-1,3-Diene Interconversions
Studied by Dolbier et al.

19
equilibria of each butadiene system was examined. Z-1-Fluoro-1,3-butadiene
was found to be more stable than the E-diene 30 with K(z/E) of 1.77 at 60 °C and
E-5,5,5-trifluoro-1,3-pentadiene (32) was more stable than Z-33 with AH0 = 2.5
kcal/mol for the E<-»Z equilibrium. No significant thermodynamic difference
between the Z and E-alkenes was observed in any of the cases examined, as
evidenced by these small differences in AH0 values. Therefore in these
systems, the observed kinetic difference must derive from substituent effects on
the relative transition state stability for the two competing conrotatory processes.
Considering all of the data, it was determined that in thermal conrotatory
cyclobutene ring openings, inward rotation of fluorine raises the activation
energy for the process by 10 kcal/mol while outward rotation lowers it by 4
kcal/mol.43
Theoretical Study of the Thermal Cvclobutene/1.3-Diene Interconversion
From the variety of examples and the nature of substituents examined for
this 4tc, thermal process, it was obvious that the stereoselectivities observed
were not steric in origin except in a minor number of cases. Rather, the
stereoselectivities originate from a strong electronic effect involving interaction
of cyclobutene C3 and C4 position substituents with molecular orbitals of the 4n
transition state. Substituents at the C3 and C4 positions able to act as n
electron donors such as F, Cl, OCH3, and OCOCH3, kinetically favored outward
rotation whereas n electron acceptors such as CHO and COOH favored inward
rotation.
Rondan and Houk developed a hypothesis around results obtained by
theoretical ab initio level calculations on the cyclobutene/1,3-diene thermal
conrotatory process.48 Figure 1-13 is a representation of their proposed HOMO
(Highest Occupied Molecular Orbital) and LUMO (Lowest Unoccupied

20
'Stabilization
a* (LUMO)
Destabilizatior
4-
a (HOMO)
Figure 1-13. Representation of Donor Orbital Interactions with the HOMO and
LUMO of the Cyclobutene Conrotatory Transition Structure.
Molecular Orbital) for the cyclobutene thermal electrocyclic, conrotatory ring
opening transition structure with the donor orbital system indicated for either
outward or inward rotation. Upon inward rotation, a donor orbital (rccH3 on CH3
or a lone pair of electrons on a heteroatom) destabilizes the transition state due
to a repulsive interaction with the occupied bonding o orbital, while minimal
interaction exists with a* as the donor orbital is directed at the nodal surface.
Outward rotation of a donor is slightly stabilizing due to overlap with the a* and
the fact that the donor orbital experiences less repulsion with a upon rotating
out. Interaction of acceptors containing a n bond is more complicated due to the
interactions of occupied n bonding and unoccupied n* antibonding orbitals with
the a and o* orbitals of the cyclobutene transition state. The maximal stabilizing
interaction in the case of acceptors containing a n bond is proposed to occur
upon inward rotation. The two electron interaction between the cyclobutene

21
C3-C4 a orbital and the n* orbital on the acceptor leads to a small preference
for inward rotation. Experimentally, acceptors show little preference for inward
or outward rotation, the reason being that the stabilizing n*-o interaction is
countered by a repulsive interaction between the occupied n orbital and C3-C4
a orbital of the cyclobutene transition structure. Rondan and Houk suggested a
powerful electron acceptor such as the empty p orbital on a BH2 group would
favor inward rotation due to the strong interaction with the occupied cyclobutene
a bonding orbital. Table 1-748 illustrates calculated AEa's for inward versus
outward rotation for BH2 and other donor and acceptor substituents which
further demonstrate strong rotational selectivities.
Table 1-7. Calculated AEa's for Inward versus Outward Rotation in Substituted
Cyclobutenes.
Substituents
Ea°ut. £>
trans-3,4-diboryl
+13
trans-3,4-dimethyl
-13
trans-3,4-dichloro
-22
trans -3,4-difluoro
-29
trans-3,4-dihydroxy
-31.6
The cleavage of the a bond in the cyclobutene system biased by the
electronic character of an attached substituent was dubbed "torquoselectivity"
by Houk.49 He argues that in this system, the torque about the stretching o bond
is controlled by interaction with geminal electron donor or acceptor substituents.
It is further stated that such electronic based selectivities should be observable
in a variety of other organic pericyclic processes.

22
Conclusion
The preceding discussions have introduced the variety and fashion in
which fluorine substitution can perturb hydrocarbon chemistry and aid in
mechanistic interpretation. The body of this thesis will address experimental
results obtained from the study of fluorine as a substituent in thermal and
photochemical 67: electrocyclic (Chapter 2) and thermal [3,3]-sigmatropic
rearrangements (Chapter 3).

CHAPTER 2
THERMAL AND PHOTOCHEMICAL REARRANGEMENTS OF
9,10-BIS(TRIFLUOROETHENYL)PHENANTHRENE AND
PERFLUORO-E,E,E- AND E,Z,E-4,5-DIMETHYL-2,4,6-OCTATRIENE
Introduction
The concept of torquoselectivity, developed by Rondan and Houk to
rationalize the strong electronic control of C3 and C4 substituents upon ring
opening of cyclobutenes, was suggested to be operating in a variety of
pericyclic processes. The potential was discussed for various processes such
as 67t electrocyclic reactions, cyclopropane isomerizations, and sigmatropic
shifts, to undergo a bond cleavage in a stereoselective fashion biased by
overlap with geminally bound acceptor or donor substituents.4849 Disrotatory
electrocyclic processes are expected to exhibit rotational preferences to a
smaller degree than those observed for conrotatory cases. This is due to a
smaller difference in overlap (Figure 2-1) between the breaking o bond and
geminal substituent in inward and outward rotational configurations for
disrotatory as compared to conrotatory processes.
Outward
Disrotatory
^ Conrotatory
Inward
&
Figure 2-1. Geminal Substituent Overlap With o Bond in Outward and Inward
Rotation for Disrotatory and Conrotatory Processes.
23

24
Surprisingly, probing of torquoelectronic effects through suitably
designed systems has received minimal attention outside of the thermal
cyclobutene ring opening examples discussed in Chapter 1. Torquoselectivity
in the electrocyclic conversion of benzocyclobutenes to o-xylylenes has been
studied through Diels-Alder trapping experiments.50 A few examples involving
cyclopropane ring cleavage, such as: solvolysis of cyclopropyl halides,51 1,3-
sigmatropic shifts of substituted methylenecyclopropanes,49 and retro-ene
reactions of methyl vinylcyclopropanes,49 have been rationalized assisted by
torquoelectronic arguments.
In light of the torquoelectronic effects observed in the thermal 4;t
electrocyclic fluorinated cyclobutene/1,3-diene system and the relatively
unexplored question of applicability to other pericyclic processes, a study of the
thermal 6n electrocyclic fluorinated 1,3(Z),5-triene/1,3-cyclohexadiene
interconversion was proposed. Woodward and Hoffman described the thermal
671 1,3(Z),5-triene to 1,3-cyclohexadiene reaction as occurring through an
orbital symmetry allowed disrotatory pathway.34 Experimentally, it is found that
the cyclized products are formed in a stereospecific fashion in line with a
disrotatory closure involving rotation of terminal 1,3(Z),5-triene substituents in
an opposite sense as illustrated by the examples in Figure 2-2.52
Figure 2-2. Stereospecific Thermal Disrotatory 6tt Electrocyclizations.

25
For hydrocarbon 1,3(Z),5-trienes, a wide variety of substituted systems have
been investigated to establish the relationship between triene structure and
reactivity towards cyclization.53
Observing torqueoelectronics in thermal ring opening of this 67c system is
unlikely, as the thermodynamics for conversion of 1,3-cyclohexadiene (38) to Z-
1,3,5-hexatriene (37) are unfavorable. The enthalpy diagram in Figure 2-354
illustrates the conversion of 37 to 38 is 15 kcal/mol exothermic due to loss of
AH
(kcal/mol)
36 37 38
Figure 2-3. Enthalpy Diagram for E and Z-1,3,5-Hexatriene (36, 37) and
1,3-Cyclohexadiene (38).
the conjugated triene double bond and formation of a o bond in 1,3-
cyclohexadiene. 1,3(Z),5-Triene Z^E isomerization (37-»36) does not
compete with 67c cyclization at lower temperatures as such a process involves
homolytic cleavage of the central double bond, occurring with a transition state
16 kcal/mol higher in energy than that required for the electrocyclic process.
The large exothermicity observed for Z-1,3,5-hexatriene cyclization leads to an
estimated AH* = 44 kcal/mol for ring opening of 1,3-cyclohexadiene. This
magnitude of an energy barrier for ring opening also accommodates a variety of

26
sigmatropic shift processes. Retrocyclizations of substituted 1,3-
cyclohexadienes have been observed at higher temperatures but
stereochemical analysis of the formed 1,3(Z),5-trienes in search of
torquoelectronic effects is futile due to competing rearrangements. Ring
opening of 39 (Figure 2-4) at 560°C led to complete equilibration of the labels
and was rationalized as occurring through retrocyclizations and [1,7]-H(D)
Figure 2-4. Thermal Ring Opening of a 1,3-Cyclohexadiene.
shifts.55 1,3,5-Triene Z elevated temperatures and create another source of stereochemical
scrambling.56'57
It is obvious from the preceding discussion that productive ring opening
and observation of torquoelectronics in substituted 1,3-cyclohexadienes will
require an adjustment in the thermodynamics of this system. In effect, reduction
or reversal of the enthalpy difference between a 1,3(Z),5-triene and 1,3-
cyclohexadiene would allow retrocyclization to be observed. The achievement
of such a situation would allow for ring opening of a 1,3-cyclohexadiene system
to occur at a reasonable temperature and allow study of torquoelectronic effects

27
by observing the 1,3(Z),5-triene stereochemistry and activation parameters
required.
Development of a Suitable 1.3(Z).5-Triene/1.3-Cvclohexadiene System
In theory, the exothermicity of 1,3(Z),5-triene cyclization may be offset by
ground state stabilization of the 1,3(Z),5-triene, destabilization of the 1,3-
cyclohexadiene, or some combination of both.
A system in which the thermodynamics seem favorable for observing ring
opening of a 1,3-cyclohexadiene is one in which the 1,3(Z),5-triene/1,3-
cyclohexadiene system shares a n bond with an aromatic ring as illustrated for
a general case in Figure 2-5. Cyclization in this case is impeded by loss of the
aromatic ring n bond, in effect destroying the resonance energy for that ring in
the aromatic system. By selecting the appropriate aromatic system and
Figure 2-5. Aromatic Annulated 1,3(Z),5-Triene/1,3-Cyclohexadiene System.
placement, 1,3-cyclohexadiene ring opening can become a competitive
process with 1,3(Z),5-triene cyclization at lower temperatures. Building a
fluorinated 1,3(Z),5-triene system into an phenanthrene ring was believed to be
the best suited entry into thermal study of 1,3-cyclohexadiene ring opening.
As previously discussed, Z-1,3,5-hexatriene cyclization is exothermic by
15 kcal/mol and terminal gem-difluorination or trifluorination of an pendant
alkene will increase this value by 2-5 kcal/mol peralkene. In line with the C-C a
bond strengthening trend observed for the series of fluorinated ethanes
(Chapter 1, Table 1-2), the C5-C6 a bond in the cyclohexadiene product will be

28
stronger than the corresponding C5-C6 a bond in the hydrocarbon. Such an
effect is difficult to quantize due to the nonlinear energy changes in geminal
bond strengths upon successive fluorination. An increase in the exothermicity
of the cyclization process from formation of the tetrafluorinated C5-C6 a bond
can be estimated to have an upper limit of 8 kcal/mol obtained from the
difference in C-C a bond strength between CH3-CH3 and CF3-CF3 (Chapter
One, Table 1-2). This yields an potential enthalpy of reaction range of -19
kcal/mol to -33 kcal/mol for cyclization of the hypothetical 1,1,2,5,6,6-hexafluoro-
1,3(Z),5-hexatriene. Although conceptually straightforward, estimation of this
AH°r using AH°f of each species through Benson58 type group values cannot
be performed because of the missing groups; CD-(CD)(F), CD-(C)(F), and C-
(C)(CD)(F)(F).59 Likewise, theoretical computations at any level less than ab
initio lead to woefully incorrect energy parameters for fluorinated materials.60
The resonance energy for phenanthrene is observed to be 91 kcal/mol.61
Loss of phenanthrene's C9-C10 double bond is accompanied by an 20
kcal/mol increase in enthalpy, or the difference in resonance energy between
phenanthrene and biphenyl.61’62
Considering the energetics of the 1,3(Z),5-fluorotriene cyclization and
disruption of phenanthrene resonance energy by C9-C10 n bond cleavage
Figure 2-6. Proposed Thermal Electrocyclic Interconversion between 9,10-
Bis(trifluoroethenyl)phenanthrene (40) and 1,2,2,3,3,4-Hexafluoro-2,3-dihydro-
triphenylene (41).

29
together in a single system such as 9,10-bis(trifluoroethenyl)phenanthrene (40)
and 1,2,2,3,3,4-hexafluoro-2,3-dihydrotriphenylene (41) as illustrated in Figure
2-6, an enthalpy of reaction range of 1 kcal/mol to -13 kcal/mol for the
cyclization may be predicted based on the previous arguments. The upper limit
of such an enthalpy difference is suitable to allow for potential study of forward
and reverse reactions under reasonable conditions and, ultimately, observation
of torquoelectronic effects in a higher substituted system such as illustrated in
Figure 2-7. Due to a straightforward synthetic route available into these
perfluoroalkenyl substituted aromatics, 40 was prepared for thermal study.
Figure 2-7. Unsymmetrically Substituted, Phenanthrene Annulated, 1,3(Z),5-
Triene/1,3-Cyclohexadiene Interconversion for Torquoelectronic Study.
Synthesis of 9.10-Bis(trifluoroethenyl)phenanthrene (401
9,10-Bis(trifluoroethenyl)phenanthrene (40) was synthesized in four
steps (Figure 2-8) and isolated in a 1% overall yield. The first two steps
involved literature procedures; bromination63 of phenanthrene (45) to yield 9-
bromophenanthrene (46, 90%), then nitration64 to yield 9-bromo-10-
nitrophenanthrene (47, 13%). The actual yield of 47 from this reaction was
higher. The isolated yield reflects some difficulty in obtaining this material pure
from the other major nitration product, 9-bromo-3-nitrophenanthrene. The next
step involved nucleophillic attack of iodide on the brominated C9 of 47 to yield

30
Br 02N Br
HN03, CH3C02H
46 (90%)
(CH3C0)20, a \=/ \=
47 (13%)
ex. Nal, DMF, A
N02
XZnCF=CF2 (X = I, -CF=CF2)
40(16%)
cat. Pd(P(C6H5)3)4,
Triglyme, 110°C
48 (42%)
Figure 2-8. Synthesis of 9,10-Bis(trifluoroethenyl)phenanthrene (40).
9-iodo-IO-nitrophenanthrene (48, 42%). The best literature procedure found
for preparation of 48 involved five steps and produced the target in 1% yield
from phenanthrene.65 Our procedure is a significant improvement even in this
unoptimized state involving three steps and producing 48 in 5% isolated yield
from phenanthrene. Preparation of 40 at this point was rather fortuitous. A
Pd(P(C6H5)3)4 catalyzed coupling between iodo aryls and XZnCF=CFY (X = I or
-CF=CFY, Y = F or Z{E)-CF3) was carried out on 48.66 From the reaction
mixture, 16% of 40 could be isolated on average. It was intended to isolate 9-
nitro-10-trifluoroethenylphenanthrene by this procedure, which through
subsequent steps could be converted to 9-iodo-10-trifluoroethenyl-
phenanthrene. This material would then provide the desired 40, 42, and 44
through the appropriate coupling procedure. Preparation of 40 by this coupling
procedure with 48 was found to be reproducible over a number of runs.
Although 9-nitro-10-trifluoroethenylphenanthrene was tentatively identified as a
component in the reaction mixture by 19F NMR, it was never isolated. Having

31
40 in hand a few steps earlier than anticipated, a study of it's thermal chemistry
was initiated.
Thermal Study of 9.10-Bis(trifluoroethenvl)phenanthrene (40)
The thermolysis 40 was studied from 140°C up to 193°C as 0.1 M
solutions in CeD6. Upon thermolysis of 40, four products could be observed in
solution and were isolated pure by preparative GLPC for characterization.
Figure 2-9 illustrates the percent composition of all reaction components versus
time for thermolysis at 180.0°C. The reaction is quantitative with regard to
formation of C^HaFe structural isomers through 19 hours of thermolysis at
180.0°C and after 235 hours, a 78% yield of Ci8H8F6 isomers is obtained as a
21:1 mixture of 1,2-(9,10-phenanthro)-3,5,5-trifluoro-4-trifluoromethyl-1,3-
cyclopentadiene (51) and 1,2,2,3,3,4-hexafluoro-2,3-dihydrotriphenylene (41).
To develop the scheme of overall transformations as shown in Figure 2-
9, it was necessary to thermolyze each of the intermediate materials; 41,
1,4,4,5,6,6-hexafluoro-2,3-(9,10-phenanthro)-bicyclo[3.1.0]hex-2-ene (49), and
4-difluoromethylidene-3,3,5,5-tetrafluoro-1,2-(9,10-phenanthro)cyclopent-1 -ene
(50), alone under conditions which had been used for the parent triene 40.
Thermolysis of 41 at 180.0°C as a 6:1 purified mixture of 41:51 led to non¬
productive decomposition of 41 with no reaction of 51. Triene 40 was not
observed to be reversibly formed from the cyclized product 41, and neither 49
nor 50 were observed either. Thermolysis of purified 49 was observed at three
temperatures (180°C, 185.0°C, 192.5°C) and found to form only 50 and 51.
The conversion of 49 to 50 and 51 is quantitative at the temperatures and
times observed. Figure 2-10 illustrates the percent composition of all reaction
components versus time for thermolysis of 49 at 180.0°C. Thermolysis of 50,
as one can see at longer times in thermolysis of 40 (Figure 2-9, after 140 hours)

32
is observed to slowly form 51 In a near quantitative process. The possibility of
fluoride catalysis affording such a rearrangement was demonstrated by the
rapid conversion of 50 to 51 at 80°C in the presence of added trace amounts of
CsF.
The possibility of fluoride catalysis effecting the reaction course of 40 at
early times was ruled out by thermolyzing a sample of 40 in DMF containing
CsF at 115°C. After 3.5 hours, 70% of 40 had been consumed and three other
products were observed. Analysis of this mixture by GLPC and 19F NMR
showed that this fluoride catalyzed reaction process and the thermal process
had no products in common and was not further investigated.
The disappearance of 40 and 49 were both found to follow first-order
kinetics, and the corresponding first-order plots are given in Figure 2-11 and
Figure 2-12 respectively. Upon thermolysis of 40 up to 85% conversion, the
ratio of (49+50+51 )/41 was maintained at 4.42 ± 0.19 at 180.0°C, 5.03 ±0.11
at 184.5°C, and 5.15 ± 0.16 at 193.0°C. Upon thermolysis of 49 through 70%
conversion, the ratio of (50/51) was maintained at 1.62 ± 0.12 at the three
temperatures (180.0°C, 185.0°C, 192.5°C) examined. As previously
mentioned, the reactions of 40 and 49 were found to be irreversible in
formation of their respective products. Assuming these reactions occurred via
irreversible, competitive first-order processes, rate constants for formation of 41
and 49 from 40, and 50 and 51 from 49 were obtained from the observed rate
constants for loss of 40 and 49, and the constant ratios of respective products
formed.67 Both the observed and separated rate constants for 40 are reported
in Figure 2-11, and for 49 in Figure 2-12.
The activation parameters (AH*, AS*) for the individual processes were
kT r.AHi'i r*sn
obtained from the Eyring expression68, k = —e RT e R \ rearranged to the

33
form Ln(k/T) = -AH*/RT + AS*/R + Lr\(k/h), where k = rate constant at absolute
temperature T, k= Boltzmann constant (1.381x1 O'23 J/K), h = Planck's constant
(6.626x10*34Jxs), and R = ideal gas constant (1.9872 cal/molxK). Linear least-
squares regression plots of Ln(k/T) versus 1/T yielded AH* and AS* from the
slope and intercept respectively of the fitted line for each system. Fit of the
separated rate constant k41 (Figure 2-13) at the three observed temperatures
yielded AH* = 29.9 ± 0.1 kcal/mol and AS* = -19.6 ± 0.3 cal/molxdeg, and for
k49 (Figure 2-13) yielded AH* = 34.4 ± 2.8 kcal/mol and AS* = -6.6 ± 6.0
cal/molxdeg. Fit of the separated rate constant k50 (Figure 2-14) yielded AH* =
31.3 ± 0.4 kcal/mol and AS* = -12.7 ± 0.9 cal/molxdeg, and for k5i (Figure 2-14)
yielded AH* = 31.4 ± 0.1 kcal/mol and AS* = -13.4 ± 0.1 cal/molxdeg.
Quantitative thermal studies of fluorinated 1,3,5-trienes have no
precedent in the literature, and the formation of bicyclo[3.1.0]hex-2-ene ring
structures from 1,3,5-triene thermolyses have no precedent in fluorocarbon
literature. There has been but one such case observed in the hydrocarbon
literature, and this will be discussed later. The novelty of the chemistry
presented above, along with the general absence of thermal studies of
fluorinated 1,3,5-trienes, led to examination of the system which will be
discussed next.
Thermal Study of an Acyclic Perfluorinated 1.3.5-Triene
The unexpected thermal results obtained in the case of 40 led to our
questioning as to whether an acyclic perfluorinated 1,3(Z),5-triene would also
undergo bicyclo[3.1.0]hex-2-ene ring formation in preference to the thermal
disrotatory 6k electrocyclic process. At the time this project began, the literature
contained only one relevant reference. Perfluoro-1,3,5-hexatriene had been
reported to afford an 84% yield of perfluoro-1,3-cyclohexadiene upon pyrolysis

34
Figure 2-9. Thermolysis of 9,10-B¡s(trifluoroethenyl)phenanthrene (40) at
180.0°C as a Solution in C6D6.

bicyclo[3.1.0]hex-2-ene (49) at 180.0°C as a Solution in CeD6.
Hours
% Composition
ro oi ^-1 o
o cn o tn o

36
T fC)
k40 (x105 sec1)
k4i (x105 sec-1)
l<49 (x10s sec'1)
180.0
0.991 ± 0.12
0.183
0.808
184.5
1.55 ± 0.01
0.257
1.29
193.0
2.93 ±0.06
0.476
2.45
50 + 51
Figure 2-11. First-Order Plots and Rate Constants for Loss of 9,10-
Bis(trifluoroethenyl)phenanthrene (40) and Derived First-Order Rate Constants
for Formation of 1,2,2,3,3,4-Hexafluoro-2,3-dihydrotriphenylene (41) and
1,4,4,5,6,6-Hexafluoro-2,3-(9,10-phenanthro)bicyclo[3.1.0]hex-2-ene (49).

37
T (°C)
I<49(x105 sec-1)
l<5o(x105 sec'1)
k5i(x105 sec'1)
180.0
1.96 ±0.02
1.21
0.751
185.0
2.92 ±0.01
1.81
1.11
192.5
5.14 ±0.08
3.17
1.97
Figure 2-12. First-Order Plots and Rate Constants for Loss of 1,4,4,5,6,6-
Hexafluoro-2,3-(9,10-phenanthro)bicyclo[3.1.0]hex-2-ene (49) and Derived
First-Order Rate Constants for Formation of 4-Difluoromethylidene-3,3,5,5-
tetrafluoro-1,2-(9,10-phenanthro)cyclopent-1-ene (50) and 1,2-(9,10-
Phenanthro)-3,5,5-trifluoro-4-trifluoromethyl-1,3-cyclopentadiene (51).

38
1/T
Figure 2-13. Eyring Plots for Separated Rate Constants k4-| and k4g.
Figure 2-14. Eyring Plots for Separated Rate Constants k50 and k51.

39
in a flow system at 450°C.69 At this temperature, it is questionable whether this
is the primary process involved in this system. A lower temperature, more
quantitative study of an acyclic perfluorinated 1,3,5-triene was required.
A system whose synthetic approach potentially allowed for adaptation
into a variety of terminally substituted perfluoro-1,3,5-trienes was perfluoro-
E,Z,E- (and E,E,E-)4,5-dimethyl-2,4,6-octatriene (Z-56(E-56)). This system had
been previously synthesized and Figure 2-15 illustrates the chemistry
involved.70 This procedure was repeated and the isolated yield and product
composition obtained (60%, E,Z,E:E,E,E = 1.17:1) were similar to those reported
(68%, E,Z,E:E,E,E = 1.63:1).
Initially, an attempt was made to synthesize perfluoro-3,4-dimethyl-1,3,5-
hexatriene (58) by similar methodology; a process which had been discussed
Cd°, DMF, RT
30 min.
CuBr, DMF, RT
TH?
Similar to Above
I^F
DMF, RT, 1 Hr
CU>
‘"X
=< F
57 CF*
*Perfluoro-Z-1-iodopropene (52) was synthesized in four steps from perfluoropropene.66
Figure 2-15. Synthesis of Perfluoro-E,Z,E(E,E,E)-4,5-dimethyl-2,4,6-octatriene
(Z-56(E-56)).

40
only to the point of the chain extended copper reagent 57 in the reference.
Following the reaction progress by 19F NMR, formation of 57 was observed, but
addition of a further equivalent of iodotrifluoroethylene afforded a 5% or less
yield of 52 in the reaction mixture, which for the purpose of this project was
synthetically useless. Not having obtained useful quantities of 58, the synthesis
of 56 was repeated and it's thermal chemistry investigated.
The thermolysis of 56 was studied from 149°C to 202°C as a 0.17 M
solution in n-pentane. Due to difficulty in separation of the triene E,Z,E and
E,E,E isomers, the typical synthetic mixture of isomers (E,Z,E:E,E,E ratio of
I.17:1) was used in all studies. At temperatures around 150°C, E,Z,E-*E,E,E
isomerization was observed to occur. After longer times, one new product was
evident, being identified by 19F NMR in the reaction solution as a mixture of
periluoro-c/'s(and transj-l ,3,4-trimethyl-4-(E-1-propenyl)cyclobutene (59).
Figure 2-16 shows the percent composition versus time for thermolysis of 56 at
154°C and then at 202°C. E,Z,E-»E,E,E isomerization is observed initially
followed by appearance of 59 after 50 hours at 154°C. Raising the temperature
of the sample to 202°C sets up an equilibrium mixture of E-56/59/Z-56 =
II.4/7.6/1. Thus, this system represents a second example where a highly
fluorinated 1,3(Z),5-triene underwent thermal chemistry other than the 6k
disrotatory formation of a 1,3-cyclohexadiene. Since the thermal 6k closure
seemed to be disfavored, we were interested to see whether the photochemical
6k conrotatory formation of 1,3-cyclohexadienes would occur in these
fluorinated systems.
Photochemical Rearrangements of 9.10-BisftrifluoroethenvnDhenanthrene (401
and Perfluoro-E.Z.E(EE.EM.5-dimethvl-2.4.6-octatriene (Z-56(E-56))
Upon photochemical excitation, ground state 1,3,5-trienes may undergo

% Composition
41
E- 56
Figure 2-16. Thermolysis of Perfluoro-E,Z,E(E,E,£)-4,5-dimethyl-2,4,6-
octatriene (Z-56(f-56)) as a Solution in n-Pentane.

42
n-n* transformation to singlet excited states.71 These singlet excited states are
biradical in character and create a symmetry change in the 1,3,5-triene HOMO
from symmetric in the ground state to antisymmetric in the singlet state.
Woodward and Hoffman recognized that concerted photochemical 1,3,5-triene
cyclizations and 1,3-cyclohexadiene ring openings occurring by conrotatory
processes are an artifact of this change in the HOMO symmetry.34 More recent
theoretical study also recognizes a preferred photochemical conrotatory mode
of reaction.72 Experimentally it is found that the process occurs
stereospecifically in a conrotatory fashion as shown in Figure 2-17.73
Figure 2-17. Photochemical 671 Conrotatory Processes.
Simple observation of 1,3(Z),5-triene/1,3-cyclohexadiene photo¬
processes are complicated in many cases by other reaction pathways available
to the high energy excited state. Figure 2-18 illustrates the variety of products
which have been observed in various 1,3,5-triene/1,3-cyclohexadiene
photochemical systems.74 A variety of factors are important in dictating the
product distribution and will be discussed later.

43
Figure 2-18. Photoproduct Variation in 1,3,5-Triene/1,3-Cyclohexadiene
Systems.
Having not observed the thermal 6tt disrotatory process to any significant
extent in the cases of 40 and Z-56 at the temperatures studied, it was of interest
to determine if the photochemical 6ti conrotatory process would occur. A
question of the relative ability of the two 6n transition states (thermal disrotatory
versus photochemical conrotatory) to accommodate fluorine emerged, and a
qualitative study of the two systems photo-processes was undertaken.
Photolysis of 9.10-BisítrifluoroethenvnDhenanthrene (401
The photolysis of 40 was studied as a 0.05 M solution in n-pentane and
the samples were irradiated through Pyrex at room temperature by a heated-
cathode, low pressure mercury lamp. Four products are observed to arise from
the photolysis of 40. Figure 2-19 shows the percent composition of all reaction
components versus solution irradiation time. As found in the thermolysis of 40,
the bicyclo[3.1.0]hex-2-ene 49 is the major product from photolysis of 40. The
671 electrocyclic product 41 is formed in small and relatively constant
concentration throughout the photolysis. Two other [2n+2n] type products,

44
1,4,5,5,6,6,-hexafluoro-2,3-(9,10-phenanthro)b¡cyclo[2.1.1 ]hex-2-ene (60) and
1 ,4,5,5,6,6-hexafluoro-2,3-(9,10-phenanthro)bicyclo[2.2.0]hex-2-ene (61) are
formed roughly in a ratio of 4.5(60): 1 (61) and account for 30% of the reaction
mixture after 93% conversion of 40. Independent photolysis of pure 41 under
similar conditions used for 40 led to formation of 61 in low yields; one hour of
photolysis of 41 yields 53% 41 remaining and 28% of 61 formed with a 19%
decrease in mass balance. Photolysis of 41 for two hours leads to decrease in
amounts of all materials and 60% reduction in mass balance. Reversibility of
41 back to triene 40 was not observed to any extent in these studies. Overall
photolysis of the parent triene is quite clean and after 21 hours with the
aforementioned light source, an 11% decrease in mass balance is observed
with 8% 40 remaining. Some extent of polymerization is occurring under these
conditions and is revealed by a small amount of solid white film appearing on
the walls of the photolysis vessel.
Attempts to isolate 60 and 61 failed. The preparative packed column
GLPC conditions necessary to elute these phenanthrene derivatives led to
decomposition of 60 and 61. It was found that thermolysis of a benzene
solution containing 49, 60, and 61 at 184°C for 83 minutes led to a mixture
containing only 41,49, 50, and 51 with no 60 or 61 remaining and no new
products evident. This process was not quantified and other attempts at
isolation of 60 and 61 by TLC failed as the isomers could not be separated by
this technique.
Photolysis of Perfluoro-E.ZE(EE.F)-4.5-dimethvl-2.4.6-octatriene (Z-56(E-56))
The photolysis of 56 was studied as a 0.17 M solution in n-pentane and
the samples were irradiated through Pyrex at room temperature using a heated-
cathode, low pressure mercury lamp. Two products were observed and

45
isolated upon photolysis of 56. Figure 2-20 shows percent composition of all
materials versus solution irradiation time. Perfluoro-frans-2,3,5,6-tetramethyl-
1,3-cyclohexadiene (62) is the major photoproduct and is accompanied by
triene E,Z,E tetramethylbicyclo[2.2.0]hex-2-ene (63) is formed in the reaction mixture after
longer times and in small quantity when photolysis is carried out through Pyrex.
Photolysis of pure 62 through quartz under similar conditions used for 56 leads
exclusively to 63, and ring opening to 56 is not observed to any extent.
Attempts to obtain Diels-Alder adducts between 62 and dimethyl
acetylenedicarboxylate or N-phenyltriazoline dione in n-pentane at
temperatures up to 200°C showed no reaction and 62 was also found to be
stable at 202°C in n-pentane for 18 hours showing no rearrangement or
decomposition.
Discussion
The experimental data which have been presented point to an unique
disparity in the thermal and photochemical processes occurring in
perfluorinated 1,3,5-triene systems. While the observed photochemical
products will be shown to have related precedence in hydrocarbon 1,3,5-triene
transformations, the thermal rearrangements show little resemblance to those of
analogous hydrocarbons. It is recognized that upon such a drastic change as
perfluorination, anticipating similar results in these systems as those seen for
hydrocarbons is a dangerous assumption. As mentioned earlier, our motivation
for study of these perfluorinated systems was that they were easiest to obtain
synthetically while offering the widest variety of substitution possibilities, and
related precedence had been set in thermal studies of the 4jt perfluorinated 1,3-
diene/cyclobutene system. The results from photochemical and thermal studies

% Composition
46
Figure 2-19. Photolysis of 9,10-Bis(trifluoroethenyl)phenanthrene (40) as a
0.05 M Solution in n-Pentane by Low Pressure Mercury Lamp through Pyrex.

