Citation
(4,5-c) Furotropylidene--a ten-pi-electron carbene

Material Information

Title:
(4,5-c) Furotropylidene--a ten-pi-electron carbene
Added title page title:
Furotropylidene-a ten-pi-electron carbene
Creator:
Ledford, Thomas Howard, 1942-
Publication Date:
Language:
English
Physical Description:
vi, 73 leaves. : illus. ; 28 cm.

Subjects

Subjects / Keywords:
Alkenes ( jstor )
Carbenes ( jstor )
Furans ( jstor )
Hydrogen ( jstor )
Magnetic resonance spectroscopy ( jstor )
Magnetic spectroscopy ( jstor )
Photolysis ( jstor )
Proton magnetic resonance ( jstor )
Signals ( jstor )
Thermal decomposition ( jstor )
Carbenes (Methylene compounds) ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
City of Maitland ( local )
Genre:
bibliography ( marcgt )
non-fiction ( marcgt )

Notes

Thesis:
Thesis -- University of Florida.
Bibliography:
Bibliography: leaves 70-72.
General Note:
Typescript.
General Note:
Vita.

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:
022776604 ( ALEPH )
14081119 ( OCLC )
857367333 ( OCLC )
AA00004930 ( sobekcm )

Downloads

This item has the following downloads:

00045cfurotropylide00ledf.pdf

00045cfurotropylide00ledf_0024.txt

00045cfurotropylide00ledf_0026.txt

00045cfurotropylide00ledf_0078.txt

00045cfurotropylide00ledf_0008.txt

00045cfurotropylide00ledf_0064.txt

00045cfurotropylide00ledf_0054.txt

00045cfurotropylide00ledf_0070.txt

00045cfurotropylide00ledf_0081.txt

00045cfurotropylide00ledf_0025.txt

00045cfurotropylide00ledf_0001.txt

00045cfurotropylide00ledf_0068.txt

00045cfurotropylide00ledf_0042.txt

00045cfurotropylide00ledf_0027.txt

00045cfurotropylide00ledf_0002.txt

00045cfurotropylide00ledf_0011.txt

00045cfurotropylide00ledf_0019.txt

00045cfurotropylide00ledf_0003.txt

00045cfurotropylide00ledf_0050.txt

00045cfurotropylide00ledf_0016.txt

00045cfurotropylide00ledf_0080.txt

00045cfurotropylide00ledf_0033.txt

00045cfurotropylide00ledf_0040.txt

00045cfurotropylide00ledf_0055.txt

00045cfurotropylide00ledf_0017.txt

AA00004930_00001.pdf

00045cfurotropylide00ledf_0071.txt

00045cfurotropylide00ledf_0032.txt

00045cfurotropylide00ledf_0041.txt

00045cfurotropylide00ledf_0005.txt

00045cfurotropylide00ledf_0006.txt

EVFJDNEI7_DDPKXH_xml.txt

00045cfurotropylide00ledf_0030.txt

00045cfurotropylide00ledf_0075.txt

00045cfurotropylide00ledf_0074.txt

00045cfurotropylide00ledf_0056.txt

AA00004930_00001_pdf.txt

00045cfurotropylide00ledf_0007.txt

00045cfurotropylide00ledf_0043.txt

00045cfurotropylide00ledf_0051.txt

00045cfurotropylide00ledf_0015.txt

00045cfurotropylide00ledf_0031.txt

00045cfurotropylide00ledf_0044.txt

00045cfurotropylide00ledf_0036.txt

00045cfurotropylide00ledf_0065.txt

00045cfurotropylide00ledf_0072.txt

00045cfurotropylide00ledf_0073.txt

00045cfurotropylide00ledf_0060.txt

00045cfurotropylide00ledf_pdf.txt

00045cfurotropylide00ledf_0014.txt

00045cfurotropylide00ledf_0085.txt

00045cfurotropylide00ledf_0063.txt

00045cfurotropylide00ledf_0045.txt

00045cfurotropylide00ledf_0066.txt

00045cfurotropylide00ledf_0038.txt

00045cfurotropylide00ledf_0083.txt

00045cfurotropylide00ledf_0029.txt

00045cfurotropylide00ledf_0082.txt

00045cfurotropylide00ledf_0059.txt

00045cfurotropylide00ledf_0034.txt

00045cfurotropylide00ledf_0062.txt

00045cfurotropylide00ledf_0076.txt

00045cfurotropylide00ledf_0035.txt

00045cfurotropylide00ledf_0046.txt

00045cfurotropylide00ledf_0061.txt

00045cfurotropylide00ledf_0047.txt

00045cfurotropylide00ledf_0048.txt

00045cfurotropylide00ledf_0049.txt

00045cfurotropylide00ledf_0086.txt

00045cfurotropylide00ledf_0039.txt

00045cfurotropylide00ledf_0067.txt

00045cfurotropylide00ledf_0023.txt

00045cfurotropylide00ledf_0010.txt

00045cfurotropylide00ledf_0053.txt

00045cfurotropylide00ledf_0004.txt

00045cfurotropylide00ledf_0028.txt

00045cfurotropylide00ledf_0057.txt

00045cfurotropylide00ledf_0052.txt

00045cfurotropylide00ledf_0012.txt

00045cfurotropylide00ledf_0009.txt

00045cfurotropylide00ledf_0022.txt

00045cfurotropylide00ledf_0018.txt

00045cfurotropylide00ledf_0069.txt

00045cfurotropylide00ledf_0020.txt

00045cfurotropylide00ledf_0013.txt

00045cfurotropylide00ledf_0084.txt

00045cfurotropylide00ledf_0037.txt

00045cfurotropylide00ledf_0079.txt

00045cfurotropylide00ledf_0021.txt

00045cfurotropylide00ledf_0077.txt

00045cfurotropylide00ledf_0058.txt


Full Text


(4, 5-c)FUROTROPY LIDENE -
A TEN-PI-ELECTRON CARBENE
By
THOMAS HOWARD LEDFORD
A DISSERTATION PRESENTED TO THE GRADUATE COUNCIL OF
THE UNIVERSITY OF FLORIDA
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE
DEGREE OF DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
1973


DEDICATION
This work is dedicated to the past for my parents, to the
present for my wife, and to the future for my children.


ACKNOWLEDGMENT
I would like to express my sincere gratitude to Professor W. M.
Jones and all the members of my supervisory committee for their
scholarly guidance during the preparation of this work. A special
debt is owed to Dr. R. W. King of the University of Florida who
good-naturedly suffered all of my questions about molecular spec
troscopy. It is such men as these who keep teaching in its honored
place among the professions.
The financial aid of the Woodrow Wilson National Fellowship
Foundation, the