% Composition
47
Figure 2-20. Photolysis of Perfluoro-E,Z,E(E,£',E)-4I5-dimethyl-2,4,6-octatriene
(Z-56(E-56)) as a 0.17 M Solution in n-Pentane by Low Pressure Mercury
Lamp.

48
of perfluoro-E,E,E(E,Z,E)-4,5-dimethyl-2,4,6-octatriene (Z-56(£-56)) and 9,10-
bis(trifluoroethenyl)phenanthrene (40) will now be discussed in turn.
Discussion of the Photochemical Studies
Early studies in the photochemistry of Vitamin D and it’s many isomers
set the precedent for the possible complexities of 1,3,5-triene photochemistry.74
Previously, Figure 2-18 illustrated some of the types of products which have
been observed elsewhere in 1,3,5-triene photochemistry.
It is generally accepted that 1,3,5-triene photoproduct composition can
be directly related to the ground state conformational distribution of the system
by a principle known as the Non-Equilibration of Excited Rotamers (NEER).74
This principle states that in the excited state, an enhanced barrier for rotation
exists about the bonds which in the ground state are single bonds. Due to it's
limited lifetime, the acquiring of sufficient thermal energy by the excited state to
overcome such a barrier is unlikely. In effect, the photoproduct composition
should reflect a quantitative view of the ground state conformational equilibrium
which was irradiated. As illustrated in Figure 2-21, the ground state
conformations of Z-1,3,5-hexatriene will upon irradiation, lead in a specific
fashion to NEER dictated products.74
Although a seemingly trivial concept, the NEER principle turns out to
have good predictive value. Methods such as 1H NMR and UV spectroscopy
have been used to establish the preferred conformation in some hydrocarbon
1,3,5-trienes such as 64,75’76 and 65-67,7477 and the corresponding 254 nm
primary photoproducts are shown in Figure 2-22. Absolute proof of an
mechanistic rationale is difficult and more so in the case of NEER because of
the number of relevant untested variables and alternate mechanistic proposals.
The possibility of equilibration of excited conformers has been addressed and

49
Figure 2-21. Three "Planar" Conformations of Z-1,3,5-Hexatriene and
Corresponding Photoproducts.
(H3(2)30 ^ ^—C(CH3)3
64
cZc
65
cZc
tEt
67
cZt
Major
Product Distribution
Minor
C(CH3)3
(H3C)3C
C(CH3)3
(H3C)3C
C(CH3)3
(H3C)3C/
J-
Figure 2-22. Examples of 1,3,5-Triene Preferred Ground State Conformations
and 254 nm Primary Photoproduct Distribution.

50
dismissed by a study of the influence of wavelength on the photoproduct
distribution at low percentage conversion.7478
The preferred ground state conformation of acyclic 1,3,5-trienes changes
considerably from the hydrocarbon to perfluorocarbon systems. A variety of
studies (UV and photoelectron spectra79, theoretical consideration6080) point
toward perfluoro-1,3-butadiene (75) existing in a cis-skew structure with torsion
angle 0 = 42° (Figure 2-23), whereas 1,3-butadiene (73) exists in a planar trans
conformation with 0 = 180°. A significant hypsochromic shift is observed as the
series of fluoroethylenes (68 - 72) is transversed. This trend is also observed
between 73, 74, and 75, but here along with photoelectron spectral data, is
^max (nm)
Emax (L/molxcm)
0 (deg)
68
H2C
ch2
165
10,000
-
69
h2c
CHF
167
10,000
-
70
H2C-
— cf2
165
7,900
-
71
FHC=
cf2
162
6,800
-
72
F2C
cf2
139
11,370
-
73
/
J
210
22,300
180
cp2
74
//
/
200
19,500
180
f2c
0
75
£
162
m:f2
6,800
42°
References: 6821
, 69-7281,'
7382, 7479,
75s2
Figure 2-23. UV Data for Fluoroethylenes and Fluorobutadienes.

51
proposed to be due to non-planarity in 75 relative to 73 and 74.79 Perfluoro-
1,3-butadiene (75) is observed to have a UV spectrum identical with HFC=CF2
(71), further indicating there is little interaction between the C1-C2 and C3-C4 n
systems. This non-planarity is displayed by models where a disadvantageous
interaction is observed between fluorines on C1 and C3, and C2 and C4 in the
planar trans conformation.83 Hypsochromic shifts attributed to non-planarity
have been observed in other non-planar polyenes such as 2,3-di-f-
butylbutadiene, where Xmax = 186 nm.84
Perfluoro-E-1,3,5-hexatriene (E-76) has been subjected to theoretical
conformational study at the ab initio level.60 Two torsional angles (0i, 02) exist
in this molecule and local minima were located for two structures with syn and
anti relations of the pendant alkenes relative to the plane formed by C2-C3-C4-
C5. Figure 2-24 illustrates the conformers and the relative energies calculated.
The lowest energy conformer of E-76 was found to be a syn-skew structure as
is observed with perfluoro-1,3-butadiene (Figure 2-23, 75).
F F F
F
F
F
E-76
01 (deg)
01 (deg)
AE (kcal/mol)
180
180
3.10
146
-146
2.29
146
146
2.01
53
-53
0.10
52
52
0.00
Figure 2-24. Relative Calculated Minima for Perfluoro-E-1,3,5-hexatriene (£-
76).

52
Photochemical Study of Perfluoro-EZ.E-(andE.E.a4.5-dimethvl-2.4.6-
octatriene (Z-56ÍE-56))
Photolysis of perfluoro-E,Z,E-4,5-dimethyl-2,4,6-octatriene (Z-56) and
perfluoro-E,E,E-4,5-dimethyl-2,4,6-octatriene (E-56) yielded only two products;
perfluoro-irans-2,3,5,6-tetramethyl-1,3-cyclohexadiene (62) and perfluoro-
frans-1,2,3,4-tetramethylbicyclo[2.2.0]hex-2-ene (63) in good yield. The overall
transformation is illustrated in Figure 2-25. Triene E-56 has two possible
modes of reaction available by NEER type reasoning; 4n disrotatory ring
closure or C4-C5 double bond isomerization. The lowest energy conformer for
E-56 will most likely be similar to that of E-76, a skewed non-planar structure.
The 4k disrotatory photo-process leading to a 3-propenylcyclobutene would
require a tEc triene conformer which would be disfavored due to a repulsive
interaction between C2 fluorine and C5 trifluoromethyl groups. Therefore, the
observed process for E-56 is E,E,E->E,Z,E isomerization about the C4-C5
Figure 2-25. Photolysis of Perfluoro-E,Z,E(E,E,E)-4,5-dimethyl-2,4,6-octatriene
(Z-56(E-56)).
double bond to form Z-56. Cis triene Z-56 is found to undergo only 6k
conrotatory closure to yield 62. The lowest energy conformer of Z-56 most
likely involves skewing of the pendant E-perfluoropropenyl groups relative to
the C3-C4-C5-C6 plane, but whether it exists cis or trans skewed about the C3-
C4 and C5-C6 single bonds is unknown. It is noticed that a cis skewed

53
structure of Z-56 (Figure 2-26) is perfectly aligned with minimal repulsion to
undergo allowed 671 conrotatory bond formation between C2 and C7 leading
directly to 62.
Figure 2-26. C/s-Skewed Conformer of Perfluoro-£,Z,E-4,5-dimethyl-2,4,6-
octatriene (Z-56).
Perfluoro-i/'ans-2,3,5,6-tetramethyl-1,3-cyclohexadiene (62) undergoes a
further formal 4ji disrotatory closure to form perfluoro-trans-1,2,3,4-tetramethyl-
bicyclo[2.2.0]hex-2-ene (63) in preference to ring opening to perfluoro-£,Z,E-
4,5-dimethyl-2,4,6-octatriene (Z-56). Using experimental results and NEER
type reasoning, it has been established for hydrocarbon photochemical 1,3-
cyclohexadiene processes that the preferred ground state conformation of the
system will control whether the 6rc conrotatory ring open 1,3(Z),5-triene or 4n
disrotatory ring closed bicyclo[2.2.0]hex-2-ene is observed.85 Studies have
shown that planar or half-boat type conformers (Figure 2-27) undergo
disrotatory closure to bicyclo[2.2.0]hex-2-enes and half-chair type conformers
prefer conrotatory ring opening to 1,3(Z),5-trienes.

54
Planar Half-boat
bicyclo[2.2.0]hex-2-ene
<
Half-chair
Half-chair
Z-1,3,5-Triene
Figure 2-27. Conformationally Controlled Photo-processes of 1,3-
Cyclohexadienes.
With this precedent, it is surprising that cyclohexadiene 62 does not
undergo ring opening. Model studies83 indicate the most favored conformer of
62 (Figure 2-28) is one in which trifluoromethyl steric repulsions are minimized
in a half chair ring orientation with di-pseudoaxial C5 and C6 trifluoromethyl
groups and a C1-C2-C3-C4 torsion angle larger than that found in 1,3-
cyclohexadiene.
Figure 2-28. Favored Half-Chair Conformer of Perfluoro-frans-2,3,5,6-
tetramethyl-1,3-cyclohexadiene (62).

55
The photochemical results obtained with fluorinated triene 56 are
consistent with the few other fluorinated examples found in the literature.
Recently, it has been reported that perfluoro-Z-1,3,5-hexatriene (Z-76)
undergoes double bond isomerization and An and 6n photoclosures (Figure 2-
29) to yield a mixture of perfluoro-E-1,3,5-hexatriene (E-76), perfluoro-1,3-
cyclohexadiene (77) and perfluoro-3-ethenylcyclobutene (78).86 At low percent
conversions of Z-76, only E-76 and 77 are identified in the reaction mixture.
When the reaction is carried out to completion a mixture containing 25% 77,
40% 78, and 35% perfluoro[2.2.0]bicyclohex-2-ene (79) is obtained.
An inconsistency exists in that the formation of the perfluoro-3-
ethenylcyclobutene (78) ring structure was not observed in the case of 56. As
already discussed, E-56 will not populate the tZc conformation for steric
reasons and undergoes E,E,E->E,Z,E isomerization only. It is difficult to see
why Z-56 is not observed to form An cyclization products as are observed in the
£-76 Z- 76
\ /
78
Figure 2-29. Photoproducts Obtained from Perfluoro-Z-1,3,5-hexatriene (Z-76).
case of Z-76. Models indicate the cZt conformation of Z-56 may exist as it
must for Z-76 with little crowding of the trifluoromethyl substituents. A possible
explanation arises if one assumes only the fluorinated E-trienes are undergoing

56
the 4n cyclization. In this case, cEt E-76 can undergo 4n closure or E—»Z
isomerization, whereas tEt E-56 affords only Z-56. It is unproved whether such
an argument applies, but if so, it would be unique to these perfluorinated 1,3,5-
trienes as both E and Z hydrocarbon 1,3,5-trienes are observed to form 3-
alkenylcyclobutenes as primary photoproducts (Figure 2-22).
Photolysis of perfluoro-1,3-cyclohexadiene (77) using a low pressure
mercury lamp has been previously reported to quantitatively yield 79 as the
sole photoproduct.87 In contrast to the previous fluorinated 1,3-cyclohexadiene
results, photolysis of perfluorotricyclo[6.2.2.02-7]dodeca-2,6,9-triene (Figure 2-
30, 80) yields bicyclo[3.1.0]hex-2-ene type isomers 82 and 83. These products
are proposed to be originating from the ring opened triene 81, a species which
was never observed in this study.88 Due to the rigidity of the bicyclohexene ring
structure of 80, the cyclohexadiene ring will be very nearly planar. The
formation of 1,3,5-hexadiene 81 goes counter to the NEER predicted product
for this system, which would be formation of a bicyclo[2.2.0]hex-2-ene (Figure 2-
27) type ring structure.
83
Figure 2-30. Photolysis of Perfluorotricyclo[6.2.2.02’7]dodeca-2,6,9-triene (80).

57
Photochemical Study of 9.10-Bis(trifluoroethenyl)phenanthrene (40)
Photolysis of 9,10-bis(trifluoroethenyl)phenanthrene (40) led to formation
of four structural isomers; 41, 49, 60, and 61 as illustrated in Figure 2-31.
Figure 2-31. Photolysis of 9,10-Bis(trifluoroethenyl)phenanthrene (40).
9,10-Bis(trifluoroethenyl)phenanthrene (40) was observed by 19F NMR to
exist as a pair of torsional diastereomers with a substantial energy barrier to
interconversion, a discussion of which has been published.89 The 19F NMR
spectrum of 40 at 25°C showed signals corresponding to two types of non¬
equivalent trifluoroethenyl groups. Such a spectrum is believed to arise from a
substantial thermal barrier due to restricted rotation between conformers
involving an syn and anti relationship of the trifluoroethenyl substituents relative
to the plane of the phenanthrene ring. Observation of the 19F NMR spectra of
40 over the temperature range of -17°C to 84°C and application of classical
theory with respect to equilibrium and NMR spectra allowed an estimation of
AG* = 15 kcal/mol for interconversion of the isomers. Molecular mechanics

58
calculations estimated AH°RXn = 0.7 kcal/mol for anf/-40->syn-40 with AH* =
16.01 kcal/mol.90 Local minima for syn {syn-40) and anti {anti-AO) type
conformers were located (Figure 2-32) with trifluoroethenyl torsional angles
relative to the aromatic ring plane (tZt structure) for the anti conformer of 50° and
-75°, and for the syn conformer of 62° and 119°.
syn-40
Figure 2-32. Conformational Equilibrium of 9,10-Bis(trifluoroethenyl)-
phenanthrene (40).

59
The formation of the observed photoproducts from 40 has some
precedent from the hydrocarbon literature. Photochemical studies of 1,2-
diethenylbenzene (84, Figure 2-33) have been reported by a few authors.91'92 93
One study found that photolysis of 84 with a medium pressure mercury arc
through Pyrex yielded benzobicyclo[3.1.0]hex-2-ene (83) as the major product
in a low overall yield process (20% max) with smaller amounts of tetralin, 1,2-
dihydronaphthalene, and naphthalene observed arising from 2,3-
dihydronaphthalene (85).91 1,2-Diethenylbenzene-cf4 with four terminal
methylene deuterons was also studied to establish a carbon skeletal
rearrangement via 86 to 83, disproving a mechanism involving hydrogen
migration.91
Tetralin
—- 1,2-Dihydronaphthalene
Naphthalene
- CE7
83
Figure 2-33. Photolysis of 1,2-Diethenylbenzene (84).
Photolysis of 9,10-diethenylphenanthrene has been reported and studies
under a variety of conditions did not lead to the observation of any cyclization.94
In this case, polymerization was the only process which was observed.
The photoproducts observed from 9,10-bis(trifluoroethenyl)phenanthrene
(40) are consistent with the above hydrocarbon system results and they can
potentially be seen as arising from a NEER dictated process. Figure 2-34
shows the proposed overall primary and secondary processes. Conformer
anti-40 can form three primary photoproducts; 41,60, and 88.

60
Bicyclo[2.1.1]hex-2-ene 60 may be formed from the pendant alkenes reacting in
a photo-allowed 27ts+27ts cycloaddition and cyclohexadiene 41 may arise from
a 671 conrotatory electrocyclization. Initial formation of bicyclo[3.1.0]hex-2-ene
88 may occur through either the anti-40 or syn-40 conformers and the true
nature of the photochemical mechanism involving formation of
bicyclo[3.1.0]hex-2-enes has been the subject of much debate.
*AII bonds to fluorine except for the 1 through 8 positions of the phenanthrene ring systems.
Figure 2-34. Primary and Secondary Processes and Final Product Distribution
for Photolysis of 9,10-Bis(trifluoroethenyl)phenanthrene (40).
Photochemical formation of bicyclo[3.1,0]hex-2-enes are formally
Woodward and Hoffman allowed 4Jts+2Jta or 4Jta+2Jls processes.34 Establishing

61
the true nature of the mechanism requires labels with which to follow the
stereochemical course of the process. While there are examples of 4rts+2rta
and 47ta+27ts photoisomerizations,95'96 there are also examples of disallowed
4Jla+2Jta processes.97 Further, an explanation exists based on "cross-
bicyclization in linear conjugated polyenes" where the author's rationalization
allows for concerted 4*8+2,18 photo-processes.98 Other arguments have
involved a stepwise process which involves a concerted conrotatory closure of
the three membered ring followed by closure of the five membered ring,85’99 and
sudden polarization of the 1,3(Z),5-triene from a C3-C4 twisted diradical to a
charge separated zwitterion which undergoes closure.100'101’102
Primary photoproduct 88 was never observed most likely due to thermal
instability caused by strain in this spiro-fused system and loss of aromaticity
from the central phenanthrene ring. Under the reaction conditions, 88 most
likely undergoes a vinylcyclopropane-cyclopentene rearrangement to 49 as
rapidly as it is formed. Photolysis of 40 was attempted at -50°C looking for 88
by low temperature 19F NMR but only 49 was observed. Lower temperature
studies were abandoned due to equipment difficulties. Bicyclo[2.2.0]hex-2-ene
61 may be formed by a photo-allowed 2*s+2*s cycloaddition from syn-40 or a
secondary process involving a 4n disrotatory electrocyclization of 41. This was
found to be occurring as photolysis of pure samples of 41 led in low yield to 61
and showed no reversibility to the parent triene 40.
Discussion of Thermal Studies
The initial assumption that a suitably tailored fluorinated 1,3(Z),5-triene
system would allow for probing of the torquoelectronic effect in triene 6k thermal
chemistry turned out to be incorrect in the case of the phenanthrene annulated
system. Investigation of the thermal rearrangements of 9,10-bis(trifluoro-

62
ethenyl)phenanthrene (40) and perfluoro-E,Z,E(and E,E,E)-4,5-dimethyl-2,4,6-
octatriene (Z-56(E-56)) revealed that rearrangement pathways for these
systems have little in common with the corresponding hydrocarbons.
Thermolysis of Perfluoro-EZEfand E.EEV4.5-dimethvl-2.4.6-octatriene (Z-
$$(£-5$)
Thermolysis of the mixture of Z-56 and E-56 led to initial C4-C5 Z/E
double bond isomerization at temperatures above 150°C. The hydrocarbon
analog, Z-1,3,5-hexatriene, forms 1,3-cyclohexadiene with Ea = 29.3 kcal/mol,
while C3-C4 E to Z double bond isomerization requires temperatures in excess
of 250°C with Ea = 45.5 kcal/mol.57 Thus, the hydrocarbon Z-triene undergoes
the 6k electrocyclic process exclusively due to the AEa = 16 kcal/mol difference
between it's concerted ring closure and it's C3-C4 double bond isomerization.
Although alkyl substitution can lower the Ea for C3-C4 double bond
isomerization of 1,3,5-hexatriene by approximately 6 kcal/mol57 and
perfluorination of 2-butene leads to a lowering of the E<-»Z isomerization by 6.4
kcal/mol versus the hydrocarbon,103 it is inconceivable that the fluorination of Z-
56 will lead to lowering in energy of the C4-C5 double bond Z->E isomerization
so as to make this process exclusively preferred over the 671 ring closure.
The next process observed to occur is a 4k cyclization of triene 56. An
equilibrium ratio of 1.64:1 was established between 56 (E and Z) and 59 at
202°C in n-pentane as illustrated in Figure 2-35.
Perfluoro-1,3,5-hexatriene (76) has been reported in a patent to afford
an 84% yield of perfluoro-1,3-cyclohexadiene (77) upon pyrolysis at 450°C in a
flow system.69 Concurrent to this thesis project, a thermal study of perfluoro-
1,3,5-hexatriene at lower temperatures was reported.86 These authors offered
similar results to those obtained in our study of 56. Thermolysis of

63
Figure 2-35. Mixture Obtained from Thermolysis of Perfluoro-E,Z,E(E,E,E)-4,5-
dimethyl-2,4,6-octatriene (Z-56(E-56)) at 202.0°C in n-Pentane.
perfluoro-1,3,5-hexatriene at 160°C established an equilibrium mixture
consisting of 9% perfluoro-1,3,5-hexatriene and 90% perfluoro-3-
ethenylcyclobutene (78). Thermolysis of perfluoro-1,3,5-hexatriene at 220°C
was reported to irreversibly yield perfluoro-1,3-cyclohexadiene.
In the fluorinated 1,3,5-triene systems, formation of 3-
alkenylcyclobutenes in preference to 1,3-cyclohexadienes upon thermolysis
leads to the conclusion that the energy surfaces for the hydrocarbon and
fluorocarbon systems are quite different. It is informative to observe the
enthalpy diagram (Figure 2-36)57 for the hydrocarbon CeH8 system. Formation
of 3-ethenylcyclobutene (89) by a 4k conrotatory electrocyclic process is not
observed in hydrocarbon 1,3,5-triene thermal studies. E-1,3,5-Hexatriene (36)
isomerizes to the Z-triene (37) which then undergoes the 6n ring closure to 1,3-
cylohexadiene (38). Both processes are preferred over the 4k cyclization.
Perfluoro-1,3,5-hexatriene is seen to form perfluoro-1,3-cyclohexadiene at
higher temperatures and it is likely that perfluoro-E,Z,E-4,5-dimethyl-2,4,6-
octatriene (Z-56) would have exhibited a similar reaction path had the system
been investigated at higher temperatures.

64
Figure 2-36. Enthalpy Diagram for C6H8 Transformations.
The data obtained from these perfluoro-1,3,5-triene systems, although
qualitative in nature, require changes in the energy profile for fluorinated 1,3,5-
triene transformations (Figure 2-37). The thermal equilibrium rich in perfluoro-
3-alkenylcyclobutenes in the cases of perfluoro-1,3,5-hexatriene (76) and
perfluoro-E,Z,E(and E,E,E)-4,5,-dimethyl-2,4,6-octatriene (Z-56(E-56)) lead to
a lowering of the AH°p of the perfluoro-3-alkenylcyclobutenes relative to the
perfluoro-1,3,5-trienes. Such a change in the relative enthalpy has precedent
in the case of the earlier discussed fluorinated cyclobutene/1,3-diene
interconversions (Chapter One, Table 1-6 and Figure 1-12). In these examples,
it was found that the perfluorinated cyclobutenes were lower in energy than the
perfluoro-1,3-dienes with AAH°Ron the order of 17 kcal/mol between the
hydrocarbon and fluorocarbon systems. Irreversible formation of perfluoro-1,3-
cyclohexadienes from the fluoro-1,3(Z),5-trienes only in the high temperature
runs leads to these species having the most negative AH°f of the isomers, but
with a raised energy barrier to the 6k disrotatory transition state.

65
Figure 2-37. Enthalpy Diagram for Perfluoro-1,3,5-triene Transformations.
Thermolysis of 9.10-Bis(trifluoroethenvhDhenanthrene (40)
Thermolysis of 9,10-bis(trifluoroethenyl)phenanthrene (40) was found to
form the desired 1,2,2,3,3,4-hexafluoro-2,3-dihydrotriphenylene (41), but only
as a small component in a very complicated overall reaction process. A virtually
unprecedented process for 1,3(Z),5-triene thermal chemistry, leading to
bicyclo[3.1.0]hex-2-ene 49 and subsequent rearrangement of this species, was
observed to comprise the major reaction pathway of 40.
Thermal studies of 1,2-dialkenyl aromatics are only rarely encountered in
the literature. Any attempt to investigate the electrocyclic chemistry of such
systems would be expected to be complicated by the instability of the cyclized
non-aromatic products under the reaction conditions and the facility of these
products to undergo further rearrangement. Thermal studies of a series of 1,2-
dipropenylbenzenes has been reported.104 These systems first show pendant
alkene isomerization which was proven to occur by [1,7]-sigmatropic hydrogen
shifts. Higher temperatures yield 1,2-dihydronaphthalenes and alkyl 1,2-
dihydronaphthalenes which arise from disrotatory ring closure followed by an

66
[1,5]-sigmatropic hydrogen shift. The mechanistic nature of these processes
was established by studying suitably deuterium labeled species, and a
mechanistic rationale was proposed as seen in Figure 2-38.104
Figure 2-38. Thermal Processes Observed for 1,2-Dipropenylbenzenes.
One instance of the thermolysis of 9,10-diethenylphenanthrene at 210°C
has been reported to yield 35% triphenylene, apparently arising from formation
of the unstable 2,3-dihydrotriphenylene, which undergoes loss of hydrogen.94
From the thermodynamic argument offered early in this chapter, it was
believed that 9,10-diperfluoroalkenylphenanthrenes offered a chance to
observe a reversible thermal 6n electrocyclization in a 1,3(Z),5-triene system.
The thermodynamics seemed favorable and the potential for relatively
unprecedented fluorine shifts nonexistent due to the greater strength of the C-F
versus C-H bond. In this light, it was initially discouraging to observe such a
complex mixture upon thermolysis of 40.

67
Thermolysis of 9,10-bis(trifluoroethenyl)phenanthrene (40) led to
formation of two primary products and two secondary products as illustrated in
Figure 2-39. One of the primary thermal products, 1,2,2,3,3,4-hexafluoro-2,3-
dihydrotriphenylene (41), was observed to be formed to no more than 15% in
the reaction mixture over the temperatures examined. Contrary to expectations,
thermolysis of purified 41 under identical conditions used for cyliization of the
parent triene demonstrated that the cyclization was irreversible. The cyclized
Figure 2-39. Transformations Observed Upon Thermolysis of 9,10-
Bis(trifluoroethenyl)phenanthrene (40).
product 41 was predicted to be in an enthalpy range of 1 to -13 kcal/mol relative
to the parent triene 40. The fact that reversibility is not observed to any extent in
this system leads to the conclusion that this process is occurring with AHR< -5
kcal/mol. A higher temperature study of this material was not undertaken as
significant non-productive decomposition was found to be occurring at
temperatures used to study 40. As discussed earlier, having observed a good
fit to first-order theory for the loss of 40 and a constant ratio of (49+50+51 )/41
over the individual runs examined, activation parameters of AH* = 29.9 ± 0.1

68
kcal/mol and AS* = -19.6 ± 0.3 cal/molxdeg were obtained for formation of 41
from 40. Such parameters for the formation of 41, being formally a 6k
disrotatory process from 40, are difficult to rationalize as no comparative kinetic
data exists for cyclization of any other fluorinated 1,3(Z),5-triene system.
Formation of 1,4,4,5,6,6-hexafluoro-2,3-(9,10-phenanthro)bicyclo[3.1.0]-
hex-2-ene (49) was observed to be the major process early in the reaction of
40. This thermal cyclization of a fluorinated 1,3(Z),5-triene to form a fluorinated
bicyclo[3.1.0]hex-2-ene is unprecedented in fluorocarbon literature and only
one example, accompanied by minimal discussion, has been found in the
corresponding hydrocarbon literature and is illustrated in Figure 2-40.105 As
Figure 2-40. Thermal and Photoproducts of £-1-(f-Butylamino)-1,3(Z),5-
hexatriene.
discussed earlier, the activation parameters obtained for formation of 49 from
40 are AH* = 34.4 ± 2.8 kcal/mol and AS* = -6.6 ± 6.0 cal/molxdeg. The
unprecedented nature of this transformation does not allow for conjecture as to
the mechanistic significance of these values. Thus, potential processes
involved will be offered, with rationalization of the activation parameters left to
the future.
The thermal closure of a 1,3(Z),5-triene system to a bicyclo[3.1.0]hex-2-
ene ring is formally a Woodward and Hoffman allowed 47ta + 2na or 4rcs + 2ns
process.34 Determining the true stereochemical nature of the process requires
at a minimum, labels at each terminus of the reacting 1,3,5-triene system. Due
to the unprecedented nature of this thermal process, and the lack of

69
stereochemical labels in the aforementioned and 40 systems, the question of
symmetry conservation can not begin to be addressed. The formation of 49
from 40 involves a further complication as the necessary primary intermediate
88 (Figure 2-41) has still to undergo a vinylcyclopropane-cyclopentene
rearrangement to afford 49. Figure 2-41 offers a representation of the potential
processes involved in formation of 41 and 49. Direct 4na + 2na or 4tis + 2ns
Figure 2-41. Mechanistic Rationale for Formation of 41 and 49.
cyclization of anti-40 could yield the primary intermediate 88. As previously
discussed, this material was also assumed to be a primary intermediate upon
photolysis of 40. Since this intermediate was not observed under the much
lower temperature photolysis conditions, it would certainly not be observable
under the thermolysis conditions. A vinylcyclopropane-cyclopentene

70
rearrangement must spontaneously occur as 88 is formed to relieve the strain
in this spiro-fused system and restore aromaticity to the central phenanthrene
ring. An alternate diradical process from anf/-40 may occur with formation of
the intermediate 90. In this case, closure of the terminus of one trifluoroethenyl
substituent on the second at its carbon attached to the phenanthrene ring would
yield the biradical 90 which may then recombine to 88 and rearrange to the
observed product 49.
1,4,4,5,6,6-Hexafluoro-2,3-(9,10-phenanthro)bicyclo[3.1.0]hex-2-ene
(49) was observed to further rearrange under the thermolysis conditions to form
50 and 51 (Figure 2-39). Since 49 was unreactive with trace fluoride at lower
temperatures and since disappearance of 49 follows first-order kinetics and
yields linear Eyring plots over the temperatures and through the 70% extent of
reaction examined, a mechanism involving fluoride catalysis can effectively be
ruled out.
A hydrocarbon analog, bicyclo[3.1.0]hex-2-ene (91, Figure 2-42), is
known to undergo thermal C1-C5 cyclopropane bond homolysis to yield
biradical 92, in which 1,2-H shifts may occur in two possible directions leading
to the observed products 1,4- and 1,3-cyclohexadiene (93, 94).54
91
94
Figure 2-42. Thermolysis of Bicyclo[3.1.0]hex-2-ene (91).

71
Thermolysis of benzobicyclo[3.1.0]hex-2-ene (95, Figure 2-43) has been
studied by the flash vacuum technique.106 Over the high temperatures
investigated (500-900°C), it was found that the major primary product was
FVT
700°C
96 (30%)
84 (5%)
+ Naphthalene (12%)
95
97 (8%)
98 («1%)
Figure 2-43. Flash Vacuum Thermolysis of Benzobicyclo[3.1.0]hex-2-ene (95).
1,2-dihydronaphthalene (96) with a variety of minor products (84, 97, 98) also
observed. These products were proposed as arising from homolytic cleavage
of the appropriate cyclopropane ring bond followed by a hydrogen shift (96, 97,
98) and electrocyclic process (84).
Gas and solution phase thermal rearrangement of
perfluorobenzobicyclo[3.1.0]hex-2-ene (100, Figure 2-44) has been reported in
a study addressing the reaction of perfluoroindene (99) with sources of
difluorocarbene.107’108 Perfluoroindene (99) was found to react with
difluorocarbene generated from thermolysis of hexafluoropropylene oxide
(HFPO). At lower temperatures, perfluorobenzobicyclo[3.1.0]hex-2-ene (100)
was found to be the major product with smaller amounts of
perfluorodihydronaphthalenes (101, 102) and perfluoro-2-methylindene (103)
also being observed. Thermolysis of 100 was also independently investigated.
Thermolysis of neat 100 at 230°C yielded an 1:1:7 mixture of 99:102:103 and
thermolysis at 670°C in a flow system yielded an 3:1 mixture of 99:103.

72
HFPO, 670°C
Figure 2-44. Reaction of Perfluoroindene (99) with Difluorocarbene and
Thermolysis of Perfluorobenzobicyclo[3.1.0]hex-2-ene (100).
Elimination of difluorocarbene6 can be a facile process in highly
fluorinated cyclopropanes and was observed in the thermal study of
perfluorobenzobicyclo[3.1.0]hex-2-ene (100), albeit at higher temperatures
than were involved in our study of 49. This process was revealed by formation
of significant amounts of perfluoroindene 99 upon thermolysis of 100. The
analogous compound in the case of 49 was never observed in any of the
thermolysis runs with 40 or 49. On these grounds, a mechanism involving
difluorocarbene can be ruled out.
Considering the above results, the observed thermal rearrangement of
49 to form 50 and 51 is not out of character. Figure 2-45 illustrates the
possible mechanistic route involved. Homolytic cleavage of only one out of the
three cyclopropane bonds in 49 is found to productively lead to products.
Cleavage of bonds a (104) or b (105) leads to biradicals which in both cases

73
Figure 2-45. Mechanistic Rationale for Thermal Decomposition of 1,4,4,5,6,6-
Hexafluoro-2,3-(9,10-phenanthro)bicyclo[3.1.0]hex-2-ene (49).
have one benzylic center; the other being on a secondary (104) and primary
(105) carbon. Appreciable overlap with the C9-C10 phenanthrene k system
early in cleavage of bond b may also facilitate such a process relative to
cleavage of bond a or c. Geminal difluorination of cyclopropanes is known to
weaken the C-C bond opposite to the fluorinated site and those adjacent to the
fluorinated site, although the weakening of the opposite bond is significantly
greater.6 Such an effect may be thought to possibly lead to facilitation of
cleavage of bond a. Here this factor is unlikely to be significant since this
cyclopropane system also contains fluorine at sites p to the geminally
difluorinated site which would counter such a disparity in bond strengths. The

74
final observed products require a 1,2-fluorine atom shift from the intermediate
biradical. A 1,2-fluorine atom shift in the case of 104 will be a higher energy
process than one in 105 due to the cleavage of the stronger C-F bond at the
difluorinated site in the former. This fact together with the stereoelectronic
preference for bond b cleavage and benzylic stabilization in 105 leads to
observation of products arising only from cleavage of 49 to 105. The other
possible ring cleavage route cto form biradical 106 is disfavored as such a
system affords no benzylic stabilization. The final observed products 50 and
51 then arise from 1,2-fluorine atom shifts of Fa (Figure 2-45) in one of two
directions in 105. The slightly favored product 50 is formed by shift towards the
stabilized radical center.
Fluorine atom shifts lack unambigous precedent in the literature.
Thermal [1,3] and [1,5]-fluorine atom shifts have been invoked in studies
involving isomerizations of dihydrohexafluorocyclohexa-1,3-dienes109 and
perfluoroisoindenes.110 Photochemical [1,5]-fluorine atom shifts have been
invoked in the isomerization of perfluoroindene to perfluoroisoindene111 and a
rearrangement of perfluorotricyclo[5.2.2.02-6]undeca-2,5,8-triene (107) to
perfluorotricyclo[5.2.2.02-6]undeca-2,3,8-triene (108).88
Figure 2-46. Photochemical [1,5]-Fluorine Atom Shift in Perfluorotricyclo-
[5.2.2.02-6]undeca-2,5,8-triene (107).

75
Steric Effects in Thermal 1.3(Z).5-Triene Electrocyclizations
The rule of orbital symmetry conservation for a concerted process
requires that C1-C6 bond formation in the thermal rearrangement of a 1,3(Z),5-
triene to a 1,3-cyclohexadiene occur by overlap of n orbitals on the same side of
the triene plane; hence defining a disrotatory process. A consequence of this
type of process is that 1,3(Z),5-triene C1 and C6 cis substituents are forced into
a more crowded position in the transition state than in the ground state. It is
found that higher activation energies are required to bring C1 and C6 within
bonding distance in the transition state due to this crowding, and often the
energy of the 6tc process will be sufficiently high so that alternate processes are
observed to varying extents.
Activation parameters for a variety of systems in the literature
demonstrate this steric effect and a few examples are given in Figure 2-47.
Many of the examples found (109,52 110,52 111,112 112112) show little change in
activation entropy, indicating similar transition state geometry and timing is
being maintained, therefore, the strain being built into the transition state is
manifesting itself as a measurable increase in activation enthalpy. Sufficiently
hindered systems (11373) often do not undergo 6k cyclization from the initial
1,3(Z),5-triene, but rearrange by other processes such as hydrogen shifts to
trienes which are more suited for the disrotatory process.
An interesting result has been reported for the thermal study of 6k ring
closure in a C1 and C6 deuterated Z-1,3,5-hexatriene (Figure 2-48).113
Secondary isotope effects (kH/ko) of 1.05 for 1E,5E-D2 (114) and 0.88 for 1Z,5Z-
D2 (115) were observed. The two transition states involved are
diastereomerically related with respect to the deuterium substituents. Due to
the different stereochemical environments in the transition state, an increase in

76
intramolecular non-bonding interactions was proposed to increase the force
constants in the case of the terminally c/'s-deuterated material 115 and give rise
to the inverse kn/ko effect observed .
AH* (kcal/mol)
28.6
32
28.2
AS* (eu)
-7
-6
-1
34 -1
c6h5
CH2CH3
Figure 2-47. Activation Parameters for Non-Hindered versus Hindered 1,3(Z),5-
Triene Cyclizations.
Figure 2-48. 1E,5E-D2 (114) and 1Z.5Z-D2-1,3(Z),5-Hexatriene (115).
1,3(Z),5-Triene cyclizations have received considerable theoretical
interest. In calculated transition states for the disrotatory 6rc 1,3(Z),5-triene
electrocyclization, a definite steric crowding in is found between the C1 and C6

77
cis substituents.72'113'114'115'116 The transition state is a boat-like ring conformation
(Figure 2-49) with C1 and C6 cis hydrogens twisted in and separated by less
than the sum of their van der Waal's radii.
Figure 2-49. Approximate Representation of the Calculated 1,3(Z),5-Triene
Disrotatory Transition State.
Conclusions
It is believed that for the cases of the fluorinated 1,3(Z),5-trienes
examined in this study and found in the literature; 9,10-
bis(trifluoroethenyl)phenanthrene (40), perfluoro-E,Z,E-4,5-dim ethyl-2,4,6-
octatriene (Z-56), and perfluoro-Z-1,3,5-hexatriene (76), significant repulsion
must develop between the C1 and C6 1,3(Z),5-triene cis fluorines upon
approach to the boat-like disrotatory transition state. This repulsion leads to an
increase in the energy barrier for this process and subsequently, increased
potential for occurrence of competing processes. The observation of
cyclobutene products from 4tc conrotatory ring closure in these systems seems
reasonable in light of this increased barrier. Closure in a An conrotatory
manner is proposed to have a transition state which does not contain crowding
of the terminal cis substituents as illustrated in Figure 2-50.117'118 This together
with the observed reversal of the relative thermodynamics in the perfluorinated

78
and hydrocarbon cyclobutene/1,3-diene systems lead to An closures as facile
and primary processes in the thermolysis of fluorinated 1,3(Z),5-trienes.
Figure 2-50. Approximate Representation of the Calculated 1,3-Diene
Conrotatory Transition State.
An analogous process to the reported 6tc thermal closure of perfluoro-Z-
1,3,5-hexatriene at higher temperatures was never observed in thermal studies
of perfluoro-E,Z,E-4,5-dimethyl-2,4,6-octatriene (Z-56) most likely because
sufficiently high temperatures were not used in the study of this material.
The fact that terminal cis fluorines impede the 1,3(Z),5-triene disrotatory
process should not be surprising in light of the previous discussions. It is
surprising though, in terms of the magnitude of the effect. The fact is that in
these fluorinated systems, An cyclization is favored over 6n, and occurring
roughly at temperatures necessary for the hydrocarbon 6n rearrangement. This
large deviation in the thermal chemistry of fluorocarbon from hydrocarbon
precedent upon terminal 1,3(Z),5-triene cis fluorination created the impetus for
further study of fluorine's effect on thermal processes involving disrotatory and
conrotatory transition states. Out of this interest, a strategy designed to provide
more insight to this seeming steric influence of fluorine was developed and it's
study is described in Chapter 3.

CHAPTER 3
[3,3]-SIGMATROPIC REARRANGEMENTS OF
TERMINALLY FLUORINATED 1,5-DIENES
Introduction
The observation that 6n thermal disrotatory closure of perfluorinated
1,3(Z),5-trienes is disfavored to such an extent that other primary processes
occur exclusively, is unprecedented and encouraged further attention. The
usual strong electronic influence of fluorine on a reaction process seemed in
the disrotatory process to be offset by an factor more steric in origin. As
discussed in Chapter 1, such influences are rarely responsible for the course of
reaction in fluorinated organic systems due to the small difference between
fluorine and hydrogen in size and bond length to carbon. Nevertheless, the
tightly bound nature of the concerted transition state which is required for
1,3(Z),5-triene disrotatory cyclization leads to a twisting in and crowding of the
terminal cis substituents which is believed to be at least partially responsible for
the observed deviation of perfluorocarbon chemistry from that of analogous
hydrocarbons. While precedent from the hydrocarbon literature indicated
destabilization of such a transition state by groups substantially larger than
hydrogen at the 1,3(Z),5-triene terminal cis positions, it seemed surprising that
upon substitution of hydrogen by fluorine at these positions, rather than
observing an higher energy disrotatory process, alternate rearrangements were
observed. It was then the intention to study another system with a lesser degree
of fluorination rearranging from a specific conformation which would allow a
79

80
more quantitative understanding of the effect terminal fluorination has on
pericyclic processes.
The f3.31-Siqmatropic Shift of 1.5-Dienes: The Cope Rearrangement
A hydrocarbon system which has been thoroughly scrutinized
experimentally and theoretically is the Cope Rearrangement. This process is
formally a subset of the family of sigmatropic shifts, which involve migration of a
a bonded atom or n system from one terminus of a conjugated it system to the
other in a concerted fashion. The all carbon [3,3]-sigmatropic shift was
discovered by Hurd119 and later by Cope120 and the most simple case involving
the degenerate rearrangement of 1,5-hexadiene is illustrated in Figure 3-1.
5
1
4%^ 6
5
Figure 3-1. The Cope Rearrangement of 1,5-Hexadiene.
Orbital symmetry considerations dictate that the process occur in a [3S,3S]
fashion, meaning that bonding occurs from the same face at the terminus of
each three carbon fragment.34 Such a restriction still allows for the
rearrangement to occur through a number of viable conformations of the 1,5-
diene system. Among the conformations available to this system, it has been
experimentally demonstrated that the Cope rearrangement occurs preferentially
through a chair conformation transition state except in cases where the system
is geometrically constrained so as to make the chair inaccessible. A variety of
studies involving stereochemically labeled 1,5-diene systems have

81
demonstrated the exclusive nature of this process and estimate the chair is
favored over a boat conformation transition state by at least 6 kcal/mol in
enthalpy.54 Semiempirical121 and more recent ab initio122 123 level theoretical
studies confirm by similar barriers the experimental preference found for the
chair over the boat transition state conformation. The energy difference and
hence the exclusive chair transition state for this process is rationalized as
being due to a through space, destabilizing antibonding interaction between
orbitals on C2 and C5 in the boat conformation.34’124 Although there is no
question as to the preferred conformation of the transition state, the aspect of
synchronicity or bond timing in this concerted process has been under
continuous debate. Such mechanistic finepoints will be addressed later in
discussion but at this point, only the aspect of favored conformation will be
considered.
The Cope system appears to be ideal for study of the effect of terminal
fluorination, as the transition state geometries (Figure 3-2) contain the same
bulk structural features which were rationalized as influencing the fluorinated
thermal electrocyclic processes discussed in Chapter 2. The calculated
transition state conformation for the thermal 6k disrotatory process113 is
structurally similar to a boat Cope process121-122 and the photochemical 6k
conrotatory process125 is similar to the chair Cope process.121-122 The Cope
system surpasses the electrocyclic process in terms of utility for thermal study in
that both the boat and chair Cope processes are orbital symmetry allowed
thermal processes, whereas the electrocyclic disrotatory and conrotatory
processes are allowed only for thermal and photochemical excitation
respectively. The fundamental differences between the ground and excited
state processes in the 6k electrocyclic study do not allow for easy comparison of
activation parameters or discussion of steric and electronic effects of terminal

82
substituents between the two conformations. Seeing as both conformations may
undergo symmetry allowed thermal Cope processes, design of appropriate
terminally fluorinated 1,5-dienes and measurement of the activation parameters
for Cope rearrangement would allow for a more quantitative understanding as
to the effect of terminal fluorination on these transition state conformations.
Figure 3-2. 6k Electrocyclic and Cope Transition State Conformations.
Fluorinated Cope Systems
The thermal study of fluorinated 1,5-dienes has received little qualitative
or quantitative attention. Two recent reviews offer the minimal literature
available addressing qualitative aspects of [3,3]-sigmatropic processes in
fluorinated 1,5-dienes,126 allylvinyl ethers,126 and carbanions.127
The observation of the effect of terminal fluorine on a chair constrained
thermal Cope process was most easily studied by synthesizing terminally
fluorinated dienes which would complement hydrocarbon systems for which
reliable activation parameters had been previously reported. Due to the
degeneracy in the system, the parent 1,5-hexadiene had been studied as

83
1,1-dideutereo-1,5-hexadiene (Figure 3-3, 116).128 The partially fluorinated E-
and Z-1-fluoro-1,5-hexadiene129 (118, 119), and 1,1-difluoro-1,5-hexadiene129
(121) thermal studies had already been reported in the literature with reliable
activation parameters. To complete the simple 1,5-hexadiene series required
synthesis and thermal study of 1,1,6,6-tetrafluoro-1,5-hexadiene (123).
Figure 3-3. Fluorinated 1,5-Hexadiene Cope Processes of Interest.
The experimental study of boat constrained Cope systems has received
a variety of interest, and again, systems were chosen for mechanistic novelty,
activation parameter reliability of the reported hydrocarbons, and synthetic
simplicity. Two hydrocarbon systems (Figure 3-4) which have been
investigated where geometrical constraints force a boat conformation Cope
rearrangement are 1,4-dimethylenecyclohexanes130’131 such as 125, and meso-
1-(2-methylidenecyclopentyl)-2-methylidenecyclopentane132 (meso-126). An
artifact of the synthetic route into meso-126, the d,/-1 -(2-methylidene-
cyclopentyl)-2-methylidenecyclopentane isomer d,l-126 is also afforded. This

84
diastereomer is constrained to undergo the Cope rearrangement through a
chair conformation, creating another system for comparison with those of Figure
3-3.
d,M 26
Figure 3-4. Cope Rearrangements in Conformationally Constrained Systems.
There is a subtle but important difference between the two boat
conformations involved with 125 and meso-126. Due to the symmetry of the
system, the boat type transition state for 125 will constrain the two terminal
methylenes to approach one another in a coplanar eclipsed fashion with no
twisting in of terminal substituents. In contrast, the meso-
bismethylenecyclopentane meso-'\26 will be able to accommodate a true boat
transition state which involves a significant turning in of the two terminal cis
substituents. A thermal study of 1,4-dideuteriomethylidenecyclohexane (125)
has been reported as has a study of the hydrocarbon d,l- and

85
meso-bismethylenecyclopentanes {d,l-126, meso-126), and all are reported
with reliable activation parameters.
The materials then of interest in this study are illustrated in Figure 3-5. To
probe the effect of terminal fluorination in these different systems, the synthesis
of a variety of materials was required to complete each series from
hydrocarbon, to terminally gem-difluorinated, to terminally bis-gem-difluorinated
1,5-diene. Having reliable reported activation parameters for 116, 121, 125,
and meso and cf,/-126, it was necessary to carry out syntheses and thermal
studies of 123, 128, 129, meso and d,l-130, and meso and cf,/-131.
Although interest existed in meso and d,l-130, this system was not studied
due to time limitations. The synthetic routes and thermal results for 123, 128,
129, and meso and d,l-131 will now be discussed.
Figure 3-5. Three Hydrocarbon to Terminally Fluorinated 1,5-Diene Series.

86
Synthesis and Thermolysis of Terminally Gem-difluorinated 1.5-Diene Systems
1.1.6.6-Tetrafluoro-1,5-hexadiene (123)
1,1,6,6-Tetrafluoro-1,5-hexadiene (123) was synthesized in six steps
from 1,4-butanediol in an overall isolated yield of 6%. The reaction sequence is
illustrated in Figure 3-6. 4-[(Tetrahydro-2/-/-pyran-2-yl)oxy]-1-butanal (132) was
prepared by a literature procedure133 from 1,4-butanediol in two steps and
subjected to a Wittig-type fluoroolefination134 to yield 5-[(tetrahydro-2F/-pyran-2-
yl)oxy]-1,1-difluoropent-1-ene (133). Deprotection to 5,5-difluoro-4-penten-1-ol
(134) and pyridinium dichromate (PDC) oxidation yielded 5,5-difluoro-4-
pentenal (135). Wittig-type fluoroolefination then afforded the desired 1,1,6,6-
tetrafluoro-1,5-hexadiene (123). Initial attempts to obtain 123 through Wittig-
type fluoroolefination of 1,4-butanedial did not afford any amount of fluoroolefin
and was not further pursued.
H
132
OTHP
Figure 3-6. Synthesis of 1,1,6,6-Tetrafluoro-1,5-hexadiene (123).
Due to appreciable volatility, the thermolysis of 123 was examined in the
gas phase as described in Appendix A. Quantitative conversion of 123 to

Ln[%123]
87
207.2°C
216.2°C
224.4°C
228.8°C
235.7°C
241.6°C
Temperature (°c)
k (x105 sec'1)
R2
207.2
2.24 ±0.01
0.9999
216.2
4.13 ±0.05
0.9993
224.4
6.88 ± 0.07
0.9996
228.8
8.87 ±0.12
0.9993
235.7
13.68 ± 0.07
0.9999
241.6
19.76 ±0.10
0.9999
k^CF2 ^ %^CF2
123 124
Figure 3-7. First-Order Rate Plots and Rate Constants for Thermolysis of
1,1,6,6-Tetrafluoro-1,5-hexadiene (123).

88
3,3,4,4-tetrafluoro-l,5-hexadiene (124, Figure 3-7) was observed. The
thermolysis was examined at six temperatures from 207.2°C to 241.6°C and the
conversion was observed to follow first-order kinetics with no degree of
reversibility observed. Figure 3-7 offers the first-order plots and rate constants
for the temperatures examined.
The activation parameters (AH*, AS*) for the cyclization were obtained
using the Eyring expression,68 k = — e^ RT V R J, rearranged to the form
h
Ln(k/T) = -AH*/RT + AS*/Ft + Lr\(k/h), where k = rate constant at absolute
temperature T, k= Boltzmann constant (1.381x10 23 J/K), h = Planck's constant
(6.626x1 O'34 Jxs), and R = ideal gas constant (1.9872 cal/moIxK). A linear least-
squares regression plot of Ln(k/T)versus 1/T, as illustrated in Figure 3-8, yielded
AH* = 29.9 ± 0.2 kcal/mol and AS* = -18.5 ± 0.5 cal/molxdeg for the Cope
rearrangement of 123 to 124 with the errors reported as one standard
deviation.
Figure 3-8. Eyring Plot for Thermolysis of 1,1,6,6-Tetrafluoro-1,5-hexadiene
(123).

89
1-Difluoromethylidene-4-methvl¡denecvclohexane (1281
1-Difluoromethylidene-4-methyl¡denecyclohexane (128) was prepared
in three steps from 1,4-cyclohexanedione mono-ethylene ketal (136) in a 37%
isolated yield. The reaction sequence is illustrated in Figure 3-9.
136
(C6H5)3PCH3Br
n-BuLi, THF, 0°C
ch>=0<
137 (69%)
15% H2S04
Silica Gel
CH2CI2
138 (90%)
P(N(CH3)2)3
CF2Br2
THF, 0°C-RT, 4 hr
128 (38%)
Figure 3-9. Synthesis of 1-Difluoromethylidene-4-methylidenecyclohexane
(128).
4-Methylidene-1-cyclohexanone ethylene ketal (137) was prepared from 1,4-
cyclohexanedione mono-ethylene ketal (136) by a Wittig reaction135 then
deprotected136 to yield 4-methylidenecyclohexanone (138). This material was
subjected to Wittig-type fluoroolefination134 to yield the desired 128.
Due to appreciable volatility, the thermolysis of 128 was examined in the
gas phase as described in Appendix A. Quantitative conversion of 128 to 1,1-
difluoro-2,5-dimethylidenecyclohexane (139, Figure 3-10) was observed. The
thermolysis was examined at six temperatures from 279.9°C to 309.1°C. The
conversion was observed to follow first-order kinetics and no degree of
reversibility was observed. Figure 3-10 offers the first-order plots and rate
constants for the temperatures examined.

90
Temperature (°C)
k (x10s sec1)
R2
279.9
3.78 ± 0.09
0.9976
287.8
6.72 ± 0.04
0.9998
292.1
8.88 ±0.19
0.9977
297.6
12.51 ±0.19
0.9989
303.0
18.12 ± 0.15
0.9996
309.1
25.72 ± 0.16
0.9998
cf2
A
^^CF2
128
139
Figure 3-10. First-Order Plots and Rate Constants for Thermolysis of
1 -Difluoromethylidene-4-methylidenecyclohexane (128).
279.7°C
287.8°C
292.1 °C
297.6°C
303.0°C
309.1 °C

91
A linear regression plot of Ln(k/T) versus 1/T (Figure 3-11), as described
in the case of 123, yielded AH* = 40.8 ± 0.5 kcal/mol and AS* = -6.1 ± 0.9
cal/molxdeg for the Cope rearrangement of 128 to 139.
Figure 3-11. Eyring Plot for Thermolysis of 1-Difluoromethylidene-4-
methylidenecyclohexane (128).
1.4-Difdifluoromethvlidene1cvclohexane (1291
1,4-Di(difluoromethylidene)cyclohexane (129) was synthesized in one
step (Figure 3-12) from 1,4-cyclohexanedione (140) by a Wittig-type
fluoroolefination134 and isolated in an 36% yield.
P(N(CH3)2)3
CF2Br2
THF, 0°C-RT, 4 hr
cp2=0=
CFo
129 (36%)
140
Figure 3-12. Synthesis of 1,4-Di(difluoromethylidene)cyclohexane (129).

92
Temperature (°C)
k (xIO4 sec1)
R2
329.2
1.35 ±0.02
0.9993
336.9
2.07 ± 0.05
0.9980
343.2
3.00 ± 0.02
0.9998
349.1
4.02±0.10
0.9980
354.5
5.47 ± 0.15
0.9968
359.8
7.40 ±0.11
0.9993
cf2
cf2
129 141
279.7°C
287.8°C
292.1 °C
297.6°C
303.0°C
309.1 °C
Figure 3-11. First-Order Plots and Rate Constants for Thermolysis of
1,4-Di(difluoromethylidene)cyclohexane (129).

93
Due to appreciable volatility, the thermolysis of 129 was examined in the
gas phase as described in Appendix A. Quantitative conversion of 129 to
1,1,2,2-tetrafluoro-3,6-dimethylidenecyclohexane (141, Figure 3-13) was
observed. The thermolysis was examined at six temperatures from 329.2°C to
359.8°C. The conversion was observed to follow first-order kinetics and no
degree of reversibility was observed. Figure 3-13 shows the first-order plots
and rate constants for the temperatures examined.
A linear regression plot of Ln(k/T)versus 1/T, as described in the case of
123, yielded AH* = 40.7 ± 0.5 kcal/mol and AS* = -10.1 ± 0.8 cal/molxdeg for
the Cope rearrangement of 129 to 141.
Figure 3-14. Eyring Plot for Thermolysis of 1,4-Di(difluoromethylidene)-
cyclohexane (129).

94
meso- and c/.H-(2-Difluoromethvlidenecvclopentvl)-2-difluoronnethvlidene-
cvclopentane (roeso-131 ,d./-131)
Meso-131 and cf,/-131 were prepared in four steps and isolated in 7%
overall yield as illustrated in Figure 3-15. 2-Chlorocyclopentanone was added
to the sodium enolate of ethyl 2-oxocyclopentanecarboxylate (142), and the
resultant material decarboxylated under acid catalysis to yield 2-(2-
oxocyclopentyl)cyclopentanone (143).137 This material was subjected to Wittig-
type fluoroolefination134 to yield 1-(2-difluoromethylidenecyclopentyl)-2-
difluoromethylidenecyclopentane (131) in a 5.41:1 ratio of dj to meso. Due to
1.) Na°, toluene, A
2.) 2-chlorocyclopentanone
3.) HCI, HpO, EtOH
142
143 (26%)
P(N(CH3)2)3 (4)
CF2Br2 (2)
THF, 0°C-RT, 4 hr
131 (28%)
d, 1/meso = 5.41
Figure 3-15. Synthesis of meso- and d>1-(2-Difluoromethylidenecyclopentyl)-
2-difluoromethylidenecyclopentane {meso-131 ,d,/-131).
insufficient vapor pressure at the operating conditions of the gas kinetics line
and problems with condensation of the material on cool line sections and joints,
it was necessary to study the thermolysis of 131 in solution. A 0.54 M solution
of 131 was prepared in n-dodecane and the extent of conversion was followed
versus internal standard by 19F NMR. The temperatures necessary to afford the
rearrangement of meso-131 were roughly 200°C higher than those required
for rearrangement of cf,/-131. This allowed the mixture of diastereomers to be
thermolyzed and kinetics observed independently. Disappearance of the d,l
material was studied first at a lower temperature, followed by higher
temperature study of the rearrangement of the meso material, thus enabling two
rate constants to be obtained from one sample. Due to difficulties with the

95
apparatus and time involved for the quantitative NMR observations, a limited
number of temperatures were utilized for these systems. Quantitative
conversion of d,l-131 to 1-(2-(1-cyclopentenyl)-1,1,2,2-tetrafluoroethyl)-
cyclopentene (144, Figure 3-16) was observed. The thermolysis of d,l-130
was examined at four temperatures from 94.0°C to 124.0°C. Transformation of
meso-131 to 143 was observed at three temperatures from 274.4°C to
293.1°C. Small amounts (<10%) of unidentified materials were observed by 19F
NMR after longer periods of time at these elevated temperatures. Conversions
of both cf,/-131 and meso-131 were observed to follow first-order kinetics and
no extent of reversibility was observed. Figures 3-16 (cf,/-131) and 3-17
(meso-131) show the first-order plots and rate constants for the temperatures
examined.
Linear regression plots of Ln(k/T)versus 1/T, as described in the case of
123, yielded AH* = 22.4 ± 0.2 kcal/mol and AS* = -17.5 ± 0.4 cal/mol deg for the
Cope rearrangement of d,l-131 to 144 (Figure 3-19) and AH* = 49.5 ± 1.0
kcal/mol and AS* = 8.1 ± 1.7 cal/molxdeg for the rearrangement of meso-131
to 144 (Figure 3-20).
Discussion
Increasing the degree of terminal gem-difluorination in a 1,5-diene
system was found to have a small but significant influence on the Cope
processes occurring through chair transition states and a variable influence on
those occurring through boat constrained geometry. Figure 3-21 offers
activation parameters for hydrocarbon and terminally fluorinated systems from
this study and the literature undergoing chair transition state Cope
rearrangements. No significant influence is observed upon terminal

Ln[% 96
94.0°C
104.6°C
117.4°C
124.0°C
Temperature (°c)
k (x105 sec'1)
R2
94.0
5.32 ± 0.06
0.9995
104.6
13.09 ±0.13
0.9996
117.4
36.27 ± 0.33
0.9997
124.0
57.98 ± 1.01
0.9991
Figure 3-16. First-Order Plots and Rate Constants for Thermolysis of cf,/-1-(2-
Difluoromethylidenecyclopentyl)-2-difluoromethylidenecyclopentane {d,l-131).

Ln[%/T7eso-131]
97
274.4°C
288.1 °C
293.1°C
Temperature (°c)
k (xl 0s sec1)
R2
274.4
1.09 ±0.07
0.9904
288.1
3.47 ±0.11
0.9969
293.1
5.03 ± 0.32
0.9919
meso-131
144
Figure 3-17. First-Order Plots and Rate Constants for Thermolysis of meso-1-(2-
Difluoromethylidenecyclopentyl)-2-difluoromethylidenecyclopentane (meso-
131).

98
1/T
Figure 3-19. Eyring Plot for Thermolysis of d,/-1-(2-Difluoromethylidenecyclo-
pentyl)-2-difluoromethylidenecyclopentane {d,l-131).
1/T
Figure 3-20. Eyring Plot for Thermolysis of meso-1-(2-Difluoromethylidene-
cyclopentyl)-2-difluoromethylidenecyclopentane (meso-131).

99
mono-fluorination in the chair process. Within the error of the measurements,
the activation enthalpy and entropy remain unchanged from the
hydrocarbonvalues in the mono-fluorinated cases 118 and 119. The gem-
difluoro system 121 occurs with a 1.5 kcal/mol decrease in AH* but no
significant change in AS* relative to the hydrocarbon. Two terminal gem-
difluoro groups decrease AH* by 3.6 kcal/mol from 116 to 123 and 5.6 kcal/mol
from cf,/-126 to d,/-131. There is also a marked difference in the activation
entropy for these two related processes; AS* decreases by 4.7 cal/molxdeg from
116 to 123 and 6.2 cal/molxdeg from d,/-126 to d,/-131.
Figure 3-22 illustrates data for hydrocarbon and terminally fluorinated
1,5-diene systems from this study and literature constrained to boat transition
state Cope rearrangements. The 1,4-dimethylenecyclohexane system exhibits
an initial 3.6 kcal/mol decrease in AH* and 2.4 cal/molxdeg decrease in AS*
upon introduction of one terminal gem-difluoromethylene group (128 versus
125). Gem-difluorination at both termini (129) shows no change in AH* from
the half fluorinated system (128), but AS* decreases by 4.0 cal/molxdeg. The
fluorinated meso-bismethylenecyclohexane system meso-131, exhibits
increases in AH* of 7.8 kcal/mol and AS* of 8.8 kcal/molxdeg versus the
hydrocarbon meso-126.
While discussing the kinetic effects of fluorination on these systems, it is
important to keep in mind the fashion in which terminal fluorination will
influence the thermodynamics of these Cope processes. The degeneracy of the
process in 1,5-hexadiene and 1,4-dimethylenecyclohexane leads to no net
enthalpy change upon rearrangement, although the deuterated materials (116,
125) used to remove the degeneracy did exhibit Keq(32i.3»c) = 2.19 and Keq =
1.1 respectively, due to secondary isotope effects. The hydrocarbon bis-
methylenecyclopentane (126) was not observed to be reversible to any extent

100
AH* (kcal/mol)
33.5±0.5
34.010.4
33.911.2
32.0 1 0.7
AS* (cal/molxdeg)
-13.811.0
-14.010.5
-14.012.3
-12.1 1 1.4
-18.510.5
-11.312.6
-17.510.4
References: 116,128 (118, 119, 121),129 d,/-126,132 1 23 and d,/-131: This study.
Figure 3-21. Activation Parameters for Chair Transition State Cope Processes.

101
AS* (cal/molxdeg)
-3.7 ± 3.2
-6.1 ±0.9
-10.1 ±0.8
-0.7 ± 1.0
8.1 ± 1.7
References: 125,131 meso-126,132 All others (128, 129, /neso-131) from this study.
Figure 3-22. Activation Parameters for Boat Transition State Cope Processes.

102
indicating AH0 > 5 kcal/mol for 126-4 127 due to the formation of more
substituted olefins. From the earlier discussion (Chapter 1) pertaining to
fluorine’s thermodynamic preference to be bonded to saturated carbon, it is
expected that such a factor will impart anywhere from 2 to 5 kcal/mol
exothermicity to the chair or boat type cyclizations for each gem-difluoroolefin.
In fact, cyclization of 121-»122 was observed to have AH0 = -5 kcal/mol.129 As
might be expected, the conversions of 123->124 and d,/-131-»144 are not
reversible to any extent in line with simple additivity of the above indicated
exothermicities for two such gem-difluoro groups. A similar situation is
observed for the boat constrained systems in Figure 3-22.
With the precedent set for increasing exothermicity in each of these Cope
series as the degree of terminal pem-difluorination is increased, it is not
surprising that the series of fluorinated chair Cope processes examined show a
steady decrease in AH* as the number of terminal gem-difluoro groups
Increases. Such a trend Is in line with the Flammond Postulate138'139 in that an
increasingly exothermic process will lead to an earlier transition state, one
being more reactant-like in structure and energy. Any steric effect that fluorine
imparts on the chair transition state (Figure 3-2) must then be minimal or non¬
existent, as increased fluorination showed only incremental decreases in AFI*.
The trend of decreasing activation enthalpies based on changing relative
thermodynamics with increasing degree of terminal gem-difluorination would be
expected to be observed In the boat constrained Cope systems as it was in the
chair systems if there was no detrimental steric influence due to fluorine. The
series of terminally fluorinated 1,4-dimethylenecyclohexanes (125, 128, 129,
Figure 3-22) seems to be showing a balance between thermodynamic based
AH* lowering and a kinetic destabilization of the transition state as the degree of
terminal olefin gem-difluorination increases. The activation enthalpy decreases

103
from 125 to 128 and does not change from 128 to 129, implying that the
transition state involving coplanar eclipsed approach of the terminal carbons
(Figure 3-4) is encountering some resistance. Physical overlap of the fluorines
is unlikely in this case and resistance would most likely arise from difluoroolefin
dipole or field repulsions. It is more likely though, that the decrease in activation
entropy from 128 to 129 may explain the fact that AH* is constant between
these two systems. The decrease in activation entropy is consistent with a
higher degree of bond formation between the terminal 1,5-diene carbons with
minimal C2-C3 a bond cleavage at the transition state of 129. In effect, this is a
higher degree of bicyclo[2.2.2]octane-1,4-diyl character which would impart
more strain to the transition state in the tetrafluorinated (129) versus the
difluorinated (128) case. If this increase in strain was influencing the transition
state energy in a similar magnitude as the stabilizing effect of saturation of the
additional difluoromethylene group, then as observed, one would expect no net
change in the value of AH* to occur between 128 and 129.
In meso-1 -(2-difIuoromethylidenecyclopentyl)-2-difluoromethylidene-
cyclopentane (meso-131), the true boat conformation (Figure 3-2) allows for
significant twisting in of two terminal c/'s substituents. The 7.8 kcal/mol increase
in AH* between meso-126 and meso-131 is believed to be due to strong
repulsion between the two terminal cis fluorines directed at one another. It is
also possible that this increase may be explained by a coplanar approach of the
terminal olefinic carbons creating repulsion between hydrogens endo on the
two cyclopentyl rings. It is difficult to postulate which situation will occur in the
transition state of meso-131. Either way, the large increase in AH* between
meso-126 and meso-131 indicates that terminal c/'s-fluorination creates
significant resistance to approach of terminal olefinic carbons through a boat
conformation transition state. The activation enthalpy and entropy for this

104
rearrangement are the highest of the boat Cope systems observed. These
energy parameters are consistent with a near-dissociative mechanism involving
cleavage of the 1,5-diene C3-C4 bond (bond a in meso-131, Figure 3-23) to
form a pair of allyl radicals (145) which may recombine to form the observed
product 144 or potential [1,3]-shift adduct 146. The dissociation energy (AH°d)
for bond a in this system may be estimated by subtracting AH°f = +6.4 kcal/mol
for 3,4-dimethyl-1,5-hexadiene from twice the heat of formation of 1-butene-3-yl
(2 x (AH°f = +30.2 kcal/mol)).59 This yields AH°d * 54.0 kcal/mol for cleavage of
this system to a pair of allylic radicals (145). Such an approximation is valid as
each five membered ring is bonded to a nodal carbon in the allylic system and
gem-difluorination has little effect on the stability of an allylic radical (Figure 1-
5).27
146
Figure 3-23. Thermal Rearrangement of meso-1-(2-Difluoromethylidene-
cyclopentyl)-2-difluoromethylidenecyclopentane (meso-131).
This excercise indicates that the observed process is occurring with an
activation enthalpy 4.6 kcal/mol below that necessary for cleavage of meso-
131 to the hypothetical pair of allyl radicals (145). This difference can be
thought of as the energy of concert for this boat conformation Cope process.

105
The activation entropies for both the chair and boat Cope processes are
observed to become increasingly negative as the number of gem-difluoro
groups increases (Figures 3-21 and 3-22) except as discussed in the case of
meso-131. The 1,5-hexadiene systems, from hydrocarbon to terminally gem-
difluorinated cases (116,118, 119, and 121), show similar AS* values within
the measured errors. Between 1,1-difluoro-1,5-hexadiene and 1,1,6,6-
tetrafluoro-1,5-hexadiene (121 and 123) though, a 6.4 cal/molxdeg decrease is
observed. A decrease is also observed between bismethylenecyclopentane
systems cf,/-12 6 and d,l-131 and down the series of
dimethylenecyclohexanes, 125, 128, 129; in all cases as the degree of
terminal gem-difluorination is increased.
Such a substituent effect on the activation entropy of the Cope process
has been previously observed in phenyl substituted diene systems and leads to
the question of concert in the Cope process, which is a topic of current debate.
One may envision the process as potentially occurring somewhere along a
continuum involving concerted or one of two nonconcerted pathways. The
nonconcerted extremes involve either the generation of two allyl radical
fragments or formation of a 1,4-cyclohexanediyl. Two allyl radical fragments are
argued to be too high in energy to possibly be involved in the Cope process of
1,5-hexadiene, as such a path occurring by C3-C4 bond homolysis requires an
additional 24 kcal/mol in enthalpy above the transition state for the concerted
process.118 As a consequence, 1,3-shift products are not observed upon
thermolysis of 1,5-dienes.
The 1,4-cyclohexanediyl alternative is the point of contention. Based on
arguments that the heat of formation of bicyclo[2.2.0]hexane is 9 kcal/mol
greater than 1,5-hexadiene and cleavage to 1,5-hexadiene occurs with AH* =
36 kcal/mol, the cyclohexanediyl transition state is estimated to be 12 kcal/mol

106
higher in energy than the concerted structure and inaccessible to simple alkyl
substituted 1,5-hexadienes.54 This fact has been countered extensively by
Dewar,140’141 who through theoretical ab initio level study has argued the
mechanism of the boat and chair processes are different. Dewar makes claim
that the boat processes would be formally concerted and the concerted chair
processes are actually occurring through a 1,4-cyclohexanediyl which involves
strong "through bond coupling", making the transition state behave like a closed
shell species. In contrast, there are those who argue in favor of the historical
concerted process, such as Houk, who studied the system at the ab initio level
and concluded concerted bond reorganization is occurring in the transition
state.118 Although disagreement is observed even with high levels of theory,
these authors are consistent in agreeing that the mechanism of the Cope
process will vary strongly across the possible allyl diradical/concerted/1,4-
cyclohexanediyl spectrum depending on the electronic nature of substituents
and their position of placement upon the 1,5-diene system.
The extent of bond making and bond breaking in the Cope
rearrangement has been probed by observing secondary deuterium isotope
effects in substituted 1,5-dienes.54'142 From these results, it is generally agreed
that radical stabilizing substituents at C2 and C5 lead to increased bond order
between C1 and C6, in line with a 1,4-cyclohexanediyl type structure, and such
substituents at C3 and C4 lead to transition states which more resemble a pair
of allyl radicals. The notion of the 1,4-cyclohexanediyl has been further probed
by comparison of the thermal chemistry of 2,6-diphenyl-1,6-heptadiene (147)
and 2,5-diphenyl-1,5-hexadiene-7,6-13C2 (150)143 Heptadiene 147 was
termed a "frustrated" Cope system as it contains an additional methylene unit,
making a concerted process impossible and offering a chance to probe the
diradical. For 150, it was found that AH* = 22.0 ±0.18 kcal/mol and

107
Figure 3-24. Thermal Rearrangements of 2,6-Diphenyl-1,6-heptadiene (147)
and 2,5-Diphenyl-1,5-hexadiene-7,6-13C2 (150).
AS* = -20.7 ± 0.4 cal/molxdeg and for 147 it was found that AH* = 28.9 ± 0.6
kcal/mol and AS* = -23.6 ±1.1 cal/molxdeg. From this data and improved MM2
force field calculations, it was concluded that by introduction of benzyllic
resonance into the 1,4-cyclohexanediyl, the diradical process occurs with an
enthalpy of activation 14 kcal/mol below the concerted transition state for 1,5-
hexadiene.
Recently the [3,3]-sigmatropic rearrangement of perfluoroallylvinyl ether
to perfluoro-4-pentenal has been reported144 with activation parameters AH* =
18.5 kcal/mol and AS*= -33.0 cal/molxdeg which differ significantly from the
analogous hydrocarbon allylvinyl ether activation parameters54 of AH*= 25.7
kcal/mol and AS*= -14.1 cal/molxdeg. A qualitative study (Figure 3-25) of
perfluoro-1,5-hexadiene (153) and perfluoro-3-chloro-1,5-hexadiene (155)
has also been recently reported.145 At 250°C, 153 equilibrates with 152 with
Keq » 0.7, and at temperatures greater than 300°C, 154 is formed quantitatively

108
F
- F ^
152
153
154
CL ^
_ “v^/T9
F
9 ^
o
f9
155
156
157
Figure 3-25. Thermal Rearrangements of Highly Fluorinated 1,5-Hexadienes.
from the mixture. Thermolysis of 156 leads to a mixture of 155 and 157 with
the latter being the major reaction component. Since the formation of 152 and
157 require formation of a boat 1,4-cyclohexanediyl, it was tentatively
concluded that the perfluorinated Cope system prefers initial boat conformation
closure to such a diyl rather than closure through a chair followed by chair to
boat conversion of the diyl, which was proposed to be impeded by "a large
barrier". Formation of such a diyl may then be followed by bond formation to
bicyclo[2.2.0]hexanes or ring opening to 1,5-cyclohexadienes. Such a process
would seem unlikely in light of the strong disfavoring of such a transition state
conformation observed with meso-131.
The increasingly negative activation entropies in the fluorinated Cope
series (Figure 3-21 and 3-22) has limited precedent in the perfluoro Claisen
rearrangement of perfluoroallylvinyl ether and is similar in trend to the C2 and
C5 substituted hydrocarbon Cope systems which are argued to proceed
through 1,4-cyclohexanediyl type intermediates. A mechanism involving a pair
of allylic radicals is not consistent with the observed activation parameters as
activation entropies and enthalpies would be expected to be larger than those

109
of corresponding hydrocarbons upon increasing fluorination and the stability of
an allyl radical is known to be insensitive to partial fluorination (Figure 1-5).
It is more likely the case that the entropy of activation together with the
enthalpy of activation data collected for the terminally gem-difluorinated 1,5-
dienes, with the exception of meso-131, are indicating a concerted process
which involves non-synchronous bonding changes at C1-C6 and C3-C4. The
formation of the stronger and shorter a bond in the case of the terminally
tetrafluorinated 1,5-diene systems, would create a tighter transition state
involving a higher degree of bond formation between C1-C6 than bond
cleavage between C3-C4. Such non-synchronous bonding changes would
impart radical character at the C2 and C5 positions. The changes in the
activation parameters in these systems from those in the hydrocarbons must
then be a result of the changing relative thermodynamics in these fluorinated
systems as (3-fluorination is known to stabilize radicals to a negligible degree5
and therefore should not directly influence the transition state energy.
Conclusions
The influence of terminal gem-difluorination in pericyclic processes
involving chair versus boat transition states is seen from these results to be
fundamentally different. The chair type transition states are seen to
accommodate terminal fluorine to any degree without detrimental kinetic effects.
The changes in the activation parameters in this case can be attributed to
changes in the relative thermodynamics of the 1,5-diene systems as the degree
of terminal gem-difluorination is increased and are consistent with a mechanism
involving a high degree of 1,5-diene C1-C6 bond formation with little C3-C4
bond cleavage. The boat type transition state is undergoing the same relative
changes in thermodynamics upon increased fluorination, but the twisting in of

110
terminal cis fluorines in this conformation leads to highly repulsive interactions
which give rise to activation parameters consistent with a transition state more
resembling a pair of allyl radicals, involving a high degree of C3-C4 bond
cleavage without a similar degree of C1-C6 bond formation.

CHAPTER 4
EXPERIMENTAL
General Methods
Nuclear magnetic resonance (NMR) chemical shifts are reported in parts
per million (ppm) downfield (8) from internal reference TMS for 1H and 13C
spectra, and in ppm upfield (cp) from internal standard CFCI3 for 19F spectra. All
NMR spectra were obtained on Varían VXR-300 or Varían XL-200 instruments.
The format (field strength, solvent, reference) is included for all NMR spectra
reported.
Gas chromatographic separations were performed by Gas-Liquid Phase
Chromatography (GLPC) on packed columns. Quantitative GLPC was
performed on a Hewlett Packard 5890 Series II gas chromatograph with a flame
ionization detector and a Hewlett Packard 3396A integrator. Preparative GLPC
was performed on a Varían Aerograph A-90 gas chromatograph equipped with
a thermal conductivity detector. Conditions and columns used are discussed in
relevant experimental sections.
Mass spectra and exact masses were determined on a Kraytos/AEI-30
spectrometer at 70 ev.
Ultra-violet (UV) spectra were obtained on an Perkin-Elmer Lambda 9
UVA/IS/NIR spectrophotometer.
Melting points were obtained on a Thomas Hoover Uni-Melt capillary
melting point apparatus and are uncorrected.

112
Experimental text discussing a "dry" solvent indicates such material was
purified (distilled) off of the appropriate drying agent and stored under an inert
atmosphere. The following solvents and drying agents were used:
dimethylformamide (CaH2 or P2O5, =60°C/20 mm Hg), triglyme (CaH2 or sodium
benzophenone ketyl, 0.5 mm Hg), tetrahydrofuran (sodium benzophenone
ketyl), diethyl ether (sodium benzophenone ketyl), n-alkanes (CaH2). All other
special preparations are discussed in the appropriate experimental section.
Experimental Procedures
Preparation of 9-Bromo-10-nitrophenanthrene (47)
9-Bromo-10-nitrophenanthrene (47) was prepared by adaptation of a
procedure as described by Callow and Gulland.64 9-Bromophenanthrene63
(26.33 g, 1.025x1 O'1 mol) was dissolved in 60 ml of glacial acetic acid in a 250
ml, three neck, round bottom flask equipped with a magnetic stirrer, stopper,
and a condenser with a piece of polyethylene tubing for directing nitrogen
oxides evolved up into the hood. 30 ml of acetic anhydride was added, and the
mixture was warmed to 90°C. Concentrated (70%, 10 ml) nitric acid was placed
in the addition funnel and added dropwise with vigorous stirring over 30
minutes. Upon completion of addition, the mixture was heated at a gentle reflux
for 1 hour. Analysis of the mixture by TLC (Merck Kieselgel 60 F254 glass
backed plates) in 2.5 hexanes/1 CH2CI2 showed eight spots. Rf values: 0.64 (w,
9-bromophenanthrene), 0.39 (w), 0.36 (s), 0.29 (w), 0.25 (m), 0.20 (m), 0.11 (w),
0 (w). After the reflux period, the reaction mixture was allowed to cool to room
temperature and an amorphous, deep brick-red solid fell out of a solution of the
same color. This material was recrystallized from acetone, CCU, then twice
from methyl ethyl ketone. Crystalline 47 is afforded pure from the last
recrystallization in methyl ethyl ketone as 8.01 g (25.9%) light yellow needles

113
melting 202-204°C (Lit. 195°C),64 with Rf = 0.36 in the above solvent system. A
fine yellow precipitate was obtained out of the CCU and first methyl ethyl ketone
filtrates, Rf = 0.36 (weak) and 0.25 (strong). One further recrystallization from
methyl ethyl ketone yields 3.0 g (13.2%) pale yellow crystals of 9-bromo-3-
nitrophenanthrene melting 189-190°C, with Rf = 0.25 in the above solvent
system.
9-Bromo-10-nitrophenanthrene (47): 1H NMR (300 MHz, CDCI3, TMS)
7.60-7.82 (m, 5H), 8.41 (d with fine splitting, 1H, 3JHh = 8.0 Hz, JHh = 1-74 Hz),
8.65 (d, 1H, 3JHH = 7.80 Hz), 8.66 (d, 1H, 3JHH = 8.02 Hz); 13C NMR (75 MHz,
CDCI3, TMS) 113.1, 122.2, 122.9, 123.1, 123.5, 128.5, 128.7, 128.7, 129.3,
129.3, 130.1, 130.6; Low Resolution Mass Spectrum: m/z (% relative intensity)
303 (27), 301 (28), 245 (28), 243 (29), 222 (16), 178 (18), 177 (18), 176 (100),
164 (21), 163 (18), 150 (18)
9-Bromo-3-nitrophenanthrene: 1H NMR (300 MHz, CDCI3, TMS) 7.81 (m,
2H), 7.90 (d, 1H, 3Jhh = 8.78 Hz), 8.16 (s, 1H), 8.38 (d, 1H, 3JHh = 8.7 Hz), 8.43
(d, 1H, 3Jhh = 8.56 Hz), 8.73 (d, 1H, 3JHH = 9.4 Hz), 9.53 (d, 1H, 4JHH = 2.18 Hz);
13C NMR (75 MHz, CDCI3, TMS) 119.3, 121.2, 123.2, 126.7, 128.7, 128.8,
128.9, 129.0, 129.5, 130.9, 131.2, 135.6; Low Resolution Mass Spectrum: m/z
(% relative intensity) 303 (52), 302 (8), 301 (49), 245 (12), 243 (12), 177 (16),
176 (100), 175 (16), 174 (13), 150 (13), 88 (14), 87 (9)
Preparation of 9-lodo-10-nitroDhenanthrene (481
9-Bromo-10-nitrophenanthrene (47, 1.0 g, 3.3x10‘3 mol), dry Nal (5.64 g,
3.76x1 O’2 mol), and 40 ml of DMF were combined in a 100 ml, three neck, round
bottom flask equipped with a magnetic stirrer, condenser, and two stopcocks.
The reaction mixture was brought to a gentle reflux for 16 hours while following
the reaction by TLC (Merck Kieselgel 60 F254 glass backed plates) in 2.5

114
hexanes/1 CH2CI2. After 16 hours, TLC shows one major and two minor
products. Rf = 0.32 (s), 0.1 (w), 0 (m). (9-bromo-10-nitrophenanthrene has Rf =
0.36 in the same system.) The reaction mixture was cooled and added to a
separatory funnel containing 250 ml of water. The aqueous mixture was
extracted with diethyl ether (4 x 150 ml). The ether extracts were combined and
washed with 3 x 250 ml of water. The ether solution was dried over anhydrous
MgS04, and distilled by rotary evaporator to yield 0.49 g (42%) burnt-orange
crystals of 48 melting 196-198°C (Lit.198-200°C).65
9-lodo-10-nitrophenanthrene (48): 1H NMR (300 MHz, CDCI3, TMS)
7.58-7.78 (m, 5H), 8.31 (d with fine splitting, 1H, 3JHh = 7.4 Hz, 4JHh = 1.5 Hz),
8.59 (d, 1H, 3JHh = 7.5 Hz, 4JHH = 1.5 Hz), 8.66 (d, 1H, 3JHH = 7.8 Hz); 13C NMR
(75 MHz, CDCI3, TMS) 122.3, 122.5, 122.9, 123.1, 123.7, 128.6, 128.7, 128.9,
129.1, 129.3, 130.0, 130.7, 130.8, 134.9; Low Resolution Mass Spectrum: m/z
(% relative intensity) 350 (12), 349 (75), 291 (16), 192 (12), 178 (11), 177 (17),
176 (100), 164 (30), 163 (15), 150 (16), 88 (14); Elemental Analysis on
Ci4H8IN02 Calculated %: C:48.17, H:2.31, N:4.01, Measured %: C:48.47,
H:2.21, N:3.86
Preparation of lodotrifluoroethvlene
lodotrifluoroethylene was either purchased from Peninsular Chemicals
Research, Gainesville, Florida, or prepared by the method of Hansen.70 Flame
dried apparatus was assembled under N2 purge as follows: 1 liter, three neck,
round bottom flask fitted with cold finger condenser, jacketed addition funnel,
stopper, and magnetic stirrer. Acid activated zinc powder (32.8 g, 0.502 mol)
was added to the reaction vessel followed by 500 ml of dry DMF. BrFC=CF2
(90.0 g, 0.559 mol) was condensed into the dry-ice/isopropyl alcohol cooled,
jacketed addition funnel from a tared Rotaflow tube. The BrFC=CF2 was added

115
drop-wise over 30 minutes and the reaction vessel was cooled with an ice-
water bath to contain the generated exotherm. Upon completion of addition, the
mixture was stirred for 1 hour, then the condenser was replaced with a vacuum
takeoff. A liquid N2 cooled, two necked Rotaflow trap was placed between the
vacuum pump and reaction vessel and the reaction mixture was evacuated for
30 minutes at 0.1 mm Hg to remove and trap unreacted BrFC=CF2. The
reaction vessel was then refitted with the condenser and N2 purge and 127.0 g
(1.0 mol) of l2 was added from a solid addition tube to the reaction vessel over
10 minutes while cooling the mixture with an ice-water bath. After the l2 addition
was complete, the cooling bath was removed and the mixture was stirred
rapidly for 3 hours at room temperature. The condenser was then replaced with
a vacuum takeoff and a two necked Rotaflow trap cooled with liquid N2 was
placed between the vacuum pump and the reaction vessel. The reaction
mixture was then flash distilled at room temperature. The IFC=CF2 distillate was
rinsed with 2 x 200 ml of ice-water, keeping the trap in ice at all times. Water
floated over the IFC=CF2 and was removed by cannula using a positive
pressure of N2 over the liquid. The IFC=CF2 was then vacuum transferred into
an evacuated Rotaflow tube containing 4 Á sieves. Low boiling (reported
boiling point of 30-32°C) clear liquid (58.7 g, 56%) , gradually turning pink, was
obtained. 19F NMR of this material is consistent with samples obtained from
Peninsular Chemicals Research, Gainesville, Florida.
lodotrifluoroethvlene: 19F NMR (282 MHz, CDCI3, CFCI3) -84.4 (dd, 1F,
2Jff = 64.3 Hz, 3JcisFF = 51.3 Hz), -109.9 (dd, 1F, 3JtransFF = 128.9 Hz, 2JFf = 64.3
Hz), -146.7 (dd, 1F, 3JtransFF = 128.9 Hz, 2Jff = 51.3 Hz)

116
Preparation of ZnlFC=CF¿ and Zn(CF=CF212
ZnlFC=CF2 and Zn(CF=CF2)2 solutions were prepared by the method of
Heinze and Burton.66 An 100 ml, 2 neck, round bottom flask with a magnetic
stirrer, stopper, and septum was flame dried under Ar purge. Acid activated Zn
powder (8.6 g, 0.13 mol) was added followed by 300 ml of dry triglyme. The
mixture was stirred rapidly and cooled to 0°C. IFC=CF2 (5.61 g, 2.70x1 O'2 mol)
was added by cannula from a tared bottle. After 12 hours stirring at room
temperature, the solution had turned a maple syrup brown from initially clear
and colorless. The yield (based on starting IFC=CF2 by 19F NMR versus internal
standard) is 82% and the ratio of mono to b/s-trifluoroethenylsubstituted Zn
reagent is 3:2.
ZnlFC=CF£ and Zn(CF=CF2)2- 19F NMR (282 MHz, triglyme, CFCI3) mono:
-94.7 (dd, 1F, 2Jff = 91 Hz, 3Jcísff = 33 Hz), -128.4 (dd, 1F, 3J,ransFF = 106 Hz,
2Jff = 91 Hz), -193.3 (dd, 1F, 3J,ransFF = 106 Hz, 2JFF = 33 Hz), bis: -95.4 (dd, 1F,
3Jc¡sFF = 33 Hz, 2Jff = 92 Hz), -129.4 (dd, 1F, 3J,ranSFF = 105 Hz, 2JFF = 92 Hz),
-194.6 (dd, 1F, 3J,ransFF= 105 Hz, 2JFf = 33 Hz)
Preparation of 9.10-Bis(trifluoroethenvhohenanthrene (401
9,10-bis(trifluoroethenyl)phenanthrene (40) was prepared by adaptation
of a procedure as described by Heinze and Burton.66 Apparatus as follows was
flame dried under N2 purge: 100 ml, three neck, round bottom flask fitted with a
septum, glass stopper, condenser with N2 purge, and a magnetic stirrer. Dry
triglyme (15 ml) was added by syringe followed by 0.400 g (1.14x1 O'3 mol) 9-
iodo-10-nitrophenanthrene (48), 0.070 g (5.7x10‘5 mol) Pd(P(C6H5)3)4
(weighed in drybox and transferred by solid addition tube) and 6.0 ml of
perfluoroethenyl zinc iodide solution (-CF=CF2 concentration is 0.65 M by
internal standard 19F NMR, 6.0 ml is 3.9x10‘3 mol) by syringe. The mixture was

117
stirred and heated to 110-112°C. After 7.5 hours, 9-iodo-10-nitrophenanthrene
is consumed as indicated by TLC (Merck Kieselgel 60 F254 glass backed plates)
in 8 hexane/3 THF. Seven spots are evident: Rf = 0.57 (s), 0.44 (w), 0.42 (w),
0.32 (w), 0.26 (w), 0.23 (s), 0.14 (m). The reaction mixture was decanted from a
small amount of black solid into a separatory funnel and diluted with 300 ml of
water, then extracted with 5 x 100 ml of diethyl ether. The ether extracts were
then combined and washed with 5 x 100 ml of water. The ether solution was
dried over anhydrous MgS04 then concentrated by rotary evaporator to yield
0.20 g of brownish-yellow solid. This solid was dissolved in ether and 5 g of
silica gel was added, then the ether evaporated under a stream of N2. The dry
reaction mixture deposited on silica gel was taken up in hexanes and added to
a 2 x 30 cm silica gel column packed by slurry in hexanes. The column was
eluted under flash conditions with hexanes, 9 hexanes/1 THF, and last acetone.
0.063 g (16.2%) 40 was obtained as white flakes melting 133-134°C, Rf = 0.57
in the above solvent system. Other fractions were not pure and accounted for
0.176 g material, which were not further analyzed.
Purification of 9,10-Bis(tnfluoroethenvl)phenanthrene (40) bv Preparative
GLPC
The coupling reaction was carried out using similar conditions as
described previously using 1.0 g 9-iodo-10-nitrophenanthrene (48).
Extractions were carried out as in the previous preparation and the resultant
0.55 g brown oil was dissolved in 0.5 ml of diethyl ether and separated by
preparative GLPC in 50 pi aliquots. (Column: 0.25 inch x 5 feet, 20% QF-1 on
Chromasorb WHP 80/100; Oven: constant at 193°C; Injector: 245°C; TCD block:
232°C; He flow : 120 ml/minute; 40 retention time: 11.0 minutes) White flakes of

118
40 (0.143 g, 15%) were obtained melting at 134°C. The purity of this material is
=100% by analytical GLPC.
9.1 Q-Bis(trifluoroethenyl)phenanthrene (401: 1H NMR (300 MHz, CDCI3,
TMS) 7.67 (t, 2H, 3JHH = 8.0 Hz), 7.75 (t, 2H, 3JHH = 8.0 Hz), 8.07 (d, 2H, 3JHH =
8.1 Hz), 8.68 (d, 2H, 3JHH = 8.1 Hz); 19F NMR (282 MHz, CDCI3, CFCI3, 22°C)
syn diasteromer: low field (= -100) signal overlapped with anti diastereomer,
-115.7 (dd, 2F, 3JtransFF = 117 Hz, 2JFF = 75 Hz), -159.3 (dd, 2F, 2JFF = 75 Hz,
3JcisFF = 20 Hz), anti diasteromer: -100.2 (dd, 2F, 2jff = 70.9 Hz, 3JcisFF = 27.1
Hz), -115.0 (dd, 2F, 3JtransFF = 119.1 Hz, 2jFF = 70.9Hz), -160.6 (dd, 2F, 2JFF =
70.9 Hz, 3JcisFF = 27.1 Hz); NMR (75 MHz, CDCI3, TMS) 123.0, 126.6 (bm),
127.9, 129.1, 131.6; UV Spectrum in n-pentane: X(nm) (E(cm2/moi)), 209 (23742.6),
224 (25146.7), 257 (49706.5), 295 (10428.9), 306 (11760.7); Low Resolution
Mass Spectrum: m/z (% relative intensity) 339 (17), 338 (100), 288 (80), 287
(19), 269 (89), 267 (17), 238 (15), 134 (17); High Resolution Mass Spectrum:
Calculated for CisH8F6 = 338.0530, Measured = 338.0539
Thermolysis of 9.10-Bis(trifluoroethenvnphenanthrene (40): Isolation of
Products 1.2,2,3.3.4-Hexafluoro-2.3-dihvdrotriDhenvlene (41), 1,4,4.5,6,6
Hexafluoro-2.3-(9.10-phenanthro)bicvclof3.1 .Olhex-2-ene (49). 4-Difluoro
methvlidene-3.3.5.5-tetrafluoro-1.2-(9.10-phenanthro)cyclopent-1-ene (50).
and 1,2-(9.10-Phenanthro)-3.5.5-trifluoro-4-trifluoromethvl-1.3-
cvclopentadiene (511
A solution of 0.076 g (2.2x1 O'4 mol) 40 in 1.9 g CeH6was prepared and
flame sealed in a Carius tube under N2. The sample was then placed in a
Statim thermostated oil bath at 180°C and heated for 54 hours. The tube was
opened and GLPC analysis showed starting material and four new products
(Column: 0.125 inch x 10 feet, 20% QF-1 on Chromasorb WHP 100/120; Oven:
constant at 205°C; Injector: 210°C); percentages of total mass balance being:
20% 40, 7% 49, 6% 50, 10% 41, and 57% 51. The solvent was evaporated
under a stream of N2, then the sample was subject to vacuum (0.1 mmHg for 1

119
hour) to yield 0.066 g of yellowish-tan powder, corresponding to an 86% yield of
C18H8F6 isomers. This mixture was taken up in 0.5 ml diethyl ether and
separated into five fractions by preparative GLPC, for a 54% yield of Ci8H8F6
isomers isolated. (Column: 0.25 inch x 5 feet, 20% QF-1 on Chromasorb WHP
80/100; Oven: constant at 193°C; Injector: 245°C; TCD block: 232°C; He flow :
120 ml/minute; Retention times: Compound (minutes), 40 (11.0), 49 (16.5), 50
(18.3), 41 (22.5), 51 (30.5))
Fraction 1: By comparison of 1H and 19F NMR spectra and melting point
with earlier obtained sample, the material is found to be 40. White flakes (6 mg,
9% isolated) were obtained melting 132-134°C and =100% pure by analytical
GLPC.
Fraction 2: 1.4.4.5.6.6-Hexafluoro-2.3-(9.10-phenanthro)bicyclo[3.1.01-
hex-2-ene (49): White powder (2 mg, 3% isolated) was obtained, actually a 2:1
mixture of 49 and 50. A second careful separation of such a mixture by the
aforementioned preparative GLPC conditions would yield ratios around 24:1,
respectively. 1.4.4.5.6.6-Hexafluoro-2.3-(9.10-phenanthro)-bicyclo[3.1.0]hex-2-
ene (49): 1H NMR (300MHz, CDCI3, TMS) 7.72-7.86 (m, 4H), 8.25-8.30 (m, 2H),
8.74 (d, 1H, 3Jhh = 8.4 Hz), 8.76 (d, 1H, 3jHH = 8.4 Hz); 19F NMR (188 MHz,
CDCI3, CFCI3) -87.8 (dddm, 1F, 2JFF = 267.3 Hz, 3JFF = 13.7 Hz, 4JFF = 3.4 Hz),
-112.4 (dm, 1F, 2JFF = 268.0 Hz), 137.7 (dddm, 1F, 2JFF= 173.2 Hz, 3JFF=13.7
Hz, 4Jff = 5.7 Hz), -147.7 (dtd, 1F, 2JFF = 173.2 Hz, 3JFF = 15.3 Hz, 4JFF = 7.6 Hz),
-216.1 to-216.4 (m, 1F), -230.2 (ddddd, 1F, 3JFF = 28.3 Hz, 3jff =15.1 Hz, 3JFF =
8.2 Hz, 4Jff = 4.2 Hz, 4JFF = 1.0 Hz); Low Resolution Mass Spectrum: m/z (%
relative intensity) 339 (16), 338 (97), 288 (71), 287 (16), 269 (97), 238 (17), 134
(29), 119 (49); High Resolution Mass Spectrum: Calculated for C-|8H8F6 =
338.0530, Measured = 338.0547

120
Fraction 3: 4-Difiuoromethvlidene-3.3.5.5-tetrafluoro-1,2-(9.10-phen-
anthro)cyclopent-1-ene (50): A light yellow powder (4 mg, 5% isolated) being a
32.3:1 mixture of 50 and 51 was obtained. 4-Difluoromethvlidene-3.3.5.5-
tetrafluoro-1.2-(9.10-phenanthro)cvclopent-1-ene (50): 1H NMR (300 MHz,
CDCI3, TMS) 7.77 (t with fine splitting, 2H, 3JHh = 7.2 Hz, 4JHh = 1-4 Hz), 7.68 (t
with fine splitting, 2H, 3JHh = 7.1 Hz, 4JHh = 1.4 Hz), 8.39 (d, 2H, 3JHh = 7.7 Hz),
8.78 (d with fine splitting, 2H, 3JHH = 7.6 Hz, 4JHH = 1.4 Hz); 19F NMR (282 MHz,
CDCI3, CFCI3) -70.56 to -70.65 (m, 2F), -89.6 (ddm, 4F, 4JFf = 3.9 Hz, 4JFf = 3.3
Hz); Low Resolution Mass Spectrum: m/z (% relative intensity) 339 (18), 338
(100), 319 (36), 269 (39), 159 (18), 134 (22); High Resolution Mass Spectrum:
Calculated for C-i8H8F6 = 338.0530, Measured = 338.0552
Fraction 4: 1.2.2.3.3.4-Hexafluoro-2.3-dihvdrotriphenvlene (411: A light
yellow solid (4 mg, 5% isolated) 85% pure with contamination by 3% 50 and
12% 51 was obtained. 1.2.2.3.3.4-Hexafluoro-2.3-dihydrotriphenylene (41): 1H
NMR (300MHz, CDCI3, TMS) 7.38 (t, 2H, 3JHH = 8.7 Hz), 7.47 (t, 2H, 3JHh = 8.7
Hz), 7.93 (d, 2H, 3JHh = 8.4 Hz), 8.06 (d, 2H, 3JHH = 8.4 Hz); 19F NMR (282 MHz,
CDCI3, CFCI3) -132.6 (dm, 4F, 3JFF = 12.4 Hz), -135.9 (tm, 2F, 3JFF = 12.4 Hz);
Low Resolution Mass Spectrum: m/z (% relative intensity) 339 (14), 338 (90),
288 (45), 287 (72), 238 (12), 134 (27), 124 (13), 119 (24); High Resolution Mass
Spectrum: Calculated for C18H8F6 = 338.0530, Measured = 338.0540
Fraction 5: 1.2-(9.10-Phenanthro)-3.5.5-trifluoro-4-trifluoromethyl-1,3-
cyclopentadiene (51): Light yellow needles (24 mg, 32% isolated) were
obtained. A second seperation of such material by the previous preparative
GLPC conditions could yield material =100% pure by analytical GLPC, melting
125-126°C. 1.2-(9.10-Phenanthro)-3.5.5-trifluoro-4-trifluoromethyl-1,3-cyclo-
pentadiene (51): 1H NMR (300 MHz, CDCI3, TMS) 7.76 (t, 2H, 3JHh = 8.4 Hz),
7.81 (t, 2H, 3Jhh = 8.4 Hz), 8.30 (d, 1H, 3JHH = 8.0 Hz), 8.40 (d, 1H, 3JHH = 8.1

121
Hz), 8.76 (d, 1H, 3JHh = 8.3 Hz), 8.78 (d, 1H, 3JHH = 8.4 Hz); 19F NMR (282 MHz,
CDCI3, CFCI3) -59.3 (dt, 3F, 4JFf= 14.1 Hz, 4JFF = 2.3 Hz), -103.7 (m,1F), -121.6
(dm, 2F, 4Jff = 8.7 Hz); Low Resolution Mass Spectrum: m/z (% relative
intensity) 339 (17), 338 (100), 319 (12), 270 (9), 269 (64), 249 (10); High
Resolution Mass Spectrum: Calculated for C18H8F6 = 338.0530, Found =
338.0518
Solution Phase Thermolysis of 9.10-Bis(trifluoroethenvnphenanthrene (401: A
Quantitative Study Followed bv ,I3£ NMR
A stock solution of 40 in C8D6 was prepared as follows: 0.0481 g
(1.42x1 O'4 mol) preparative GLPC purified 40 (GLPC conditions as in previous
synthetic section) was dissolved in 1.1 ml of C6D6 and 7 mg C6H5F was added
as an 19F NMR internal standard. An aliquot of the solution was syringed into
each of three thick walled NMR tubes (base rinsed, deionized water rinsed,
acetone rinsed, flame dried) and then the tubes were flame sealed under N2.
Thermolysis was carried out by submerging the sample in a Statim
thermostated oil bath for a time period then rapidly removing and cooling the
sample in an ice bath. The sample was then observed by 19F NMR using a T1
delay of 10 seconds and collecting a minimum of 128 transients before Fourier
transforming the spectrum. The relative concentrations of all fluorinated
products was arrived at by integration of the sample signals and comparison
versus the internal standard C6H5F. (See Tables 4-1, 4-2, and 4-3 for data.)
Solution Phase Thermolysis of 1.4.4,5.6.6-Hexafluoro-2.3-i9.10-Dhenanthro1-
bicyclo[3.1.0]hex-2-ene (49): A Quantitative Study Followed bv-i^F NMR
A stock solution of 49 in C8D8 was prepared as follows: 0.0078 g
(2.3x1 O'5 mol) preparative GLPC purified 49 (preparative GLPC as in synthetic
discussion section, containing traces of 50 and 51) was dissolved in 0.52 g

122
Table 4-1. Relative Percent Composition Data for Thermolysis of 40 at
180.0°C.
Seconds
%40
%49
%50
%41
%51
%MB
0
100.0
0
0
0
0
5040.
94.20
4.87
0
0.91
0
18960.
80.15
13.57
1.68
2.52
1.08
m
33360.
73.26
16.48
3.35
5.08
1.84
37920.
67.73
18.08
4.67
5.81
3.69
_
66720.
51.05
20.45
11.17
9.28
8.04
100
82560.
44.62
20.45
14.36
10.53
10.03
98.4
105060.
35.33
19.68
19.80
11.61
13.56
97.6
112980
33.61
17.65
21.42
12.37
14.95
95.9
183060
15.83
11.48
34.28
14.68
23.71
94.6
264300
7.56
5.41
41.94
14.16
30.93
90.8
445980
0
0
42.14
12.05
45.81
83.7
598740
0
0
22.34
9.13
68.52
83.2
665700
0
0
12.19
7.66
80.15
81.1
716520
0
0
4.93
6.95
88.12
80.0
844500
0
0
0
4.59
95.41
77.8
Table 4-2. Relative Percent Composition Data for Thermolysis of 40 184.5°C.
Seconds
%4 0
%49
%5 0
%41
%51
%MB
0
100.0
0
0
0
0
16920
76.22
14.99
1.49
3.98
3.34
_
26160
66.43
18.41
1.93
5.67
7.56
-

123
Table 4-2 - Continued-
Seconds
%40
%49
%50
%41
%51
%MB
38820
54.60
20.37
3.55
7.56
13.92
42840
51.32
20.35
3.72
8.07
16.54
•
59520
39.59
19.35
8.23
9.73
23.10
96.7
Table 4-3. Relative Percent Composition Data for Thermolysis of 40 193.0°C.
Seconds
%40
%49
%50
%41
%51
%MB
0
100.0
0
0
0
0
7200.
76.69
14.94
1.78
3.82
2.76
15840.
58.97
19.99
2.53
6.84
11.67
22620.
48.14
20.10
1.55
8.49
21.70
33180.
35.35
17.72
1.16
10.48
35.29
45000.
24.85
13.84
1.03
11.71
48.56
60900.
16.67
9.34
0.87
12.07
61.04
100
C6D6 and 10 mg of C6F6 was added as an 19F NMR internal standard. An
aliquot of the solution was syringed into each of three thick walled NMR tubes
(base rinsed, deionized water rinsed, acetone rinsed, flame dried) and then the
tubes were flame sealed under N2. Thermolysis was carried out by submerging
a sample in a Statim thermostated oil bath for a time period then rapidly
removing and cooling the sample in an ice bath. The sample was then
observed by 19F NMR using a Ti delay of 10 seconds and collecting a minimum
of 128 transients before Fourier transforming the spectrum. The relative
concentrations of all fluorinated products was arrived at by integration of the

124
sample signals and comparison versus the internal standard C6F6. (See Tables
4-4, 4-5, and 4-6 for data.)
Table 4-4. Relative Percent Composition Data for Thermolysis of 49 at
180.0°C.
Seconds
%49
%50
%51
%MB
0
90.69
7.63
1.68
9660.
74.71
17.50
7.79
14220.
68.66
21.19
10.14
_
21000.
60.33
26.48
13.18
_
27780.
51.72
31.14
17.14
38220.
42.61
37.41
19.90
_
45420.
37.37
40.54
22.09
_
52800.
32.14
43.78
24.08
100
Table 4-5. Relative Percent Composition Data for Thermolysis of 49 at
185.0°C.
Seconds
%49
%50
%51
%MB
0
90.45
7.70
1.85
10500
66.50
22.57
10.87
_
14520
58.86
27.27
13.86
_
25920
42.07
37.93
19.99
31500
35.93
41.33
22.74
39900
28.25
45.39
26.35
100

125
Table 4-6. Relative Percent Composition Data for Thermolysis of 49 at
192.5°C.
Seconds
%49
%50
%51
%MB
0
90.47
7.57
1.96
2220.
80.67
13.64
5.68
•
5820.
67.18
21.83
11.01
8640.
57.38
27.97
14.65
11340.
50.76
32.06
17.17
100
Reaction of 9.10-Bis(trifluoroethenyl)phenanthrene (40) with CsF
9,10-Bis(trifluoroethenyl)phenanthrene (40, 0.0103 g, 3.05x10'5 mol)
was dissolved in 2.0 ml of dry DMF to which was added 0.0113 g (7.43x10‘5
mol) dry CsF. The reaction mixture was stirred rapidly for 2.5 hours at room
temperature and a small aliquot of the reaction mixture was taken, diluted with
water, extracted with diethyl ether, concentrated under a stream of N2, then
analyzed by analytical GLPC (Column: 0.125 inch x 10 feet, 20% QF-1 on
Chromasorb WHP 100/120; Oven: constant at 205°C; Injector: 210°C) showing
no reaction had occurred. The sample was then heated at 115°C. After 3.5
hours, an aliquot was taken as earlier and GLPC analysis shows three products
with 40 approximately 70% consumed. Comparison with a 40 thermolysis
reaction mixture sample (containing materials 40, 41,49, 50, and 51) shows
that the CsF reaction has no products in common with the thermal reaction.
After 19 hours further heating, GLPC analysis shows 40 has been consumed
and one major and two minor products are observed. The reaction mixture was
transferred to a separatory funnel with 50 ml of water and extracted with diethyl
ether. The ether was then dried over anhydrous MgSC>4 and evaporated to

126
yield a small amount of brown oil. The oil was taken up in CDCI3 and it's 19F
NMR spectrum observed. The spectrum shows two clusters of signals: -60 to
-82 ppm (13 signals of various intensities) and -166 to -170 ppm (4 signals).
Comparison of this spectrum with known spectra of 40 thermolysis products 41,
49, 50, and 51 shows these two reactions have no products in common. No
further characterization or separation was performed on the CsF reaction
mixture.
Reaction of 4-Difluoromethvlidene-3.3.5.5-tetrafluoro-1.2-(9.10-phenanthro)-
cvclopent-1-ene (50) with Catalytic CsF
To an NMR sample in C6D6 with C6F6 internal standard containing 30.0%
49, 44.6% 50, and 25.4% 51 was added 20 pi of C6Ü6 containing traces of
CsF. This fluoride spiked C6D6 solution was prepared by adding 2 ml of dry
C6D6 to 10 mg of dry CsF then heating to reflux for 10 minutes. Visually, no CsF
dissolved. The NMR sample was then flame sealed and placed in a Statim
thermostated oil bath at 81 °C for 57 minutes. After this time, the sample was
cooled and found to contain 30.7% 49, 19.7% 50, and 49.5% 51 by integration
of the 19F NMR signals versus the C6F6 internal standard. The overall mass
balance of 49, 50, and 51 versus the starting mixture is 95%.
Thermolysis of 1.2.2.3.3.4-hexafluoro-2.3-dihvdrotriphenvlene (411 Followed bv
GLPC
Two milligrams of a mixture being 62% 41 and 38% 51 was dissolved in
1.0 g of benzene and a small amount (a few mg) of phenanthrene was added
as an internal standard. The solution was syringed into capillary tubes which
were then flame sealed. The samples were placed in a Statim thermostated oil
bath at 179.5°C. The progress of the reaction was followed by removing sealed
samples over time and observing the reaction solution by analytical GLPC.

127
(Column: 0.125 inch x 10 feet, 20% QF-1 on Chromasorb WHP 100/120; Oven:
constant at 205°C; Injector: 210°C) 41 decomposes and after 5.25 hours is
67% consumed. No new products were observed by GLPC of the reaction
mixture, and there was no increase in the relative concentration of 51 over the
thermolysis period. After 17 hours, 41 has been completely consumed, the 51
concentration has not changed, and there were no new products observed by
GLPC.
Thermolysis of 1.2.2.3.3.4-Hexafluoro-2.3-dihvdrotriphenvlene (41) Followed
bylf>FNMR
Three milligrams of a mixture being 85% 41 and 15% 51 was dissolved
in 1.0 g of C6D6 containing traces of C6F6 as an internal standard. An aliquot of
the solution was then transferred to an thick walled NMR tube and flame sealed
under N2. The sample was placed in a Statim thermostated oil bath at 179.5°C,
taken out at specific time intervals and cooled rapidly in an ice-water bath, then
observed by 19F NMR. The sample's 19F NMR spectrum was obtained five times
over 799 minutes. The amount of 41 was clearly observed to decrease, and
after 799 minutes, 32% of the 41 had been consumed. There were many new
low intensity signals in the 19F NMR spectrum observed in the region of -110 to
-130 ppm. There was no change in the amount of 51, and no 40, 49, nor 50
were observed to have formed. Disappearance of 41 (Ln(%41) versus time)
did not follow first-order kinetics.
Solution Phase Photolysis of 1.2.2.3,3.4-Hexafluoro-2.3-dihvdrotnphenvlene
im
A 0.003 g sample being 76.7% 41 and 23.3% 51, was dissolved in 1.0 g
of n-pentane containing traces of C6H5F. The solution was freeze-thaw
degassed and an aliquot was syringed into a 5 mm quartz NMR tube and flame

128
sealed under N2. The sample was photolyzed using a Rayonet reactor (model
RPR-204, four low pressure mercury bulbs of type RUL 2537 Á from Southern
N.E. Ultraviolet Co., Middleton, Connecticut) and the concentrations of all
materials were monitored versus internal standard by 19F NMR. (See Table 4-7
for data.) A fine film of insoluble solid was observed to have formed on the
interior of the NMR tube. 1,4,5,5,6,6-Hexafluoro-2,3-(9,10-
phenanthro)bicyclo[2.2.0]hex-2-ene (61) was observed in solution by 19F NMR
but not isolated due to the small amount of material.
1.4.5.5.6.6-Hexafluoro-2.3-(9.10-phenanthro)bicvclo[2.2.0]hex-2-ene
(61): 19F NMR (282 MHz, n-pentane, CFCI3) -115.6 (dm, 2F, 2JFF = 213.7 Hz),
-127.9 (dm, 2F, 2JFF = 213.7 Hz), -185.1 (bs, 2F)
Table 4-7. Relative Composition Data for Solution Phase Photolysis of 41.
Minutes
%41
%61
%MB
0
100.
0
100.
61.
53.
28.
81.
114.
16.
22.
38.
Solution Phase Photolysis of 9,10-Bis(trifluoroethenyl)phenanthrene (40)
A sample consisting of 0.024 g (7.1x10‘5 mol) 40 and 0.005 g (5x10‘5
mol) CeH5F was dissolved in 1.5 ml of dry n-pentane and the solution was
freeze-thaw degassed. The solution was syringed into an NMR tube and flame
sealed under N2 . The sample was irradiated by Rayonet reactor (model RPR-
204, 4 low pressure mercury bulbs of type RUL 2537 Á from Southern N.E.
Ultraviolet Co., Middleton, Connecticut) and the composition of the reaction
mixture was monitored by 19F NMR over a period of 21.6 hours. (See Table 4-8
for data.) After this time, the solution had turned clear light yellow from clear

129
colorless and a thin solid film had developed on the inside of the sample tube.
Three materials identified earlier were seen in the reaction mixture; those being
41,49, and 61. Also observed in solution by 19F NMR but not isolated was
1,4,5,5,6,6,-hexafluoro-2,3-(9,10-phenanthro)bicyclo[2.1.1 ]hex-2-ene (60).
1.4.5.5.6.6-hexafluoro-2.3-(9.10-phenanthro)bicyclo[2.1.1 jhexene (60):
19F NMR (282 MHz, n-pentane, CFCI3) -115.3 (dtt, 2F, 2JFF = 162.7 Hz, 3JFF =
34.3 Hz, 4Jff = 7.3 Hz), -140.5 (dtt, 2F, 2JFF = 162.7 Hz, 3JFF = 34.3 Hz, 4JFF = 7.3
Hz), -211.7 (p, 2F, 4Jff = 7.3 Hz)
Table 4-8. Relative Composition Data for Solution Phase Photolysis of 9,10-
Bis(trifluoroethenyl)phenanthrene (40).
Minutes
%40
%41
%49
%60
%61
%MB
0.
100.
0
0
0
0
m
12.
98.8
1.2
Trace
Trace
Trace
_
37.
97.3
2.7
Trace
Trace
Trace
87.
79.3
2.5
8.0
8.3
1.9
_
204.
58.0
2.8
20.7
14.8
3.6
281.
50.1
3.0
26.6
15.1
5.1
620.
27.1
1.4
42.4
24.0
5.2
_
1090.
13.8
1.4
50.3
28.9
5.5
_
1295.
7.8
1.3
53.6
27.2
6.0
89
An attempt to separate this resultant mixture was performed by preparative
GLPC. (Column: 0.25 inch x 5 feet, 20% QF-1 on Chromasorb WHP 80/100;
Oven: constant at 193°C; Injector: 200°C; TCD block: 212°C; He flow : 120
ml/minute.) Two fractions were isolated: Fraction 1, 5.3 mg light yellow solid, 49

130
(54%), 50 (38%), 51 (8%); Fraction 2, 4.1 mg light yellow solid, 50 (6%), 41
(20%), 51 (74%).
Photolysis of 9.10-Bis(trifluoroethenvl)phenanthrene (40) and Thermolysis of
Subsequent Reaction Mixture
A sample of 40 (0.021 g, 6.2x10‘5 mol) was dissolved in 10 ml of dry,
freeze-thaw degassed n-pentane and photolyzed with a Rayonet reactor (model
RPR-204, 4 low pressure mercury bulbs of type RUL 2537 Á from Southern N.E.
Ultraviolet Co., Middleton, Connecticut) through a Pyrex rotaflow tube for 21
hours and 45 minutes. After this time, the solution had turned from clear
colorless to clear yellow with a fine film forming on the inside of the tube. The
tube was then opened and the solvent removed under a stream of N2. The
remaining solid was dissolved in C6D6 and 19F NMR shows at this time: 49
(47%), 60 (40%), 61 (13%). The sample was then flame sealed in a thick
walled NMR tube. Heating this sample at 99°C for 1 hour effected no change.
The sample was then heated at 184°C for 83 minutes. After this heating period,
examining the reaction mixture by 19F NMR showed: 49 (74%), 50 (3%), 41
(8%), 51 (15%) with no 60 or 61 remaining and no other new signals in the 19F
NMR spectrum. Internal standard was not used so the overall mass ballance
from 40 was not established.
Preparation of Perfluoro-EZ.Hand EE.a-4.5-dimethyl-2.4.6-octatriene (Z-
56ÍE-56)
Perfluoro-E,Z,E(E,E,E)-4,5-dimethyl-2,4,6-octatriene (Z-56(E-56) was
prepared by the method of Hansen.70 A 100 ml, three necked, round bottom
flask was assembled with two septa, a stopper, and a magnetic stirrer then
flame dried under Ar purge. Dry, degassed DMF (25 ml) was syringed into the
reaction vessel. Cd° powder (3.38 g, 3.00x10'2 mol) was weighed out into a

131
solid addition tube in a drybox then added to the reaction vessel. The mixture
was cooled to 0°C, then 6.13 g (-2.8 ml, 2.38x10'2 mol) perfluoro-Z-1 -
iodopropene146 was added dropwise. The mixture was allowed to warm to RT
and stirring was continued for 16 hours. Internal standard 19F NMR at this time
shows a 95% yield of Z-(XCd)FC=CF(CF3) (where X = I and Z-CF=CF(CF3) as a
deep brown-red solution. Excess Cd° was removed by Schlenk filtering the
solution into another three necked round bottom flask under Ar. Recrystallized
CuBr (3.40 g, 2.37x10‘2 mol) was weighed out into a solid addition tube in a
drybox then added to the solution at RT. This mixture was stirred vigarously for
1 hour at RT, then the solids were removed by Schlenk filtering the solution into
another three necked round bottom flask under Ar. A cold finger trap with a gas
inlet port was added to the apparatus and 5.0 g (3.08x1 O’2 mol) hexafluoro-2-
butyne was slowly added from a tared Rotaflow tube over 10 minutes while
maintaining the temperature of the system at RT by use of a water bath. This
mixture was stirred vigarously at RT for 1 hour to yield a cloudy, orange-brown
suspension. The condenser was removed and replaced with a vacuum takeoff.
The reaction mixture was evacuated at 0.3 mm Hg and RT for 30 minutes and
excess hexafluoro-2-butyne was trapped. Perfluoro-Z-1-iodopropene146 (5.45 g,
2.11x1 O'2 mol) was then slowly added by syringe and the mixture stirred
vigarously for 14 hours. When stirring was stopped, the mixture separated into
an upper dark brown layer of DMF (majority of volume) and a clear colorless
layer of perfluoroolefin on the bottom, with tan solid settling on the sides of the
vessel. The mixture was then flash distilled using a bath temperature up to
60°C and vacuum of 1-2 mm Hg. Approximately 5 ml of clear, light yellow liquid
was obtained with =1 ml of a dark yellow DMF layer on top. The bottom
perfluoroolefin (56) layer was drawn out by syringe and transferred to a large,
septum capped vial. The material was washed with 5 x 5 ml of cold water,

132
transferred to a new vial and dried over MgS04) then syringed through a 0.45
pm syringe filter into a vial containing activated 4 Á sieves. A 6.07 g (60%)
sample of clear faint yellow 56 was obtained being 95% pure by GLPC.
Z-(XCd)FC=CF(CFg) (X = I and Z-CF=CF(CF2): NMR (188MHz, DMF,
CFCI3) -65.7 (dd, 3 or 6 F, 4JFf = 22 Hz, 3JFF = 13 Hz), -141.3 (m, 1 or 2 F),
-177.5 (dm, 1 or 2 F, 3JFF = 103 Hz)
Perfluoro-£.Z.E(E.E.a-4.5-dimethyl-2.4.6-octatriene (Z-56(E-56): 19F
NMR (188 MHz, n-pentane, CFCI3) E,Z,E: -60.3 (bs, 6F), -69.2 (dd overlapped
with E,E,E triene signal, 6F, 4JFF = 19 Hz, 3JFF « 10 Hz), -139.8 (dq, 2F, 3JFF =
141.7 Hz, 4Jff = 19.2 Hz), -158.2 (dm overlapped with E,E,E triene signal, 2F,
3Jff ® 141 Hz), E,E,E: (pure sample obtained by preparative GLPC, after
enrichment via photolysis of triene mixture through Pyrex) -63.1 (bs, 6F), -69.7
(dd, 6F, 4Jff = 20.2 Hz, 3JFF = 10.0 Hz), -136.3 (dq, 2F, 3JFF = 143.3 Hz, 4JFF =
20.2 Hz), -158.2 (dm, 2F, 3JFF = 143.3 Hz); UV in n-pentane, >*max = 257nm, Emax
= 1882.4 cm2/mol; Low Resolution Mass Spectrum: m/z (% relative intensity)
424 (43), 336 (7), 317 (34), 286 (53), 267 (100), 217 (67); High Resolution Mass
Spectrum: Calculated for C10F16 = 423.9744, Measured = 423.9741
Solution Phase Thermolysis of Perfluoro-E.Z.E(E.E.g)-4.5-dimethvl-2.4.6-
octatriene (Z-56(E-56))
A 0.23 g (5.5x10‘4 mol) sample of Eand Z56was dissolved in 4.0 ml of
dry n-pentane and 10 pi CeH5F added. The solution was freeze-thaw degassed
and a 0.5 ml aliquot taken and transferred to a 5 mm, thick walled NMR tube
(base rinsed, deionized water rinsed, acetone rinsed, flame dried) and flame
sealed under N2. The sample was then heated for a given time in a Statim
thermostated oil bath and concentrations of all materials followed by integration
of 19F NMR signals versus internal standard C6H5F. (See Table 4-9 for data.)

133
Table 4-9. Relative Composition Data for Thermolysis of 56 at 154.5°C then
202.0°C.
Minutes
%Z-56
%E- 56
%59
%MB
0
51.8
48.2
0
655.
41.6
58.4
0
_
895.
38.9
61.0
0
_
1795.
30.7
69.3
0
_
2145.
29.4
70.6
0
_ ¡
3057.
26.7
73.3
Trace
100
8822.
13.7
63.9
22.3
.
-Temperature was raised to 202.0°C and thermolysis continued-
9937.
6.3
54.7
38.9
10907.
5.6
51.9
42.5
15537.
6.0
54.0
40.4
_
19387.
5.3
56.8
37.8
95
Perfluoro-c/'s(and frans)-1,3,4-trimethyl-4-(£:-1-propenyl)cyclobutene (59) were
observed in the reaction solution by 19F NMR and GLPC. (Column: 0.125 inch x
10 feet, 20% SE-30 on Chromasorb WHP 100/120; Oven: constant at 40°C;
Injector: 120°C; N2 flow: 20 ml/minute; Retention times: 56 3.8 minutes, 59 4.2
minutes).
Perfluoro-c/s(and trans)-"\ .3,4-trimethvl-4-(E-1-propenvl)cvclobutene
(59): 19F NMR (188 MHz, n-pentane, C6H5F (-113.15)) -62.2 (bs, 3F), -63.3 (bs,
3F), -70.1 (bs, 6F), -119.5 (bs, 1F), -136.5 (dq, 1F, 9JFF = 144 Hz, 4JFF = 20 Hz),
-144.5 (bs, 1F), -158.7 (dbs, 1F, 3JFF = 144 Hz)

134
Photolysis of Perfluoro-E.ZE(E.E.E)-4.5-dimethyl-2.4.6-octatriene (Z-56ÍE-56)
A sample being 0.293 g (6.91x1 O'4 mol) 56 was dissolved in 4.0 ml of dry
n-pentane and 10 pi C6H5F was added. The solution was freeze thaw
degassed then a 0.5 ml aliquot was drawn and syringed into an 5 mm, Pyrex
NMR tube (base rinsed, deionized water rinsed, acetone rinsed, flame dried),
and the sample flame sealed under N2. The photolysis was carried out by
suspending the sample in a Rayonet reactor (model RPR-204, four low pressure
mercury bulbs of type RUL 2537 Á from Southern N.E. Ultraviolet Co.,
Middleton, Connecticut) for a period of time then observing the reaction mixture
by 19F NMR. Relative concentrations of all species were obtained by integration
versus internal standard C6H5F. (See Table 4-10 for data.)
Table 4-10. Relative Composition Data for Photolysis of Perfluoro-E,Z,E(E,E,£)-
4,5-dimethyl-2,4,6-octatriene (Z-56(E-56).
Minutes
%Z-56
%E- 56
%62
%63
%MB
0
53.7
46.3
0
0
255.
30.9
41.7
27.3
0
_
885.
5.0
27.9
58.4
8.6
_
2145.
0
2.0
80.0
18.0
90
For isolation of perfluoro-frans-2,3,5,6-tetramethyl-1,3-cyclohexadiene (62), a
reaction solution after a suitable period of photolysis (composition being: 10%
56 (11 E, E, E: 1 E,Z,E), 75% 62, 15% perfluoro-f/-ans-2,3,5,6-
tetramethylbicyclo[2.2.0]hex-2-ene (63)) was frozen in liquid nitrogen and
carefully thawed. This freeze-thaw cycle was repeated twice and resulted in
phase seperation between the perfluoroorganics and n-pentane. While still
cool (=-50°C), the upper n-pentane layer could be syringed away containing

135
less than 3% perfluoroorganics by GLPC. The remaining perfluoroorganics
(containing on average 10% or less n-pentane) were seperated by preparative
GLPC. (Column: 0.25 inch x 12 feet, 20% SE-30 on Chromasorb P 60/80;
Oven: constant at 60°C; Injector: 125°C; TCD block: 150°C, He flow: 20
ml/minute; Retention times: £-56 10.2 minutes (19F NMR data for this material is
given in perfluorotriene preparation experimental discussion), 62 14.2
minutes).
Perfluoro-frans-2.3.5.6-tetramethvl-1.3-cyclohexadiene (62): 19F NMR
(188 MHz, n-pentane, C6H5F (-113.15)) -59.5 (m, 6F), -75.5 (m, 6F), -108.0 (m,
2F), -201.4 (m, 2F); UV in n-pentane, Xmax = 261 nm, Emax = 915.6 cm2/mol;
Low Resolution Mass Spectrum: m/z (% relative intensity) 424 (52), 336 (17),
317 (37), 267 (100); High Resolution Mass Spectrum: Calculated for C-ioF16 =
423.9744, Measured = 423.9746
Photolysis of Perfluoro-frans-2.3.5.6-tetramethvl-1.3-cvclohexadiene (62)
A solution being 10% 62 and 2% C6H5F was prepared in dry n-pentane
and freeze-thaw degassed. An 0.5 ml aliquot was syringed into a 5 mm, quartz
NMR tube which had been rinsed with base, deionized water, acetone, then
flame dried under N2 purge. The solution was then flame sealed under N2. The
sample was photolyzed using a Rayonet reactor (model RPR-204, four low
pressure mercury bulbs of type RUL 2537 Á from Southern N.E. Ultraviolet Co.,
Middleton, Connecticut) and concentrations of all materials followed by
integration of 19F NMR signals versus internal standard C6H5F. (See Table 4-
11 for data.)

136
Table 4-11. Relative Composition Data for Photolysis of Perfluoro-frans-2,3,5,6-
tetramethyl-1,3-cyclohexadiene (62).
Minutes
%62
%63
%MB
0
100.0
0
100.
20.
93.5
6.5
98.
80.
73.4
26.6
95.
504.
27.9
72.1
71.
624.
25.6
74.4
58.
Perfluoro-frans-2,3,5,6-tetramethylbicyclo[2.2.0]hex-2-ene (63) was isolated out
of the reaction solution after a suitable photolysis period. The solution was
frozen in liquid nitrogen and carefully thawed. This freeze-thaw cycle was
repeated twice and resulted in phase seperation between the perfluoroorganics
and n-pentane. While still cool (=-50°C), the upper n-pentane layer was
carefully syringed away containing less than 3% perfluoroorganics by GLPC.
The remaining perfluoroorganics (containing on average 10% or less n-
pentane) were separated by preparative GLPC. (Column: 0.25 inch x 12 feet,
20% SE-30 on Chromasorb P 60/80; Oven: constant at 60°C; Injector: 125°C;
TCD block: 130°C, He flow: 18 ml/minute; Retention times: 63 7.1 minutes, 62
8.6 minutes, n-pentane 9.2 minutes)
Perfluoro-/rans-2.3.5.6-tetramethylbicvclo[2.2.01hex-2-ene (63): 19F NMR
(188 MHz, CHCI3, CFCI3) -63.7 (bs, 3F), -64.2 (m, 3F), -73.2 (m, 3F), -75.9 (m,
3F), -174.4 (m 1F), -187.5 (m, 1F), -190.0 (m, 1F), -192.0 (dm, 1F, JFF - 15 Hz);
Low Resolution Mass Spectrum: m/z (% relative intensity) 424 (5), 336 (4), 317
(17), 286 (10), 151 (11), 119 (100), 113 (13); High Resolution Mass Spectrum:
Calculated for CiqF16 = 423.9744, Measured = 423.9749

137
Preparation of 4-f(Tetrahydro-2H-pvran-2-vnoxv1-1 -butanol
4-[(Tetrahydro-2/-/-pyran-2-yl)oxy]-1-butanol was prepared by the method
of Hoffmann and Rabe.133 1,4-Butanediol (60.0 ml, 0.68 mol) was placed in a
round bottom flask equipped with a strong magnetic stirrer. Diethyl ether (50
ml) and 5 drops of concentrated HCI were then added. 3,4-Dihydro-2H-pyran
(DHP, 41.1 ml, 37.9 g, 0.45 mol) was dissolved in 50 ml diethyl ether and
added dropwise at RT with rapid stirring to the heterogenous diol/ether mixture.
The reaction mixture became homogenous after addition of approximately 10
ml of the DHP/ether solution. Upon completion of addition of the DHP solution,
the reaction mixture was stirred for 3 hours at RT then extracted with 2 x 50 ml
10% aqueous KOH. The aqueous solution was back extracted with 50 ml
diethyl ether then the ether extracts were combined and dried over MgS04. The
ether was then removed by rotary evaporator and the remaining clear, colorless
liquid was fractionally distilled through an 12 cm vigeraux column. 4-
[(Tetrahydro-2H-pyran-2-yl)oxy]-1-butanol (52.8 g, 67%) was obtained as an
early fraction boiling 100-109°C at 0.1 mm Hg as a colorless, viscous liquid.
4-[(Tetrahvdro-2A7-pvran-2-v0oxv1-1 -butanol: 1H (200 MHz, CDCI3, TMS)
1.45-1.85 (m, 10H), 3.22 (s, 1H), 3.37-3.95 (m, 6H), 4.60 (t, 1H, 3JHH « 3 Hz); 13C
(50 MHz, CDCI3, CHCI3) 19.3, 25.2, 26.1,29.6, 30.4, 62.0, 62.1, 67.2, 98.6
Preparation of 4-r(Tetrahvdro-2H-pyran-2-vl)oxv1-1-butanal (132)
4-[(Tetrahydro-2H-pyran-2-yl)oxy]-1-butanal (132) was prepared by
adaptation of a procedure as described by Corey and Schmidt.147 A 1 L round
bottom flask was flame dried under Ar purge and equipped with a strong
magnetic stirrer and septum. 4-[(Tetrahydro-2H-pyran-2-yl)oxy]-1-butanol (17.9
g, 1.03x10-3 mol) was syringed into the flask followed by 400 ml of dry CH2CI2.
Pyridinium dichromate (PDC, 58.3 g, 1.55x10"1 mol) was quickly added and

138
rapid stirring begun. The solution turned dark brown-black within minutes of
addition of the PDC. Stirring was continued for 15 hours at RT, then the
reaction mixture was diluted with 400 ml diethyl ether. The black solid residue
was gravity filtered and the resultant brown-black solution filtered through a bed
of 150 mesh, basic activated (Brockmann I), aluminum oxide. The resultant
solution was concentrated by rotary evaporator to yield a clear, colorless,
slightly viscous liquid. This material was fractionally distilled through a 6 cm
vigeraux column and 12.7 g (72%) clear, colorless, pleasant smelling 132 was
obtained in an early fraction boiling 85-90°C at 0.05 mm Hg.
4-[(Tetrahydro-2/-/-pyran-2-yl)oxy1-1-butanal (132): 1H (200 MHz, CDCI3,
TMS) 1.45-1.85 (m, 6H), 1.94 (p, 2H, 2JHH = 6.7 Hz), 2.54 (dt, 2H, 3JHH = 7.0 Hz,
3jHH = 1.7 Hz), 3.35-3.55 (m, 2H), 3.73-3.88 (m, 2H), 4.56 (t, 1H, 3jHH - 3 Hz),
9.78 (t, 1H, 3Jhh= 1.7 Hz); 13C (50 MHz, CDCI3, CHCI3) 19.5, 22.7, 25.5, 30.6,
41.1, 62.2, 66.4, 98.8, 202.2
Preparation of 5-i(Tetrahvdro-2F/-pyran-2-vl)oxv1-1.1-difluoropent-1-ene (133)
5-[(Tetrahydro-2H-pyran-2-yl)oxy]-1,1 -difluoropent-1 -ene (133) was
prepared by adaptation of a procedure as described by Naae and Burton.134 A
three neck, 1 L flask was assembled under Ar purge with a mechanical stirrer,
septum, and two addition funnels. The system was then flame dried under Ar
purge. Dibromodifluoromethane (29.1 g, 1.39x10'1 mol) was transferred to a
Rotaflow tube, dissolved in 60 ml of dry THF, then syringed into the reaction
vessel followed by an additional 160 ml of dry THF. This solution was cooled to
-5°C by an ice/salt bath. Dry THF (140 ml) was placed in an addition funnel
followed by 50.0 ml (44.9 g, 2.75x10‘1 mol) P(N(CH3)2)3. Rapid stirring was
begun and the P(N(CH3)2)3 was added dropwise over 1 hour to the CF2Br2
solution with cooling. A fine white precipitate formed as addition continued.

139
Upon completing addition of the P(N(CH3)2)3, the mixture was stirred at -5°C for
1 hour then brought to RT. 4-[(Tetrahydro-2H-pyran-2-yl)oxy]-1-butanal (132,
16.0 g, 9.29x10‘2 mol) was dissolved in 50 ml of dry THF and placed in the
second addition funnel. The 132 solution was then added to the ylide solution
over 15 minutes at RT, then stirred for 16 hours at RT. At this time, the reaction
mixture is a yellow-brown solution with a fine yellow precipitate settling on the
bottom of the reaction vesel. The solids were gravity filtered and rinsed with
100 ml of diethyl ether. This solution was concentrated on a rotary evaporator
to «25 ml volume which was taken up in 200 ml of fresh diethyl ether and
exhaustively extracted with water. The ether solution was then dried over
MgSCU and the ether removed by distillation up to 75°C at 115 mm Hg. 5-
[(Tetrahydro-2H-pyran-2-yl)oxy]-1,1-difluoropent-1-ene (11.1 g, 58% by internal
standard 19F NMR; «80% pure, the remainder being ether and trace THF) was
obtained as a clear, light brown liquid.
5-fn~etrahydro-2H-pvran-2-y0oxv1-1.1-difluoropent-1-ene (1331: 1H (200
MHz, CDCI3, TMS) 1.45-1.85 (m, 8H), 2.03-2.17 (m, 2H), 3.33-3.57 (m, 2H),
3.75-3.92 (m, 2H), 4.17 (dtd, 1H, 3JtransHF = 25.2 Hz, 3jHH = 7.94 Hz, 3Jcíshf =
2.54 Hz), 4.55 (t, 1H, 3JHH » 3 Hz); 13C (50 MHz, CDCI3, CHCI3) 18.9 (d, 1C, 3JCf
= 4.3 Hz), 19.4, 25.3, 29.3 (t, 1C, 4JCf - 2 Hz), 30.6, 62.1, 66.3, 77.6 (t, 1C, 2JCf =
21.2 Hz), 98.7, 156.2 (t, 1C, 1JCF = 283.9 Hz); 19F(188 MHz, CDCI3) CFCI3) -89.8
(d, 1F, 2Jff = 48.4 Hz), -92.3 (dd, 1F, 2JFF = 48.4 Hz, 3JHF = 25.2 Hz)
Preparation of 5.5-Difluoro-4-penten-1-ol (1341
5-[(Tetrahydro-2W-pyran-2-yl)oxy]-1,1-difluoropent-1-ene (133) was
deprotected to 5,5-difluoro-4-penten-1-ol (134) by adaptation of a procedure as
described by Beier and Mundy.148 5-[(Tetrahydro-2/-/-pyran-2-yl)oxy]-1,1-
difluoropent-1-ene (133, 11.1 g, 4.3x10'2mol delivered (80% pure, impurities

140
being ether and trace THF)) was dissolved in 70 ml 1,4-butanediol. Acid
activated Dowex 50 x 80-200 ion exchange resin (5.0 g) was added and the
mixture stirred rapidly for 2.5 hours. The reaction was then flash distilled down
to a pressure of 0.5 mm Hg. Approximately 2 ml of THF and ether was collected
upon pump down of the system. The fraction boiling between 55 and 110°C
(applied bath temperature) was collected to yield «5 ml clear, colorless liquid.
Being slightly acidic, this material was distilled off of 2 g of dry NaHC03 to yield
4.37 g (83%) clear, colorless 134 distilling from 74-78°C at 115 mm Hg.
5.5-Difluoro-4-penten-1 -ol (134): 1H (200 MHz, CDCI3, TMS) 1.63 (tt, 2H,
3Jhh = 7.42 Hz, 3JHh = 6.36 Hz), 2.07 (m, 2H), 2.78 (bs, 1H), 3.62 (t, 2H, 3JHH =
6.34 Hz), 4.16 (dtd, 1H, 3JtransHF = 25.38 Hz, 3JHH = 7.78 Hz, 3JcisHF= 2.54 Hz);
13C (50 MHz, CDCI3, CHCI3) 18.5 (d, 1C, 3JCF = 4.2 Hz), 32.1 (t, 1C, 4JCf = 2.1
Hz), 61.6, 77.3 (t, 1C, 2JCf = 21.3 Hz), 156.3 (dd, 1C, 1JCf= 284.9 Hz, 1JCF =
285.1 Hz); 19F (188 MHz, CDCI3, CFCI3) -89.6 (d, 1F, 2JFF= 48.6 Hz), -92.1 (dd,
1F, 2Jff= 48.6 Hz, 3JtransHF= 25.5 Hz); Low Resolution Mass Spectrum: m/z (%
relative intensity) 104 (100), 84 (16), 77 (69)
Preparation of 5.5-Difluoro-4-pentenal (1351
5.5-Difluoro-4-pentenal (135) was prepared by adaptation of a
procedure as described by Corey and Schmidt.147 A round bottom flask was
flame dried under Ar purge and 150 ml of dry CH2CI2 added. 5,5-Difluoro-4-
penten-1-ol (134, 4.37 g, 3.58x10'2 mol) was then added followed by 20.17 g
(5.36x10‘2 mol) pyridinium dichromate. The reaction mixture was stirred at RT
for 18 hours then dilluted with 250 ml diethyl ether. The mixture was then
gravity filtered to remove the black solids which were rinsed with diethyl ether,
then, the resultant brown-black solution was filtered through a bed of 150 mesh,
base activated (Brockmann I) aluminum oxide. Contamination by pyridine was

141
detected by GLPC so the reaction solution was extracted with 2 x 50 ml half
saturated CUSO4, then 2 x 50 ml water. By GLPC, the pyridine had been
removed, so the solution was dried over MgSC>4. The ether and CH2CI2 were
carefully distilled through a 6 cm vigeraux column and the remainder
transferred to a micro distillation apparatus. As the heating bath temperature
was raised to =40°C with an applied pressure of 100 mm Hg, the remainder of
material bumped over. Due to the small amount of material, distillation was not
attempted again. A clear, light yellow liquid was obtained being 87% pure 135
(3.37 g, 70%) contaminated with diethyl ether and CH2CI2.
5.5-Difluoro-4-pentenal (135): 1H (200 MHz, CDCI3, TMS) 2.22-2.35 (m,
2H), 2.53 (tm, 2H, 3JHH = 6.92 Hz), 4.22 (dtd, 1H, 3JtransHF = 25.10 Hz, 3JHH = 7.78
Hz, 3JcisHF = 2.38 Hz), 9.76 (t, 1H, 3JHH = 1.2 Hz); 13C (50 MHz, CDCI3, CHCI3)
14.9 (d, 1C, 3JCf = 4.9 Hz), 43.0 (t, 1C, 4JCf = 2.6 Hz), 77.0 (t, 1C, 2JCf = 31.9
Hz), 156.2 (dd, 1C, 1JCf = 285.6 Hz, 1JCf = 286.2 Hz), 200.6; 19F (188 MHz,
CDCI3, CFCI3) -88.9 (d, 1F, 2Jff = 46.4 Hz, -91.0 (dd, 1F, 2JFf = 46.4 Hz,
3JtransHF = 25.0 Hz); Low Resolution Mass Spectrum: m/z (% relative intensity)
120 (10), 100 (11), 91 (7), 77 (66), 69 (100), 64 (19); High Resolution Mass
Spectrum: Calculated for C5H6F2O = 120.0386, Measured = 120.0356
Preparation of 1.1.6.6-Tetrafluoro-1,5-hexadiene (123)
1,1,6,6-Tetrafluoro-1,5-hexadiene (123) was prepared by adaptation of a
procedure as described by Naae and Burton.134 A three necked round bottom
flask was assembled with two septa, a pressure equalizing addition funnel,
magnetic stirrer, and flame dried under Ar purge. Dibromodifluoromethane
(1.55 g, 7.39x1 O'3 mol) was transferred to a Rotaflow tube then dissolved in 15
ml of dry triglyme and added to the reaction vessel by syringe. This solution
was cooled to -5°C with an ice/salt bath. P(N(CH3)2)3 (2.6 ml, 2.3 g, 1.4x10-2

142
mol) was dissolved in 10 ml of dry triglyme in the addition funnel, then added to
the CF2Br2 solution over 15 minutes with good stirring and cooling at -5°C. The
resultant cloudy solution, thick with white precipitate, was stirred for 1 hour at
-5°C then brought to RT. 5,5-Difluoro-4-pentenal (135, 0.90 g, 7.5x1 O’3 mol)
was dissolved in 5 ml dry triglyme and added to the ylide solution at RT over 5
minutes. This mixture was allowed to stir for 18 hours at RT. The reaction
mixture was then flash distilled into a two necked Rotaflow trap up to a bath
temperature of 40°C at 0.5 mm Hg. 1,1,6,6-Tetrafluoro-1,5-hexadiene (0.44 g,
38%) was obtained being a clear, colorless liquid containing traces of diethyl
ether, CH2CI2, and OP(N(CH3)2)3.
1,1.6.6-Tetrafluoro-1,5-hexadiene (123): 1H (300 MHz, CDCI3, TMS)
2.05-2.08 (m, 4H), 4.06-4.20 (dm, 2H, 3J,ranSHF = 25.5 Hz); 13C (75 MHz, CDCI3,
CHCI3) 22.3 (m, 2C), 76.8 (t, 2C, 2JCf = 21.5 HZ), 156.6 (dd, 2C, 1JCF = 285.6 Hz,
1JCf = 285.7 Hz); 19F (282 MHz, CDCI3, CFCI3) -89.0 (d, 2F, 2JFF = 46.4 Hz, -91.2
(dd, 2F, 2Jff = 46.4 Hz, 3JtransHF = 25.5 Hz); Low Resolution Mass Spectrum: m/z
(% relative intensity) 154 (1), 134 (1), 115 (2), 95 (2), 85 (23), 77 (100), 64 (2);
High Resolution Mass Spectrum: Calculated for C6H6F4 = 154.0405, Measured
= 154.0410
Gas Phase Thermolysis of 1.1.6.6-Tetrafluoro-1.5-hexadiene (1231
An =100 mg sample of 123 was obtained 98% pure by preparative
GLPC seperation from an NMR solution in C6D6. (Column: 0.25 inch x 12 feet,
20% SE-30 on Chromosorb P 80/100; Oven: constant at 80°C; Injector: 100°C;
TCD block: 110°C; He flow rate: 35 ml/minute) Eight millimeter Hg samples of
123 were expanded into the gas kinetics vessel as described in Appendix A,
and conversion to 3,3,4,4-tetrafluoro-1,5-hexadiene (124) followed by GLPC.
(See Table 4-12 for data, Column: 0.125 inch x 15 feet, AgN03/C6H5CH2CN

143
30% on Chromosorb Z 80/100; Oven: constant at 35°C; N2 flow rate: 30
ml/minute; Retention times: 124 5.9 minutes, 123 7.0 minutes) Following the
gas phase reaction versus internal standard n-octane showed the yield of this
transformation to be 99%. Reversibility of 124 back to 123 was not observed.
Isolation of 124: A 30% solution of 123 in CeH6 was sealed in a Carius
tube and thermolyzed at 185°C for 42 hours. 19F NMR at this time shows only
124. Pure 124 was isolated by preparative scale GLPC from this solution.
(Column: 0.25 inch x 20 feet, 20% Triton X-305 on Chromosorb W 80/100;
Oven: 90°C constant ; Injector: 120°C; TCD block: 120°C; He flow rate: 30
ml/minute)
3.3.4.4-Tetrafluoro-1,5-hexadiene (1241: 1H (300 MHz, CDCI3, TMS)
5.66-5.72 (m, 1H), 5.81-6.08 (m, 2H); 13C (75 MHz, CDCI3, CHCI3) 114.9 (tt, 1C,
1JCF = 247.1 Hz, 2JCF = 35.7 Hz), 124.0 (m, 1C), 126.5 (t, 1C, 2JCf = 24.6 Hz); 19F
NMR (282 MHz, CDCI3, CFCI3) -115.6 (dm, 4F, 3JHF = 12.1 Hz); Low Resolution
Mass Spectrum: m/z (% relative intensity) 154 (1), 135 (5), 134 (2), 115 (8), 85
(13), 78 (3), 77 (100), 57 (3), 51 (16); High Resolution Mass Spectrum:
Calculated for C6H6F4 = 154.0405, Measured = 154.0400
Preparation of 4-Methvlidene-1-cyclohexanone ethvlene ketal (1371
4-Methylidene-1-cyclohexanone ethylene ketal (137) was prepared by
adaptation of a general procedure.135 A 250 ml, three necked, round bottom
flask was assembled with a magnetic stirrer, two pressure equalizing addition
funnels, and a septum. The system was then flame dried under Ar purge.
(CeH5)3PCH3Br (22.6 g, 6.33x1 O'2 mol) was added and a slurry created by the
addition of 80 ml of dry THF. This slurry was cooled to 0°C by an ice-water bath.
n-Butyl lithium (n-BuLi) in n-pentane (31.7 ml of a 2.0 M solution, 6.34x1 O'2 mol)

144
Table 4-12. Averaged Percent Composition Data for Thermolysis of 123.
207.2°C
Seconds
%1 23
2100
95.2
3600
92.1
5760
87.7
8220
82.9
12120
75.9
15840
69.9
18000
66.7
228.8°C
Seconds
% 1 2 3
1500
86.9
3000
74.8
4500
66.4
5400
61.2
6600
55.0
8100
48.1
216.2°C
Seconds
%1 23
1800
92.7
3600
86.0
5400
79.2
7200
74.1
9000
69.4
10800
63.9
14700
54.2
235.7°C
Seconds
%1 23
1200
84.1
2520
69.6
3600
60.4
4860
50.8
6000
43.5
7200
36.9
224.2°C
Seconds
%1 23
1800
88.0
3720
76.3
5460
68.2
7200
60.6
9000
53.7
10800
47.0
241.6°C
Seconds
%1 23
900
82.9
1800
69.7
2700
58.2
3600
48.8
4500
41.0
5400
34.0
was added to an addition funnel with a Teflon stopcock. While vigarously
stirring the slurry, the n-BuLi solution was added over 40 minutes. The solution
turned canary yellow upon addition of n-BuLi. At 30 minutes into the addition,
the mixture had become a clear, deep yellow-red homogenous solution. Upon
completion of addition of the n-BuLi, the solution was warmed to RT and stirred
for 1 hour. The ylide solution was then cooled to 5°C and 9.0 g (5.76x1 O'2 mol)

145
1,4-cyclohexanedione mono-ethylene ketal in 20 ml dry THF was added
dropwise from the second addition funnel over 20 minutes. The reaction
mixture was then stirred at RT for 15 hours to yield a clear, light yellow solution
containing much fine white precipitate. Water (3 ml) was then added to
decompose any possible remaining ylide. The solids were gravity filtered and
rinsed with 40 ml THF and 50 ml hexanes. The solution was then concentrated
by rotary evaporator to yield an oil with some white solid. This material was
then dissolved in 100 ml methanol and extracted with 3 x 100 ml hexanes. The
combined hexanes where then extracted with 3 x 100 ml saturated aqueous
NaCI. The hexane solution was then dried over MgS04 and concentrated by
rotary evaporator to yield =5 ml of clear oil containing some white crystals. This
material was dissolved in 25 ml hexanes and set aside in a freezer at -5°C for
18 hours. The solution was vacuum filtered (while cold) through a fritted filter to
remove the white crystalline OP(C6Hs)3. The resultant clear, colorless solution
was concentrated by rotary evaporator to yield 6.2 g (69%) clear, colorless 137.
4-Methylidene-1-cyclohexanone ethvlene ketal (1371: 1H (200 MHz,
CDCI3, TMS) 1.69 (t, 4H, 3JHh = 6.2 Hz), 2.27 (t, 4H, 3JHH = 6.2 Hz), 3.96 (s, 4H),
4.66 (s, 1H); (50 MHz, CDCI3, CHCI3) 31.9, 35.8, 64.2, 108.1, 108.5, 147.2
Preparation of 4-Methvlidenecvclohexanone (1381
4-Methylidenecyclohexanone (138) was prepared by adaptation of a
procedure as described by Huet et a/.136 Silica gel (73 g) was suspended in
180 ml of CH2CI2 by rapid stirring in a round bottom flask. Sulfuric acid (15%,
7.3 g) was added to the silica gel slurry dropwise. After 5 minutes, the beads of
aqueous acid had been adsorbed onto the silica gel. 4-Methylidene-1-
cyclohexanone ethylene ketal (137, 6.2 g, 4.0x1 O’2 mol) was then added and
rapid stirring continued. After 3 hours, GLPC analysis shows a 4:1 ratio of

146
deprotected to protected ketone. The solution was filtered, then subjected to a
second treatment as above (38 g silica gel, 4.8 g of 15% H2SO4). After 3 hours
stirring, GLPC analysis shows 10.2:1 ratio of 138:137. The solution was then
filtered and the silica gel rinsed with 2 x 100 ml CH2CI2 and then concentrated
by rotary evaporator to yield 4.6 g of light yellow oil. This material was distilled
yielding and inital fraction of CH2CI2 followed by 3.9 g (90%) clear, colorless
138 boiling from 99-102°C at 115 mm Hg.
4-Methylidenecvclohexanone (1381: 1H (200 MHz, CDCI3, TMS) 2.35-
2.60 (m, 8H), 4.89 (s, 2H); 13C (50 MHz, CDCI3, CHCI3) 32.9, 41.4, 110.5, 144.2,
210.3
Preparation of 1-Difluoromethvlidene-4-methvlidenecvclohexane (1281
1-Difluoromethylidene-4-methylidenecyclohexane (128) was prepared
by adaptation of a procedure as described by Naae and Burton.134 A 250 ml,
three necked, round bottom flask was equipped with a septum, pressure
equalizing addition funnel, and strong magnetic stirrer. The system was then
flame dried under Ar purge. Dibromodifluoromethane (5.8 g, 2.8x1 O'2 mol) was
weighed out into a Rotaflow tube, dissolved in 75 ml dry THF, then transferred to
the reaction vessel by syringe. This solution was cooled to -5°C. P(N(CH3)2)3
(10.2 ml, 9.1 g, 5.6x10'2 mol) was transferred to the addition funnel and
dissolved in 40 ml of dry THF then added to the CF2Br2 solution dropwise over
30 minutes with cooling. The resultant slurry of white precipitate was stirred 1
hour then brought to RT. 4-Methylidenecyclohexanone (138, 1.92 g, 1.74x1 O'2
mol) was dissolved in 5 ml dry THF and added dropwise to the ylide solution.
This mixture was stirred for 14 hours at RT. The yellow solid was gravity filtered
and the solution concentrated to =10 ml volume by simple distillation. The
liquid was then dissolved in 200 ml diethyl ether and exhaustively extracted

147
with water. This ether solution was then dried over MgSC>4, filtered, and
distilled off through a 6 cm vigeraux column. The remainder of the material was
transferred to a micro distillation apparatus and distilled under vacuum to yield
1.5 g (60%) 128 as an end fraction boiling 55-59°C at 115 mm Hg.
1-Difluoromethylidene-4-methvlidenecvclohexane (1281: 1H (300 MHz,
CDCl3, TMS) 2.18 (m, 8H), 4.70 (s, 2H); 13C (50 MHz, CDCI3, CHCI3) 25.5, 34.4
(t, 2C, 3Jcf - 2 Hz), 87.1 (t, 1C, 2JCf = 18.9 Hz), 108.6, 147.3, 150.9 (t, 1C, 1 JCf =
279.5 Hz); 19F (282 MHz, CDCI3, CFCI3) -98.4 (m, 2F); Low Resolution Mass
Spectrum: m/z (% relative intensity) 144 (100), 129 (65), 127 (12), 115 (20), 109
(40), 97 (9), 79 (15), 77 (18); High Resolution Mass Spectrum: Calculated for
C8H10F2 = 144.0750, Measured = 144.0753
Gas Phase Thermolysis of 1-Difluoromethvlidene-4-methvlidenecvclohexane
am
An «100 mg sample of 128 was obtained 99% pure by preparative
GLPC. (Column: 0.25 inch x 12 feet, 20% SE-30 on Chromosorb P 80/100;
Oven: constant at 145°C; Injector: 175°C; TCD block: 170°C; He flow rate: 30
ml/minute) Eight millimeter Hg samples of 128 were expanded into the gas
kinetics vessel as described in Appendix A, and conversion to 1,1 -difluoro-2,5-
dimethylidenecyclohexane (139) followed by GLPC. (See Table 4-13 for data,
Column: 0.125 inch x 11.5 feet, 20% DNP on Chromosorb WHP 60/80; Oven:
constant at 140°C; N2 flow rate: 30 ml/minute; Retention times: 128 5.3 minutes;
139 7.3 minutes) Following the gas phase reaction versus internal standard n-
octane showed the yield of this transformation to be 98%. Reversibility of 139
back to 128 was not observed. 1,1-Difluorc-2,5-dimethylidenecyclohexane
(139) was isolated by twice thermolyzing 12 mm Hg samples of 128 in both

148
thermolysis vessels for 150 minutes at 332.6°C and collecting the product in a
Rotaflow tube for analysis.
1.1-Difluoro-2.5-dimethylidenecyclohexane (1391: 1H (300 MHz, CDCI3,
TMS) 2.25-2.30 (m, 2H), 2.36-2.41 (m 2H), 2.67 (tt, 2H, 3JHF = 13.7 Hz, 4JHH =
1.2Hz), 4.87 (m, 1H), 4.92 (m, 1H), 5.09 (m, 1H), 5.39 (m, 1H); 19F (282 MHz,
CDCI3, CFCI3) -100.9 (t, 2F, 3Jhf = 13.7 Hz); Low Resolution Mass Spectrum:
m/z (% relative intensity) 144 (100), 129 (88), 115 (27), 109 (86), 97 (29); High
Resolution Mass Spectrum: Calculated for C8Hi0F2 = 144.0750, Measured =
144.0748
Table 4-13. Averaged Percent Composition Data for Thermolysis of 128.
287.8°C
Seconds
128
1260
91.8
2460
85.1
3480
79.3
4800
72.5
6180
66.9
9180
54.8
13860
39.6
19920
26.2
279.9°C
Seconds
128
2400
90.8
4500
84.3
6120
79.4
7980
73.4
14880
58.3
21000
44.5
292.1°C
Seconds
128
1500
87.5
3060
75.4
5280
62.7
7320
52.0
9240
43.8
11940
36.0
14880
25.9

149
Table 4-13 - Continued-
297.6°C
Seconds
128
1200
87.2
2880
70.2
4620
56.4
6000
47.1
11160
23.6
13740
18.0
16380
13.3
303.0°C
Seconds
128
600
89.9
1440
77.4
2100
68.8
2760
61.4
4620
44.7
8340
22.3
10200
15.6
309.1°C
Seconds
128
600
85.8
1320
71.4
1920
60.7
2520
51.8
3120
43.4
3720
38.0
10680
6.4
Preparation of 1.4-Di(difluoromethvlidene)cvclohexane (129)
1,4-Di(difluoromethylidene)cyclohexane (129) was prepared by
adaptation of a procedure as described by Naae and Burton.134 A 500 ml, three
necked, round bottom flask was equipped with a mechanical stirrer, septum and
pressure equalizing addition funnel and flame dried under Ar purge.
Dibromodifluoromethane (16.93 g, 8.07x10-2 mol) was transferred to a Rotaflow
tube then dissolved in 70 ml of dry THF. This solution was transferred to the
reaction vessel by syringe followed by an additional 70 ml dry THF.
P(N(CH3)2)3 (29.5 ml, 26.5 g, 1.62x10'1 mol) was dissolved in 90 ml dry THF in
the addition funnel. The CF2Br2 solution was cooled to -5°C with an ice/salt
bath then the P(N(CH3)2)3 solution was added dropwise over 1 hour. This
mixture was stirred at -5°C for 2 hours then brought to RT. 1,4-
Cyclohexanedione (4.5 g, 4.0x10'2mol) was dissolved in 40 ml dry THF and
added to the ylide solution over 35 minutes. The reaction mixture was then
stirred for 18 hours at RT. The pale yellow solids were then filtered away from

150
the yellow-brown solution. The solution was then concentrated by rotary
evaporator down to a volume of *15 ml which was taken up in 200 ml diethyl
ether. The ether solution was exhaustively extracted with water then dried over
MgSCU. The ether was distilled off through a 6 cm vigeraux column to leave *3
ml of clear brown liquid. This material was transferred to a micro distillation
apparatus and vacuum applied down to 15 mm Hg and *1 ml of ether frothed
over. As a later fraction, 2.5 g (36%) clear, light yellow 129 was obtained
boiling 60-62°C at a pressure of 12-10 mm Hg.
1.4-Di(difluoromethylidene)cvclohexane (1291: 1H (300 MHz, CDCI3,
TMS) 2.15 (p, 8H, 4JHf= 1-3 Hz); 13C (75 MHz, CDCI3, CHCI3) 23.9 (m, 4C), 86.5
(t, 2C, 2Jcf = 19.2 Hz), 151.2 (t, 2C, 1JCf = 280.2 Hz); 19F (282 MHz, CDCI3,
CFCI3) -97.7 (septet, 4F, 4Jhf= 1.3Hz); Low Resolution Mass Spectrum: m/z (%
relative intensity) 180 (100), 165 (12), 145 (19), 127 (15), 111 (61), 109 (26),
103 (19), 77 (24); High Resolution Mass Spectrum: Calculated for C8H8F4 =
180.0562, Measured = 180.0571
Gas Phase Thermolysis of 1.4-Di(difluoromethvlidene1cvclohexane (129)
An *100 mg sample of 129 was obtained 99% pure by preparative
GLPC seperation from a solution in THF. (Column: 0.25 inch x 12 feet, 20% SE-
30 on Chromosorb P 80/100; Oven: constant at 130°C; Injector: 150°C; TCD
block: 150°C; He flow rate: 30 ml/minute) Eight millimeter Hg samples of 129
were expanded into the gas kinetics vessel as described in Appendix A, and
conversion to 1,1,2,2-tetrafluoro-3,6-dimethylidenecyclohexane (141) followed
by GLPC. (See Table 4-14 for data, Column: 0.125 inch x 10 feet, 20% QF-1 on
Chromosorb WHP 100/120; Oven: constant at 110°C; N2 flow rate: 30
ml/minute; Retention times: 129 3.4 minutes, 141 5.1 minutes) Following the
reaction versus internal standard (n-octane) showed the yield of this

151
Table 4-14. Averaged Percent Composition Data for Thermolysis of 129
329.2°C
Seconds
129
1200
85.6
2400
72.5
3600
61.8
4920
51.6
6000
45.4
7200
37.7
336.9°C
Seconds
129
2280
67.7
6000
31.5
8460
17.7
10980
10.2
16860
3.4
343.2°C
Seconds
129
1680
59.8
2700
43.6
3960
30.0
5160
21.2
6360
14.4
7560
10.3
354.5°C
Seconds
129
780
66.0
1200
51.0
1500
42.5
1920
35.1
2340
26.8
2760
22.4
349.1°C
Seconds
129
960
66.6
1800
49.1
2700
31.5
3840
20.0
4800
13.5
6600
7.1
359.8°C
Seconds
129
600
65.6
1200
40.6
1800
26.4
2400
16.7
3000
11.1
transformation to be 99%. Reversibility of 141 back to 129 was not observed.
The product 141 was isolated by twice thermolyzing 12 mm Hg samples of 129
in both thermolysis vessels for 200 minutes at 359.8°C and collecting the
product in a Rotaflow tube for analysis.
1.1.2,2-Tetrafluoro-3.6-dimethvlidenecvclohexane (1411: 1H (300 MHz,
CDCI3, TMS) 2.42 (bs, 4H), 5.35 (s, 1H), 5.63 (s, 1H); (282 MHz, CDCI3,
CFCI3) -123.1 (s, 4F); Low Resolution Mass Spectrum: m/z (% relative intensity)

152
180 (60), 165 (17), 145 (19), 111 (100), 77 (23); High Resolution Mass
Spectrum: Calculated for C8H8F4 = 180.0562, Measured = 180.0564
Preparation of 2-(2-Oxocvclopentvl)cvclopentanone (143)
2-(2-Oxocyclopentyl)cyclopentanone (143) was prepared by the method
of Paul.137 A three necked, round bottom flask was equipped with a condenser,
magnetic stirrer, and pressure equalizing addition funnel then flame dried under
Ar purge. Freshly cut sodium metal (0.75 g, 3.3x1 O'2 mol) was placed in the
flask followed by 20 ml of dry toluene. The system was heated to reflux and
stirred rapidly, breaking the Na° into small spheres. Ethyl-2-oxocyclopentane
carboxylate (5.0 g, 3.2x1 O'2 mol) was dissolved in 5 ml of toluene and added
dropwise to the Na° at reflux with rapid stirring. Upon completion of addition,
the mixture was heated at reflux for 1 hour, after which all of the Na° metal had
been consumed. 2-Chlorocyclopentanone (3.97 g, 3.34x10~2 mol) was
dissolved in 5 ml dry toluene and added dropwise to the refluxing enolate
solution. Upon completion of addition, the mixture was held at a gentle reflux
for 9 hours. The resultant solids were then gravity filtered and the reaction
solution extracted with 3 x 50 ml of water, then dried over MgS04. The toluene
was then removed by rotary evaporator to yield 3.4 g (66%) crude product
which was purified by Kughelrohr distillation to give 2.4 g (47%) pure white
solid ethyl 2,2'-bismethylenecyclopentane-2-carboxylate. This material was
added to a round bottom flask containing 15 ml of 20% HCI and assembled with
a condenser. The mixture was brought to a gentle reflux and ethanol was
added (=3 ml) until the mixture became homogenous. The solution was heated
at a gentle reflux for 24 hours at which time GLPC analysis showed the
decarboxylation to be =90% complete. The reaction solution was extracted with
4 x 50 ml diethyl ether and the ether solution was exhaustively extracted with

153
water then dried over MgS04. The ether was removed by rotary evaporator
and the resultant material purified by Kughelrohr distillation to yield 0.91 g
(55%) solid, white, 143.
2-(2-Oxocyclopentyl)cvclopentanone (143): 1H NMR (300 MHz, CDCI3,
TMS) 1.52*1.88 (m, 4\~\meso and d,i)i 1.98-2.39 (m, 8Hmesoand d,/)> 2.53 (t, 2-Hmesoor
d.l, 3Jhh * 8.9 Hz), 2.63 (t, 2Hmes00rd,/, 3Jhh - 9.1 Hz); 13C NMR (75 MHz, CDCI3,
CDCI3) meso and d,/diasteromers: 20.2, 20.4, 24.9, 26.3, 37.4, 37.6, 48.0, 48.7,
218.3, 219.2
Preparation of meso and d,/-1-(2-Difluoromethvlidenecvclopentvl)-2-difluoro-
methvlidenecvclopentane (/neso-131.cf./-131)
meso and d,/-1-(2-Difluoromethylidenecyclopentyl)-2-difluoro-
methylidenecyclopentane (n7eso-131,cf,/-131) was prepared by adaptation of
a procedure as described by Naae and Burton.134 A 500 ml, three necked,
round bottom flask was equipped with a mechanical stirrer, pressure equalizing
addition funnel, septum, and flame dried under Ar purge.
Dibromodifluoromethane (21.25 g, 1.01x10_1 mol) was transferred to a Rotaflow
tube, dissolved in 80 ml dry THF, then syringed into the reaction vessel followed
by 150 ml dry THF. The CF2Br2 solution was then cooled to -5°C. P(N(CH3)2)3
(36.0 ml, 32.3 g, 1.98x10‘1 mol) was transferred to the addition funnel and
dissolved in 100 ml dry THF. This solution was added dropwise to the CF2Br2
with cooling over 1.75 hours. The resultant slurry of white solid was stirred at
-5°C for 1.33 hours after which it was heated to 40°C. 2-(2-
Oxocyclopentyl)cyclopentanone (143, 4.27 g, 2.57x1 O*2 mol) was dissolved in
20 ml dry THF and added dropwise to the ylide mixture at 40°C over 1 hour with
vigorous stirring. The mixture was then stirred for 17 hours at 40°C. At this time,
the yield of 131 is 31%, as checked by 19F NMR versus added CeH5F. The

154
resultant reaction mixture was gravity filtered to remove the tan solids and the
solution concentrated by rotary evaporator to yield =3 ml of dark brown viscous
liquid. Diethyl ether (250 ml) was added and this solution exhaustively
extracted with water. The ether phase was then dried over MgS04, and
concentrated by rotary evaporator to yield 1.9 g (28%) light brown oil being 90%
131, 8% THF/diethyl ether, and 2% OP(N(CH3)2)3.
meso and d./-1 -(2-Difluoromethylidenecyclopentyh-2-difluoro-
methvlidenecvclopentane (meso-'i 31 d./-131): 1H NMR (200 MHz, CDCI3,
TMS) 1.43-1.86 (m, 8Hmesoand d,/)> 2.12-2.40 (m, 4Hmesoand ¿¡J), 2.78 (bs, 2H3°ch,
meso), 2.96 (bs, 2H3° ch, d,i)\ 19F NMR (188 MHz, CDCI3, CFCI3) -91.1 (d, 1 Fd.i,
2Jff = 63.0 Hz), -91.2 (d, 1Fmeso, 2JFF = 61.6 Hz), -91.5 (d, 1Fmeso, 2JFF = 61.6
Hz), -92.8 (d, 1 Fd>/, 2jff = 63.0 Hz); 13C NMR (50 MHz, CHCI3, TMS) meso and
c/,/diasteromers: 23.9, 24.6, 26.0, 26.6, 29.3, 30.9, 41.0 (m, C), 93.0 (t, C, 2JCF =
19.2 Hz), 151.2 (t, C, 1Jcf = 280.9 Hz); Low Resolution Mass Spectrum: m/z
(relative intensity): meso: 234 (21), 214 (6), 118 (7), 117 (100), 116 (12), 115
(5), 97 (23), 77 (7); d,h 234 (30), 214 (4), 118 (7), 117 (100), 116 (12), 115 (5),
97 (22), 77 (4); High Resolution Mass Spectrum: Calculated for Ci2H14F4 =
234.103, Measured (d,l) =234.104, Measured {meso) = 234.103
Solution Phase Thermolysis of meso and d./-1-(2-Difluoromethylidene-
cvclopentvl)-2-difluoromethvlidenecvclopentane (meso-131.cf./-131)
A 0.160 g sample of 1-(2-Difluoromethylidenecyclopentyl)-2-difluoro-
methylidenecyclopentane (131) was obtained 97% pure by preparative GLPC,
being 97% 131 and 3% 1-(2-(1-cyclopentenyl)-1,1,2,2-tetrafluoroethyl)-
cyclopentene (144). (Column: 0.25 inch x 5.5 feet, 20% QF-1 on Chromosorb
WHP 80/100; Oven: constant at 100°C; Injector: 105°C; TCD block: 78°C; He
flow: 190 ml/minute; Retention Times: 131 12.6 minutes, 144 15.7 minutes)

155
This material was dissolved in 1.47 g dry, freeze-thaw degassed n-dodecane
(99+% pure, Aldrich Chemical Co.) and 0.033 g C6H5F was added as 19F NMR
internal standard. As samples were needed, 0.25 ml aliquots were drawn by
syringe and placed in thick walled NMR tubes (base rinsed, deionized water
rinsed, acetone rinsed, flame dried) and flame sealed under N2. Lower
temperature rearrangement of d,/-131 to 144 was carried out by thermolyzing
the sample for a specific time in a Statim thermostated oil bath then rapidly
cooling and storing the sample on ice until 19F NMR analysis. Higher
temperature rearrangement of meso-131 to 144 was carried out by
thermolyzing the sample for a specific time in the thermostated, gas kinetics
apparatus, molten salt bath, then rapidly cooling and storing the sample at room
temperature until 19F NMR analysis. The relative concentrations of all reaction
components was monitored by integration of the 19F NMR sample signals
versus internal standard C6H5F. A T1 delay of 10 seconds was applied and a
minimum of 128 transients was collected before Fourier transforming and
integration of a spectrum. Each sealed sample yielded one rate constant for
each diasteromeric component; one from following the rearrangement of d,l-
131 at a lower temperature and one from following the rearrangement of
meso-131 at an elevated temperature. After collecting sufficient data from a
sample for thermolysis of d,l-131 at a given temperature, the sample was then
further thermolyzed at the lower temperature until no d,l-131 remained before
beginning thermolysis and data collection for meso-131 at elevated
temperatures. Rearrangement of cf,/-131 was found to follow first-order kinetics
and also found to be quantitative and nonreversible towards formation of 144
over the temperature range of 94.0 to 124.1°C. In thermolysis of meso-131,
small amounts of other materials were evidenced by 19F NMR. At longer times
in the thermolysis trials, there appeared trace amounts of a series of signals

156
from -122.6 through -128.7, a total of ten sets of multiplets. The largest
couplings observed were on the order of 15 Hz. Also observed at longer times
was a singlet of larger intensity at -148.0. Both materials would account for less
than 10% of the reaction mixture. The product 144 was obtained for
characterization by thermolyzing a crude (90% 131, 8% THF/diethyl ether, and
2% hexamethylphosphoric triamide) sample of 131 at 140°C for 2 hours then
isolating the product away from the unreacted meso-131 by preparative GLPC.
(Column: 0.25 inch x 5.5 feet, 20% QF-1 on Chromosorb WHP 80/100; Oven:
constant at 130°C; Injector: 140°C; TCD block: 150°C; He flow: 190 ml/minute)
1 -(2-H -Cyclopentenvh-1,1.2.2-tetrafluoroethvncyclopentene (1441: 1H
NMR (300 MHz, CDCI3, TMS) 1.96 (p, 4H, 3JHh = 7.54 Hz), 2.40-2.57 (m, 8H),
6.19 (bs, 2H); 13C NMR (75 MHz, CDCI3, TMS) 23.3, 31.4 (m, 2C, 3JCf = 1 -9 Hz),
32.7, 135.9 (m, 2C, 3JCf = 4.1 Hz); 19F NMR (282 MHz, CDCI3, CFCI3) -110.5 (s,
4H); Low Resolution Mass Spectrum: m/z (relative intensity): 234 (38), 118 (7),
117 (100), 116 (11), 115 (5), 97 (18), 77 (6), 67 (5); High Resolution Mass
Spectrum: Calculated for Ci2H14F4 = 234.103, Measured = 234.102.
Table 4-15. 19F NMR Ratios for Thermolysis of d,/and meso-1-(2-
Difluoromethylidenecyclopentyl)-2-difluoromethylidenecyclopentane [d,M 31,
meso-131) at 94.0 and 293.1 °C.
Thermolysis at 94.0°C
Seconds
%cf,/-1 31
%meso-1 31
%144
0
82.2
15.2
2.6
2220
73.3
15.2
11.5
5940
61.3
15.2
23.5
12660
42.2
15.2
42.6
19080
29.9
15.2
54.9

157
Table 4-15 - Continued-
-Temperature was then raised to 293.1°C-
Seconds
%d,/-1 31
%/77eso-131
% 14 4
0
0
15.2
84.8
2160
0
13.3
86.7
4260
0
11.9
88.1
7860
0
10.2
89.8
Table 4-16. 19F NMR Ratios for Thermolysis of d,l-1 -(2-Difluoro-
methylidenecyclopentyl)-2-difluoromethylidenecyclopentane (d,/-131) at
104.6°C.
Seconds
% %meso-131
%144
0
81.6
15.7
2.7
1200
70.2
15.7
14.1
2700
57.9
15.7
26.4
4800
44.5
15.7
39.8
7320
32.3
15.7
52.0
13440
14.0
15.7
70.3

158
Table 4-17. 19F NMR Ratios for Thermolysis of d,/and meso-1-(2-
Difluoromethylidenecyclopentyl)-2-difluoromethylidenecyclopentane (d,/-131,
meso-131) at 117.4 and 274.4°C.
Thermolysis at 117.4°C
Seconds
%d,/-131
%meso-131
%144
0
81.9
15.4
2.7
900
60.3
15.4
24.3
2760
30.0
15.4
54.6
4020
19.6
15.4
65
6120
8.9
15.4
75.7
Temperature was then raised to 274.4°C
Seconds
%d,l-131
%meso-"\ 31
%144
0
0
15.4
84.6
2700
0
14.4
85.6
6900
0
13.8
86.2
15660
0
12.5
87.5
27480
0
10.7
89.3
43560
0
9.3
90.7

159
Table 4-18. 19F NMR Ratios for Thermolysis of d,l and meso-1 -(2-
Difluoromethylidenecyclopentyl)-2-difluoromethylidenecyclopentane (cf,/-131,
meso-131) at 124.0 and 288.1°C
Thermolysis at 124.0°C
Seconds
%cf,/-1 31
%meso-131
%144
0
80.4
15.3
4.3
540
61.1
15.3
23.6
1140
44.5
15.3
40.2
2340
22.0
15.3
62.7
4260
6.9
15.3
77.8
Temperature was then raised to 288.1°C
Seconds
%d,/-131
% mes o-131
%144
0
0
15.3
84.7
1680
0
14.2
85.8
3900
0
12.9
87.1
11100
0
10.3
89.7
15540
0
8.8
91.2

APPENDIX A
GAS PHASE THERMOLYSIS APPARATUS
Key. 1-14 Rotaflow joints, A: molten salt bath, 1:1 by weight of NaNC>2, KNO3,
B:resistance coil, C: thermocouples, D: stirrer, E: 250 ml Pyrex kinetic bulbs, F: Rotaflow
sampling tube, G: starting material stock in Rotaflow tube, H: Pirani PR10-C gauge head, I:
Hg U-tube manometer, J: 5 L ballast at = 760 mm Hg of argon, K: liquid nitrogen trap,
L: vacuum pump
Figure A-1. Diagram of Gas Kinetics Apparatus.
All thermal isomerizations were carried out in conditioned, spherical
Pyrex 250 ml bulbs. These bulbs were submerged in a stirred (D) molten salt
bath (A, eutectic mixture, 1:1 by weight of NaN02, KNO3, mp = 180°C). The bath
was heated by a resistance coil (B) and temperature set and maintained by an
Omega Model 49 Proportioning Controller with platinum resistance
thermocouple. The temperature for a run was measured with an Omega Model
160

161
HH22 Microprocessor Thermometer with a type J (Fe-CuNi) thermocouple. The
thermocouples were immersed in the salt bath directly between the pyrolysis
vessels (Q). The temperatures were found to be constant to within 0.1 °C over a
run.
A typical run involves the following general procedure. The line and
pyrolysis vessels are pumped down with a high capacity, Welch Duo-Seal
rotary vane vacuum pump (L) and the ultimate vacuum (= 10‘3 mm Hg)
monitored with an Edwards Pirani Model 11 display and Pirani model PR10-C
gauge head (H). The pump and liquid nitrogen trap (K) are sealed off (12) and
an initial pressure of 8 ± 0.5 mm Hg of starting material (measured with a Hg U-
tube manometer, I) is introduced into the vacuum line by expansion from a
cooled Rotaflow tube (£). A sample is then expanded into the kinetics vessels
(E, 1 and 2) and timing started for the run. The excess starting material
remaining in the line at this time is condensed into the storage vessel ((¿) and
the line is pumped down. At a desired time, the pump is cut out (5.) and a
sample expanded into the sampling Rotaflow tube (E). The pump is then cut out
(131 and the sample dilluted with argon from a five liter bulb (1) to create a
sample with a total pressure of approximately 500 - 760 mm Hg, and removed
to make multiple GLPC injections via a gas sampling valve. The pump is then
cut in (2,12) and the line pumped down with a fresh sampling tube (E) in
preparation for the next sample.
Each kinetic thermolysis run was sampled at least five times. A Hewlett
Packard 5890 Series II gas chromatograph with a flame ionization detector and
a Hewlett Packard 3396A integrator was used to analyze the samples drawn.
Base-line resolution of peaks was observed for all quantitative GLPC studies.
Each point in a rate constant is an average of at least three GLPC injections.

162
The gas sampling technique utilized in all of the above-described studies
introduced multiple pressure variations per run. The fact that good uni-
molecular behavior was always observed indicates clearly the lack of significant
surface effect problems. The kinetic apparatus is modeled after the apparatus
and technique of Dr. H. M. Frey, University of Reading, England.

APPENDIX B
SELECTED NMR SPECTRA
The 19F NMR spectra of new compounds are graphically illustrated in this
appendix. The spectra are presented numerically in their respective areas in
Chapter 4. The compounds E-56 and Z-56 have been previously reported as
discussed in Chapter 2. The spectra are shown in order of their dissertation
identification number and the compounds which have been included in this
appendix are: 40 (at -17.0°, 25.0°C, and 80.0°C), 41, 49, 50, 51, £-56, Z-56,
62, 63, 123, 124, meso-131, d,l-131, and 144.
163

Figure B-1. 9,10-Bis(trifluoroethenyl)phenanthrene (40) at -17.0°C in CDCI3

KG'OOt-
i—i—|—i—i—i—i—r~>—*—•—•—|—*—*—•—1—r
-loo -no
Figure B-2. 9,10-Bis(trifluoroethenyl)phenanthrene (40) at 25.0°C in CDCI3.
165

Figure B-3. 9,10-Bis(trifluoroethenyl)phenanthrene (40) at 80.0°C in CDCI3.
166

Figure B-4. 1,2,2,3,3,4-Hexafluoro-2,3-dihydrotriphenylene (41) in CDCI3.
167

-JL , ,
ri t i i n i 11 ' I 11 i r i) i i i I M i i'i i i i i irmTi'i i i i i i i | 11 i i | i i i i ii i i i | 11 i i i i i i i | i n i ri r i i | i i i i i i i i i | i i i i |
-40 -60 -80 -100 -120 -140 -160 -180 -200 -220 PPM -240
Figure B-5. I.M.S.e.e-Hexafluoro^.S-^JO-phenanthroJbicycloIS.I.Olhex^-ene (49) in CDCI3.

Figure B-6. Expansion 1 of 6 for the 87.0 - 88.6 ppm Region of
1,4,4,5,6,6-Hexafluoro-2,3-(9,10-phenanthro)bicyclo[3.1.0]hex-2-ene (49) in CDCI3.
169

i i i i i i -i p| i ~i i i i i i i i | i i i i i i i i i | i i i i |i i i i | i i i i '|~i i i i | i i i i i ri ~i~i~| i i i i i' i i i i~| i i i i i i i i i | i i i -T ■[—i-T
-ill.6 -111.8 -112.0 -112.2 -112.4 -112.6 -112.8 -113.0 -113.2 f
Figure B-7. Expansion 2 of 6 for the 111.6 -113.3 ppm Region of
I.M.S.e^-Hexafluoro^.S-^.IO-phenanthroJbicyclotS.I.Olhex^-ene (49) in CDCI3.
170

4
rjTTTTTTT TTJT iMii ii q m i i i i i i 11 rrri i i i i | i ii i i m i i | i » rri rmrjTTTl ti i i i i » i i ii i i i i | i i rr i i i i urn-m iii'imri n ri i i
-137.2 -137.3 -137.4 -137.5 -137.6 -137.7 -137.0 -137.9 -130.0 -130.1 -130.2 PPM
Figure B-8. Expansion 3 of 6 for the 137.1 - 138.3 ppm Region of
1,4,4,5>6,6-Hexafluoro-2,3-(9)10-phenanthro)bicyclo[3.1.0]hex-2-ene (49) in CDCI3.

Figure B-9. Expansion 4 of 6 for the 147.0 - 148.2 ppm Region of
MAS.e.e-Hexafluoro^XO.IO-phenanthroJbicyclotS.I.Olhex^-ene (49) in CDCI3.
172

Figure B-10. Expansion 5 of 6 for the 216.15 - 216.45 ppm Region of
1,4,4,5,6,6-Hexafluoro-2,3-(9,10-phenanthro)bicyclo[3.1.0]hex-2-ene (49) in CDCI3.
173

-230.05
1 ] ' r
-230.10
'-23(1.2
-230.23
I | I I I
-230.30
'-23(1.3
Figure B-11. Expansion 6 of 6 for the 230.05 - 230.38 ppm Region of
I^^.S.e.G-Hexafluoro^.S-iO.IO-phenanthroJbicyclo^.I.Olhex^-ene (49) in CDCI3.

Figure B-12. 4-Difluoromethylidene-3,3,5)5-tetrafluoro-1)2-(9l10-phenanthro)cyclopent-1-ene (50) in CDCI3.
175

i J**i~ i i—r 1"r r'T i j I r~r—r-|—i—ri—i—[—i—i—i—i—|—i—i—i—\ -r i—i—i—r—i—i—i—i—i—^—t—r~i—i—|—i—r~r—»—i—r—r—r—r- t— t— t—t—i—t— t -i-t-
-¿0 -70 -00 -¿0 -100 -110 -l?0 PPM
Figure B-13. 1,2-(9,10-Phenanthro)-3,5,5-trifluoro-4-trifluoromethyl-1,3-cyclopentadiene (51) in CDCI3.
176

F
1 I II I | ! I I I 1 I I I I | I I I I ' I I I I ] I I I I! I I I I | I I I 11 II I I ] 1 II I | I 1 II | I II I | I t 1 1 J 1 M II 1 I I I | I I I I T I I I I | 1 II 1 | 1 I I 1 ] I W I 1 M II | 1 1 M M I 1 1 f M 1 1 1 1 I I I ! 1 I ) 1 1 T
0 0 -20 -40 -60 -So -100 -120 -140 -160 -100 -200 -220 PPM -240
Figure B-14. Perfluoro-E.E.E-^S-dimethyl^Ae-octatriene (E-56) in n-Pentane.
177

Figure B-15. Perfluoro-E,Z,E- and E,E,E-4,5-dimethyl-2,4,6-octatriene (Z-56(E-56)) in n-Pentane.
178

Figure B-16. Perfluoro-írans-2,3,5(6-tetramethyl-1(3-cyclohexadiene (62) in n-Pentane.
179

Perfluoro-frans-2,3,5,6-tetramethyl-1,3-cyclohexadiene (62) in n-Pentane.
180

i
i tj rn r
"H n|n n] rrr n“nTT]TrrTp*rrrpTrri mTpn ttptt rp-rrr pr ri'Tj n i rj tittjttt rj it
O -80 -100 -120 -140 -160 -180 -200
Figure B-18. Perfluoro-frans^.S.S.e-tetramethylbicyclo^.Olhex^-ene (63) in n-Pentane.
181

i j rrrrj ttt tjiti i | rrrrj rm | i » itjtt ¡ 1 | » i rr-p rn |iiii|iiii|ini Htt i jm > [ i i n |rrr i p
-6*1.18 -64.20 -64.22 -64.24 -64.26 -64.20 -64.30 -64.32 PPM
Figure B-19. Expansion 1 of 3 for the 63.6 to 64.4 ppm Region of
Perfluoro-frans-2,3,5,6-tetramethylbicyclo[2.2.0]hex-2-ene (63) in n-Pentane.
182

t j 1 i t r—j—i—t—i—i—|—7—i—i—i—|—r—i—i—i—j—i—i—r
-73.05 -73.10 -73.15 -73.20 -73.25 PPM
Figure B-20. Expansion 2 of 3 for the 72.5 to 76.5 ppm Region of
Perfluoro-f/'ans-2,3,5,6-tetramethylbicyclo[2.2.0]hex-2-ene (63) in n-Pentane.
183

Perfluoro-frans-2,3(5,6-tetramethylbicyclo[2.2.0]hex-2-ene (63) in n-Pentane.
184

t p ri
rrrrTTfT rn jrn-TrrTTrTTrr-rii r riyn rrp t tt
0 -20 -40 -60 -flO
ynTTTTiTTprTTrp rrrp i irprn pin yrm p m p
-140 -160 -180 -200 -220 PPM
ttt i}
-240
Figure B-22. 1,1,6,6-Tetrafluoro-1,5-hexadiene (123) in CDCI3.
185

-ns.ezfl
Figure B-23. 3,3,4,4-Tetrafluoro-1,5-hexadiene (124) in CDCI3.
186

J vi V A.
i I—i—i IT]—I—I—i—I—]—r
-9Ó.5 -91.0 -91.5
T—I—I—I—I—I—I—I—I—I—I
-92.0 -92.5 PPM
00
-vj
... . -
i i i i i i ri i | i i i i i i i i i i'i i11 i | i i i i | i i i i | i i i i j i i i i | rm~p~i i i | 11 i'T pv rrp i i i | i i i i | i i ittttti"| i m i i i i
-10 -60 -80 -100 -120 -1-10 -160 -180 -200
Figure B-24. d,l- and meso-1-(2-Difluoromethylidenecyclopentyl)-
2-difluoromethylidenecyclopentane (d,l-131, /?7eso-131) in CDCI3.
-92.5919

-90.8491
mesa-131
LI
TtTn rrrrrrr» i i i | i i i i | i i i rrrr nTi-rTrTmTp-rrTTiTTry nTTTrTTrf i-rrT-|-rrrrp r 11 rm rj i :
-60 -00 -100 -120 -140 -160 -100 -200 -220
00
00
Figure B-25. Thermolysis of meso-1-(2-Difluoromethylidenecyclopentyl)-
2-difluoromethylidenecyclopentane (meso-131) Sample Containing 1-(2-(1-Cyclopentyl)-
1,1,2,2-tetrafluoroethyl)cyclopentene (144) and CeH5F (113.1 ppm) in n-Dodecane.

REFERENCES
1. Fluorine: The First Hundred Years (1886 - 1986), Editor: Banks, R.E.,
Sharp, D.W.A., and Tatlow, J.C., Elsevier Sequoia, New York, NY,
(1986).
2. The Chemist's Companion, Editor: Gordon, A.J. and Ford, R.A., John
Wiley and Sons, New York, NY (1972).
3. Pauling, L, The Nature of the Chemical Bond, Cornell University Press,
Ithaca, NY (1960).
4. Bondi, A., J. Phys. Chem., 68 (1964), 441.
5. Smart, B.E. in The Chemistry of Functional Groups, Supplement D, John
Wiley and Sons, New York, NY (1983), 603.
6. Smart, B.E. in Molecular Structure and Energetics, Editors: Liebman, J.F.,
Greenburg, A., VCH Publishers, Inc., Deerfield Beach, FL, Vol. 3 (1986),
141.
7. Chambers, R.D., Fluorine in Organic Chemistry, John Wiley and Sons,
New York, NY (1973).
8. Banks, R.E., Organofluorine Chemicals and Their Industrial Applications,
Ellis Horwood Limited, Chichester, England (1979).
9. Random, L, Hehre, W.J., and Pople, J.A., J. Am. Chem. Soc., 93 (1971),
289.
10. Random, L, Hehre, W.J., and Pople, J.A., J. Am. Chem. Soc., 94 (1972),
2371.
11. Baird, N.C., Can. J. Chem., 61 (1983), 1567.
12. Bent, H.A., Chem. Rev., 61 (1961), 275.
13. Mellish, C.E. and Linnett, J.W., Trans. Far. Soc., 50(1954), 657.
14. Wiberg, K.B. and Rabien, P.R., J. Am. Chem. Soc., 7 75(1993), 614.
15. Bak, B., Kierkegaard, C., Pappas, J., and Skaarup, S., Acta Chem.
Scand., 27, No. 1 (1973), 363.
16. Bock, C.W., George, P., Mains, G.J., and Trachtman, M., J. Chem. Soc.,
Perkin Trans. II, 6(1979), 814.
17. Dolbier Jr., W.R. and Medinger, K.S., Tetrahedron, 38 [ 1982), 2415.
189

190
18. Bennett, G.M., Brooks, G.L., and Glasstone, S., J. Chem. Soc., Dalton
Trans., Part II (1935), 1821.
19. Streitwieser Jr., A. and Mares, F., J. Am. Chem. Soc., 90 (1968), 2444.
20. Bernardi, F., Mangini, A., Epiotis, N.D., Larson, J.R., and Shaik, S., J. Am.
Chem. Soc., 99 {1977), 7465.
21. Silverstein, R.M., Bassler, G.C., and Morrill, T.C., Spectrometric
Identification of Organic Compounds, John Wiley and Sons, New York,
NY .Edition 4 (1981).
22. Blint, R.J., McMahon, T.B., and Beauchamp, J.L., J. Am. Chem. Soc., 96
(1974), 1269.
23. Williamson, A.D., LeBreton, P.R., and Beauchamp, J.L., J. Am. Chem.
Soc., 98 (1976), 2705.
24. Prochaska, F.T. and Andrews, L., J. Am. Chem. Soc., 100 (1978), 2102.
25. Bernardi, F., Cherry, W., Shaik, S., and Epiotis, N.D., J. Am. Chem. Soc.,
100 (1978), 1352.
26. Rodriquez, C.F., Sirois, S., and Hopkinson, A.C., J. Org. Chem., 57
(1992), 4869.
27. Dolbier Jr., W.R., Piedrahita, C.A., and Al-Sader, B.H., Tetrahedron Lett.,
32 {1979), 2957.
28. Gordon, M.S., J. Am. Chem. Soc., 91 (1969), 3122.
29. Bunn, C.W. and Howells, E.R., Nature, 174 (1954), 549.
30. Forster, H. and Vógtle, F., Angew. Chem. Int. Edn. Engl., 16 (1977), 429.
31. Dawson, W.H., Hunter, D.H., and Willis, C.J., J. Chem. Soc., Chem.
Commun., 18 {1980), 874.
32. Baldwin, J.E., Andrist, A.H., and Pinschmidt Jr., R.K., Accts. Chem. Res., 5
(1972), 402.
33. Isaacs, N.S., Physical Organic Chemistry, Longman Scientific and
Technical, Essex, England (1987).
34. Woodward, R.B. and Hoffmann, R., The Conservation of Orbital
Symmetry, Verlag Chemie GmbH/Academic Press, Weinheim/Bergstr.
(1971).
35. Breulet, J. and Schaefer III, H.F., J. Am. Chem. Soc., 706(1984), 1221.
36. Branton, G.R., Frey, H.M., and Skinner, R.F., Trans. Far. Soc., 62(1966),
1546.
37. Winter, R.E.K., Tetrahedron Lett., 77(1965), 1207.

191
38. Curry, M.J. and Stevens, I.D.R., J. Chem. Soc., Perkin Trans. II, 10 {1980),
1391.
39. Rudolf, K., Spellmeyer, D.C., and Houk, K.N., J. Org. Chem., 52 (1987),
3708.
40. Houk, K.N., Spellmeyer, D.C., Jefford, C.W., Rlmbault, C.G., Wang, Y.,
and Miller, R.D., J. Org. Chem., 53(1988), 2125.
41. Pirkle, W.H. and McKendry, L.H., J. Am. Chem. Soc., 91 (1969), 1179.
42. Dolbler Jr., W.R., Koronlak, H., Burton, D.J., Helnze, P.L., Bailey, A.R.,
Shaw, G.S., and Hansen, S.W., J. Am. Chem. Soc., 109 (1987), 219.
43. Dolbier Jr., W.R., Gray, T.A., Celewicz, L, and Koroniak, H., J. Am. Chem.
Soc., 112{1990), 363.
44. Schlag, E.W. and Peatman, W.B., J. Am. Chem. Soc., 86(1964), 1676.
45. R. W. Carr, J. and Walters, W.D., J. Phys. Chem., 69 (1965), 1073.
46. Benson, S.W. and O'Neal, H.E., Kinetic Data on Gas Phase Unimolecular
Reactions, National Bureau of Standards, National Standard Reference
Data Series, Washington, DC (1970).
47. Greenburg, A. and Liebman, J.F., Strained Organic Molecules, Editor:
Wasserman, H.H., Academic Press, New York, NY, Vol. 38, Organic
Chemistry Series (1978).
48. Rondan, N.G. and Houk, K.N., J. Am. Chem. Soc., 107(1985), 2099.
49. Houk, K.N. in Strain and Its Implications in Organic Chemistry, Organic
Stress and Reactivity, Kluwer Academic, Dordrecht, Netherlands, Vol.
273, NATO ASI Series, Series C (1988), 25.
50. Jefford, C.W., Bernardinelle, G., Wang, Y., Spellmeyer, D.C., Buda, A.,
and Houk, K.N., J. Am. Chem. Soc., 114 (1992), 1157.
51. Dolbier Jr., W.R. and Phanstiel IV, O., Tetrahedron Lett., 29(1988), 53.
52. Marvell, E.N., Caple, G., Schatz, B., and Pippin, W., Tetrahedron, 29
(1973), 3781.
53. Marvell, E.N., Thermal Electrocyclic Reactions, Editor: Wasserman, H.H.,
Academic Press, New York, NY, Vol. 43, Organic Chemistry Series
(1980).
54. Gajewski, J.J., Hydrocarbon Thermal Isomerizations, Editor: Wasserman,
H.H., Academic Press, New York, NY, Vol. 5, Organic Chemistry Series
(1981).
55. Baumann, B.C. and Dreiding, A.S., Helv. Chim. Acta, 57(1974), 1872.
56. Von E. Doering, W. and Beasley, G.H., Tetrahedron, 29 (1973), 2231.

192
57. Von Eggers Doering, W., Roth, W.R., Boenke, M., Breuckmann, R.,
Ruhkamp, J., and Wortmann, O., Chem. Ber., 124 {1991), 1461.
58. Benson, S.W., Thermochemical Kinetics, John Wiley and Sons, New
York, NY (1976), 19.
59. NIST Standard Reference Database 25: The NIST Structures and
Properties Database and Estimation Program, Version 1.2, September,
1991, Software by S.E. Stein, J.M. Rukkers, and R.L. Brown, Distributed
by Standard Reference Data, National Institute of Standards and
Technology, Gaithersburg, MD, 20899
60. Dixon, D.A. and Smart, B.E. in Selective Fluorination in Organic and
Bioorganic Chemistry, American Chemical Society, Washington, DC,
ACS Symposium Series (1991), 18.
61. Wheland, G.W., Resonance in Organic Chemistry, John Wiley and Sons,
New York, NY (1955).
62. March, J., Advanced Organic Chemistry: Reactions, Mechanisms, and
Structure, John Wiley and Sons, New York, NY, Edition 3 (1985).
63. Dornfeld, C.A., Callen, J.E., and Coleman, G.H. in Organic Syntheses
Collective Volume 3, Editor: Horning, E.C., John Wiley and Sons, New
York, NY (1967), 134.
64. Callow, R.K. and Gulland, J.M., J. Chem. Soc., Part II (1929), 2424.
65. Barton, J.W., Grinham, A.R., and Witaker, K.E., J. Chem. Soc. (C), Part II
(1971), 1384.
66. Heinze, P.L. and Burton, D.J., J. Org. Chem., 53(1988), 2714.
67. Zuman, P. and Patel, R.C., Techniques In Organic Reaction Kinetics,
John Wiley and Sons, New York, NY (1984), 81.
68. Frost, A.A. and Pearson, R.G., Kinetics and Mechanism, John Wiley and
Sons, Inc., New York, NY (1961), 99.
69. Chvatal, Z., Brothankova, M., Hrabal, R., and Dedek, V., Czech. Patent
CS 241,840, Chem. Abstracts Volume 108, No. 133854.
70. Hansen, S.W., Exploratory Reactions with Perfluoroalkenyl
Organometallic Reagents, Ph.D. Dissertation, University of Iowa, Iowa
City, 1986.
71. Calvert, J.G. and Pitts Jr., J.N., Photochemistry, John Wiley and Sons,
New York, NY (1967), 240.
72. Pichko, V.A., Simkin, B.Y., and Minkin, V.I., J. Mol. Struct., 188 (1989),
129.

193
73. Gaasbeek, C.J., Hogeveen, H., and Volger, H.C., Rec. Trav. Chim., 91
(1972), 821.
74. Jacobs, H.J.C. and Havinga, E. in Advances in Photochemistry, John
Wiley and Sons, New York, NY, Vol. 11 (1979), 305.
75. Brouwer, A.M., Cornelisse, J., and Jacobs, H.J.C., J. of Photochemistry
and Photobiology A, 42 (1988), 117.
76. Brouwer, A.M., Cornelisse, J., and Jacobs, H.J.C., J. of Photochemistry
and Photobiology A, 42 (1988), 313.
77. Vroegop, P.J., Lugtenburg, J., and Havinga, E., Tetrahedron, 29 (1973),
1393.
78. Gielen, J.W.J., Jacobs, H.J.C., and Havinga, E., Tetrahedron Lett., 41
(1976), 3751.
79. Brundle, C.R. and Robin, M.B., J. Am. Chem. Soc., 92 (1970), 5550.
80. Stolevik, R. and Thingstad, O., J. Mol. Struct., 106 [ 1984), 333.
81. Belanger, G. and Sandorfy, C., Chem. Phys. Lett., 3(1969), 661.
82. Pottier, R.H., Semeluk, G.P., and Stevens, R.D.S., Spectroscopy Lett., 2
(1969), 369.
83. Modeled on a Silicon Graphics IRIS-4D Series Workstation running
Macro Model 3D, version 3.1X, November, 1990, from Columbia
University, Department of Chemistry, New York, NY, 10027.
84. Wynberg, H., De Groot, A., and Davies, D.W., Tetrahedron Lett., 17
(1963), 1083.
85. Dauben, W.G., Kellogg, M.S., Seeman, J.I., Vietmeyer, N.D., and
Wendschuh, P.H., Pure and Applied Chemistry, 33(1973), 197.
86. Jing, N. and Lemal, D., Thermal and Photochemistry of Fluorinated
Dienes and Trienes, Poster P23 presented at the Eleventh ACS Winter
Fluorine Conference, St. Petersburg, FL, January 25, 1993.
87. Feast, W.J., Musgrave, W.K.R., and Weston, R.G., J. Chem. Soc., Chem.
Commun., 20 (1970), 1337.
88. Feast, W.J. and Preston, W.E., Tetrahedron, 28 (1972), 2805.
89. Dolbier Jr., W.R. and Palmer, K.W., Tetrahedron Lett., 33 (1992), 1547.
90. Fiedorow, P., Koroniak, H., Dolbier Jr., W.R., and Palmer, K., J. Mol.
Struct., 273 {1992), 305.
91. Pomerantz, M. and Gruber, G.W., J. Am. Chem. Soc., 93(1971), 6615.
Pomerantz, M., J. Am. Chem. Soc., 89 (1967), 694.
92.

194
93. Meinwald, J. and Mazzocchi, P.H., J. Am. Chem. Soc., 89 {1967), 696.
94. Sukumaran, K.B. and Harvey, R.G., J. Org. Chem., 46(1981), 2740.
95. Padwa, A. and Clough, S., J. Am. Chem. Soc., 92 (1970), 5803.
96. Padwa, A., Brodsky, L, and Clough, S., J. Am. Chem. Soc., 94 (1972),
6767.
97. Courtot, P., Salaün, J., and Rumln, R., Tetrahedron Lett., 24 (1976), 2061.
98. Tanaka, K. and Fukui, K., Bull. Chem. Soc. Jpn., 51 (1978), 2209.
99. Dauben, W.G. and Kellogg, M.S., J. Am. Chem. Soc., 94 (1972), 8951.
100. Salem, L, Acc. Chem. Res., 12 {1979), 87.
101. Bonacic-Koutecky, V., J. Am. Chem. Soc., 100 {1978), 396.
102. Woning, J., Litjen, F.A.T., and Laarhoven, W.H., J. Org. Chem., 56(1991),
2427.
103. Schlag, E.W. and Kaiser Jr., E.W., J. Am. Chem. Soc., 67(1965), 1171.
104. Heimgartner, H., Hansen, H.J., and Schmid, H., Helv. Chim. Acta, 55
(1972), 1385.
105. Bellas, M., Bryce-Smith, B., Clarke, M.T., Gilbert, A., Klunkin, G.,
Krestonosich, S., Manning, C., and Wilson, S., J. Chem. Soc., Perkin
Trans. I, (1977), 2571.
106. Lamberts, J.J.M. and Laarhoven, W.H., J. Org. Chem., 49(1984), 100.
107. Karpov, V.M., Platanov, V.E., Stolyarova, T.A., and Yakobson, G.G.,
Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 10 (1976), 2295.
108. Karpov, V.M., Platanov, V.E., Stolyarova, T.A., and Yakobson, G.G.,
Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 7 (1981), 1586.
109. Feast, W.J. and Morland, J.B., J. Fluorine Chem., 78(1981), 57.
110. Feast, W.J., Hughes, R.R., and Musgrave, W.K.R., J. Fluorine Chem., 10
(1977), 585.
111. Feast, W.J. and Preston, W.E., J. Chem. Soc., Chem. Commun., 23
(1974), 985.
112. Marvell, E.N., Caple, G., Delphey, C., Platt, J., Polston, N., and Tashiro, J.,
Tetrahedron, 29 (1973), 3797.
113. Baldwin, J.E., Reddy, V.P., Hess Jr., B.A., and Schaad, L.J., J. Am. Chem.
Soc., 110 (1988), 8554.

195
114. Pichko, V.A., Simkin, B.Y., and Minkin, V.I., J. Org. Chem., 57 (1992),
7087.
115. Marvell, E.N., Tetrahedron, 29 {1973), 3791.
116. Komornicki, A. and Mclver Jr., J.W., J. Am. Chem. Soc., 98 {1974), 5798.
117. Baldwin, J.E., Reddy, V.P., Schaad, L.J., and Hess Jr., B.A., J. Am. Chem.
Soc., 110 {1988), 8555.
118. Houk, K.N., Gustafson, S.M., and Black, K.A., J. Am. Chem. Soc., 114
(1992), 8565.
119. Hurd, C.D. and Pollack, M.A., J. Org. Chem., 3(1939), 550.
120. Levy, H. and Cope, A.C., J. Am. Chem. Soc., 63(1944), 1684.
121. Brown, A., Dewar, M.J.S., and Schoeller, W., J. Am. Chem. Soc., 92
(1970), 5516.
122. Morokuma, K., Borden, W.T., and Hrovat, D.A., J. Am. Chem. Soc., 110
(1988), 4474.
123. Dupuis, M., Murray, C., and Davidson, E.R., J. Am. Chem. Soc., 113
(1991), 9756.
124. Dewar, M.J.S., Kirschner, S., Kollmar, H.W., and Wade, L.E., J. Am.
Chem. Soc., 96 {1974), 5242.
125. Share, P.E., Kompa, K.L., Peyerimhoff, S.D., and van Hemert, M.C.,
Chemical Physics, 120 (1988), 411.
126. Purrington, S.T. and Weeks, S.C., J. Fluorine Chem., 56 {1992), 165.
127. Andreev, V.G., Kolomiets, A.F., and Fokin, A.V., J. Fluorine Chem., 56
(1992), 259.
128. Von E. Doering, W., Toscano, V.G., and Beasley, G.H., Tetrahedron, 27
(1971), 5299.
129. Dolbier Jr., W.R., Alty, A.C., and Phanstiel IV, O., J. Am. Chem. Soc., 109
(1987), 3046.
130. Gajewski, J.J. and Jimenez, J.L., J. Am. Chem. Soc., 108 (1986), 468.
131. Von E. Doering, W. and Troise, C.A., J. Am. Chem. Soc., 107 (1985),
5739.
132. Shea, K.J. and Phillips, R.B., J. Am. Chem. Soc., 702(1980), 3156.
133. Hoffmann, H.M.R. and Rabe, J., J. Org. Chem., 50(1985), 3849.
134. Naae, D.G. and Burton, D.J., Synth.Commun., 3(1973), 197.

196
135. Furniss, B.S., Hannaford, A.J., Smith, P.W.G., and Tatchell, A.R., Vogel's
Textbook of Practical Organic Chemistry, Longman Scientific and
Technical, Essex, England, Edition 5 (1989).
136. Huet, F., Lechevallier, A., Pellet, M., and Conia, J.M., Synthesis, 1 (1978),
63.
137. Paul, H„ Chem. Ber., 93 (1960), 2395.
138. Hammond, G.S., J. Am. Chem. Soc., 77(1955), 334.
139. Farcasiu, D., J. Chem. Ed., 52 (1975), 76.
140. Dewar, M.J.S. and Jie, C., Acc. Chem. Res., 25 (1992), 537.
141. Dewar, M.J.S. and Healy, E.F., Chem. Phys. Lett., 141 (1987), 521.
142. Gajewski, J.J. and Conrad, N.D., J. Am. Chem. Soc., 101 (1979), 6693.
143. Roth, W.R., Lennartz, H.W., von E. Doering, W., Birladeanu, L., Guyton,
C.A., and Kitagawa, T., J. Am. Chem. Soc., 112{1990), 1722.
144. Nakai, T., Application of F-Enolate Chemistry: Claisen Rearrangement of
Fluorinated Enol Ether Systems, Presentation 13 at the Eleventh ACS
Winter Fluorine Conference, St. Petersburg, FL, January 25, 1993.
145. Lemal, D.M., Rearrangements of Fluorinated Dienes and Trienes in
Ground and Excited States, Presentation 14 at the Eleventh ACS Winter
Fluorine Conference, St. Petersburg, FL, January 25, 1993.
146. Heinze, P.L., Spawn, T.D., Burton, D.J., and Shin-Ya, S., J. Fluorine
Chem., 38(1988), 131.
147. Corey, E.J. and Schmidt, G., Tetrahedron. Lett., 5 (1979), 399.
Beier, R. and Mundy, B.P., Synth. Commun., 9(1979), 271.
148.

BIOGRAPHICAL SKETCH
Keith Winfield Palmer was born September 17, 1966, in Gainesville,
Florida. The first few years of his life were spent feeding marshmallows to the
alligators residing in Lake Alice. For fear of loss of limb, his parents decided a
move to New York was in order. Keith spent the next ten years of his life
growing up in rural Knox, New York, where he was "joined" by his three sisters.
In 1979, the family moved to Vancouver, Washington. Witnessing the eruption
of Mount St. Helens mere months after spending a vacation snowmobiling on
those very slopes was both awe-inspiring and eerie. In 1981, the family moved
to Midland, Michigan, for two years and then to Edwardsville, Illinois, in 1983.
Here Keith began his college career at Southern Illinois University at
Edwardsville with interests in biology and genetics. In 1985, the family moved
to Anoka, Minnesota, and Keith continued his education at the University of
Minnesota, Minneapolis. Chemistry became a fascination, and Keith spent his
last two years involved in undergraduate research in organic chemistry with
Professor Wayland E. Noland and received his B.S. in chemistry in July, 1988.
Keith returned to Gainesville in August, 1988, to begin graduate studies in
chemistry at the University of Florida. Running past Lake Alice one evening,
Keith came upon an old gator with a sweet tooth which hadn't been satisfied in
the past 20 years. Luckily, the gator did not hold a grudge and Keith decided to
stay in Gainesville and carry out graduate research with Professor William R.
Dolbier, Jr. Upon completion of his doctoral studies, Keith looks forward to
working for Du Pont Polymers in Wilmington, Delaware.
197

I certify that I have read this study and that in my opinion it conforms to
acceptable standards of scholarly presentation and is fully adequate, in scope
and quality, as a dissertation for the degree of Doctor of Philosophy.
Ugl I
William R. Dolbier, Jr., Chairman/
Professor of Chemistry V
I certify that I have read this study and that in my opinion it conforms to
acceptable standards of scholarly presentation and is fully adequate, in scope
and quality, as a dissertation for the degree of Doctor of Philosophy.
William M. Jone
Distinguished
Professor
I certify that I have read this study and that in my opinion it conforms to
acceptable standards of scholarly presentation and is fully adequate, in scope
and quality, as a dissertation for the degree of Doctor of Philosophy.
Kuk. -5 ,
Kirk S. Schanze
Associate Professor of Chemistry
I certify that I have read this study and that in my opinion it conforms to
acceptable standards of scholarly presentation and is fully adequate, in scope
and quality, as a dissertation for the degree of Doctor of Philosophy.
I certify that I have read this study and that in my opinion it conforms to
acceptable standards of scholarly presentation and is fully adequate, in scope
and quality, as a dissertation for the degree of Doctor of Philosophy.

This dissertation was submitted to the Graduate Faculty of the
Department of Chemistry in the College of Liberal Arts and Sciences and to the
Graduate School and was accepted as partial fulfillment of the requirements for
the degree of Doctor of Philosophy.
May, 1993
Dean, Graduate School

UNIVERSITY OF FLORIDA
3 1262 08556 9878

196
REFERENCE LIST
1. G. Tolg, Analyst, 112, 365 (1987).
2. J.R. Davis, Jr., A. Rohatgi, R.H. Hopkins, P.D. Blais, P. Rai-Choudhury, J.R.
McCormick, and H.C. Mollenkopf, IEEE Trans. Electron Devices, ED-27, 677
(1980).
3. T.Y. Kometani, Anal Chem., 49, 2289 (1982).
4. Y.H. Pao, R.N. Zitter, and J.E. Griffiths, J. Opt. Soc. Am., 56, 1133 (1966).
5. Y.H. Pao and J.E. Griffiths,/. Chem. Phys., 46, 1671 (1967).
6. C.A. Morton, Appl. Opt., 7, 1 (1968).
7. M.L. Franklin, G. Horlick, and H.V. Malmstadt, Anal Chem., 41, 2 (1969).
8. Commission Internationale de l’Eclairage, "International Lighting Vocabulary,"
Publ. No. 17, CIE, Paris 1970.
9. W. Herschel, Phil. Trans. Roy. Soc., 36, 421 (1800).
10. L.Nobili and M.Melloni, Ann. Chim. Phys., 48, 187 (1831).
11. S.P. Langley, Nature, 25, 14 (1881).
12. W.N. Hartley, Phil Trans., 175, 325 (1884).
13. H. Hertz, Ann. Phys., 31, 421 (1887).
14. H. Hertz, Ann. Phys., 31, 983 (1887).
15. H. Hertz, Ann. Phys., 36, 769 (1889).
16. A. Righi, Phil. Mag., 25, 314 (1888).
17. J. Elster and H. Geitel, Ann. Phys., 41, 161 (1890).
18. L.R. Roller, J. Opt. Soc. Am., 19, 135 (1929).
19. L.R. Roller, Phys. Rev., 36, 1639 (1930).
J.A. Rajchman and R.L. Snyder, Electronics, 13, 20 (1940).
20.

197
21. V.K. Zworykin and E.G. Ramberg, "Photoelectricity and Its Applications",
Wiley and Sons, New York 1949.
22. R.W. Wood, Philos. Mag., 10, 513 (1905).
23. J.V. Sullivan and A. Walsh, AppL Opt., 7, 1271 (1968).
24. O.I. Matveev, N.B. Zorov, and Yu. Ya. Kuzyakov, Talanta, 29, 907 (1980).
25. E.F. Zalewski, R.A. Keller and C.T. Apel, AppL Opt., 20, 1584 (1981).
26. M.A. Nippoldt and R.B. Green, AppL Opt., 20, 3206 (1981).
27. L.E. Salsedo-Torres, N.B. Zorov, Yu. Ya. Kuzyakov,/. AppL Spectrosc. USSR,
37, 488 (1982).
28. H. Rinneberg, J. Neukammer, and U. Majewski, Phys. Rev. Lett., 51, 1546
(1983).
29. B. Bolger, Lect. Notes Phys., 43, 460, NY (1975).
30. J.A. Gelbwachs, C.F. Klein, and J.E. Wessel, IEEE J. Quantum Electron., QE-
14, 77 (1978).
31. J.A. Gelbwachs, C.F. Klein, and J.E. Wessel, IEEE J. Quantum Electron., QE-
16, 137 (1980).
32. "Lasers in Chemical Analysis", G.M. Hieftje, J.C. Travis and F.E. Lytle, eds.
The Humana Press, Clifton, NJ (1981).
33. V.S. Letokhov, "Laser Photoionization Spectroscopy", Academic Press,
Orlando, FL (1987).
34. Ove Axner,"Laser Enhanced Ionization Spectroscopy", Chalmers Press,
Gotenberg, Holland (1987).
35. V.S. Letokhov in 'Tunable Lasers and Applications", T. Mooradian and P.
Stokseth, eds., Vol. 3, Springer-Veralg, Berlin (1976), p.122.
36. G.S. Hurst, M.H. Nayfeh and J.P. Young, AppL Phys. Lett. 30, 229 (1977).
37. G.S. Hurst, M.H. Nayfeh, and J.P. Young, Phys. Rev. A, 15, 2288 (1977).
G.I. Bekov, V.S. Letokhov, V.I. Mishin, and O.I. Matveev, Opt. Lett., 3, 159
(1978).
38.

198
39. 0.1. Matveev, N.B. Zorov, and Yu. Ya. Kuzyakov, J. AnaL Chem. USSR, 34,
654 (1979).
40. Yu. M. Milov, /. AppL Spectrosc. USSR, 44, 444 (1986).
41. O.I. Matveev, N.B. Zorov and Yu. Ya. Kuzyakov,/. AnaL Chem. USSR, 34,
846 (1979).
42. O.I. Matveev and V.A. Prybitkov,/. AppL Spectrosc. USSR, 46, 16 (1985).
43. T. Okada, H. Andou, Y. Moriyama and M. Maeda, Opt. Lett., 14(18), 987
(1989).
44. B.W. Smith, P.B. Farnsworth, J.D. Winefordner, and N. Omenetto, Opt. Lett.,
15, 823 (1990).
45. P.D. Foote, F.L. Mohler, Phys. Rev. 26, 195 (1925).
46. K.W. Meissner, W. Graffunder, Ann. d. Physik, 30, 109 (1927).
47. F.M. Penning, Physica, 8, 137 (1928).
48. R.B. Green, R.A. Keller, G.G. Luther, P.K. Schenck, J.C. Travis, AppL Phys.
Lett., 29, 727 (1976).
49. R.B. Green, R.A. Keller, G.G. Luther, P.K. Schenck, J.C. Travis, /. Am.
Chem. Soc., 98, 8517 (1976).
50. G.C. Turk, J.C. Travis, J.R. DeVoe, T.C. O’Haver, Anal. Chem., 50, 817
(1978).
51. R.B. Green, R.A. Keller, G.G. Luther, P.K. Schenck, J.C. Travis, IEEE J.
Quantum Electron., QE-13, 63 (1977).
52. D.S. Sing, P.K. Schenck, K.C. Smyth, J.C. Travis, AppL Opt., 16, 2617 (1977).
53. E. Nasser, "Fundamentals of Gaseous Ionization and Plasma Electronics",
Wiley Interscience, New York (1971).
54. B. Chapman, "Glow Discharge Processes: Sputtering and Plasma Etching",
John Wiley & Sons, New York (1980) p. 78.
55. M.G. Drouet, J.P. Novak, Phys. Lett., 34A, 199 (1979).
56. F.A. Sharpton, R.M. St. John, C.C. Lin, F.E. Fajen, Phys. Rev. A2, 1305 (1970)
and references therein.

199
57. D. Ton-That, M.R. Flannery ,/Viys. Rev., A15, 517 (1977) and references
therein.
58. E.W. McDaniel, "Collision phenomena in ionized gases", Wiley, New York ,
1964 p.35.
59. A.D. MacDonald, "Microwave breakdown in gases", Wiley, New York, (1966)
p.24.
60. N.H. Farhat, Proc. IEEE, 62, (1974) 279.
61. K.C. Smyth, R.A. Keller, F.F. Crim, Chem. Phys. Lett., 55, 473 (1978).
62. K.R. Hess, W.W. Harrisson, AnaL Chem., 60, 691 (1988).
63. E.M. van Veldhuizen, F.J. de Hoog, D.C. Schram, J. Appl Phys., 56, 2047
(1984).
64. E. Miron, I. Smilanski, J. Liran, S. Lavi, G. Erez, IEEE J. Quantum Electron.,
QE-15, 194 (1979).
65. A.J. Palmer, J. Wm. McGowan, J. Appl. Phys., 43, 4084 (1972).
66. D.A. Haner, C.R. Webster, P.H. Flamant, I.S. McDermid, Chem. Phys. Lett.,
96, 302 (1983).
67. C.T. Rettner, C.R. Webster, R.N. Zare, J. Phys. Chem., 85, 1105 (1981).
68. S. Fujimaki, Y. Adachi, C. Hirose, Appl Spec., 41, 567 (1987).
69. P.A. Fleitz, CJ. Seliskar, H.B. Fannin, Appl Spec., 41, 1405 (1987).
70. B.R. Reddy, P. Venkateswarlu, M.C. George, Opt. Comm., 75, 267 (1989).
71. R.A. Keller, E.F. Zalewski, Appl. Opt., 19, 3301 (1980).
72. G. Erez, S. Lavi, E. Miron, IEEE J. Quantum Electron., QE-15, 1328 (1979).
73. A. Ben-Amar, G. Erez, and R. Schuker, J. Appl. Phys., 54, 3688 (1983).
74. M. Broglia, F. Cantoni, A. Montone, P. Zampetti, Phys. Rev. A, 36, 705
(1987).
75. R.A. Keller, B.E. Warner, E.F. Zalewski, P.Dyer, R. Engleman, Jr., and B.A.
Palmer, J. Phys. (Paris), CJ 23 (1983).
76. R.A. Keller and E.F. Zalewski, Appl. Opt., 21, 3392 (1982).

200
77. K.C. Smyth, P.K. Schenck, Chem. Phys. Lett., 55, 466 (1978).
78. G.S. Hurst, M.G. Payne, S.D. Kramer, and J.P. Young, Rev. Mod. Phys. 51,
767 (1979).
79. B.B. Rossi and H.H. Staub, Ionization Chambers and Counters, McGraw-Hill,
New York, 1949 pp.20-71.
80. C.R. Vidal, Opt. Lett., 5, 158 (1980).
81. R.Engleman, Jr., R.A. Keller, Opt. Lett., 5, 465 (1980).
82. H.O. Behrens, G.H. Guthohrlein, A. Kasper, /. Phys. (Paris), Cl 239 (1983).
83. G.C. Turk, J.R. DeVoe, and J.C. Travis, AnaL Chem., 54, 643 (1982).
84. N. Omenetto, B.W. Smith, and L.P. Hart, Fresenius Z. AnaL Chem., 324, 683
(1986).
85. N. Omenetto, J.D. Winefordner, Prog. AnaL At. Spectrosc., 2, 1 (1979).
86. R.A. Keller, R. Engleman, Jr. E.F. Zalewski, J. Opt. Soc. Am., 69, 738 (1979).
87. F.A. Sharpton, R.M. St. John, C.C. Lin, F.E. Fajen, Phys. Rev., A2, 1305
(1970) and references therein.
88. C. Th. J. Alkemade, Spectrochim. Acta, 40B, 1831 (1985).
89. National Bureau of Standards (now NIST), "Atomic Energy Levels", Circular
467, Vol. I (1948).
90. F.A. Moscatelli, Am. J. Phys., 54, 52 (1986).
91. F.M. Curran, K.C. Lin, G.E. Leroi, P.M. Hunt, and S.R. Crouch, AnaL Chem.,
55, 2382 (1983).
92. W. Heitler, "The Quantum Theory of Radiation", 3rd ed., Clarendon Press,
Oxford (1970); pp. 204-9.
93. M. Stobbe, Ann. Phys. (Paris), 7, 661 (1930).
94. M. Aymar, E. Luc-Koenig, F.C. Farnoux, J. Phys. B, 9, 4279 (1976).
95. A. Msezane ans S.T. Manson, Phys. Rev. Lett., 35, 364 (1975).
R.C. Hilborn, Am. J. Phys., 50 982 (1982).
96.

201
97. E. Voigtman, Appl Spec., Feb. (1991) in press.
98. E. Voigtman and J.D. Winefordner, Prog. AnaL Atom. Spectrosc., 9, 7 (1986).
99. J.E. Lawler, A.I. Ferguson, J.E.M. Goldsmith, D.H. Jackson, and A.L.
Schawlow, Phys. Rev. Lett., 42, 1046 (1979).

BIOGRAPHICAL SKETCH
Giuseppe Antonio Petrucci was born in Faicchio (BN), Italy, on October 11,
1963. In June, 1981, he graduated from Notre Dame High School in West Haven,
Ct. In May, 1985, he graduated from the University of Toronto in Ontario, Canada,
with a Bachelor of Science degree, Specialist in Chemistry. In June, 1987, he
received a Master of Science degree in analytical chemistry from the University of
Toronto. In August, 1987, he entered the Graduate School at the University of
Florida in Gainesville, Florida.
He is a member of the American Academy for the Advancement of Science,
the American Chemical Society and the Society for Applied Spectroscopy.
202

I certify that I have read this study and that in my opinion it conforms to
acceptable standards of scholarly presentation and is fully adequate, in scope and
quality, as a dissertation for the degree of Doctor of Philosophy.
James D. Winefordner, Chairman
Graduate Research Professor of Chemistry
I certify that I have read this study and that in my opinion it conforms to
acceptable standards of scholarly presentation and is fully adequate, in scope and
quality, as a dissertation for the degree of Doctor of Philosophy.
x Richard A. Yost
Professor of Chemistry
I certify that I have read this study and that in my opinion it conforms to
acceptable standards of scholarly presentation and is fully adequate, in scope and
quality, as a dissertation for the degree of Doctor of Philosophy.
Anna Brajter-Toth
Associate Professor of Chemistry
I certify that I have read this study and that in my opinion it conforms to
acceptable standards of scholarly presentation and is fully adequate, in scope and
quality, as a dissertation for the degree of Doctor of Philosophy.
Ik
A VU. w (,|Q
Vaneica Young/
Associate Professor of Chemistry
I certify that 1 have read this study and that in my opinion it conforms to
acceptable standards of scholarly presentation and is fully adequate, in scope and
quality, as a dissertation for the degree of Doctor of Philosophy.
Eric Allen
Professor of Environmental
Engineering Sciences

This dissertation was submitted to the Graduate Faculty in the College of
Liberal Arts and Sciences and to the Graduate School and was accepted as partial
fulfillment of the requirements for the degree of Doctor of Philosophy.
December, 1990
Dean, Graduate School

,T,iy£^!71 0F FLORIDA
3 4 ¿i a x ATri1"11,11 ""i mi I
1262 08556 9506



0F florida
3 4 A J 1L 11,1111,11 *
1262 08556 9506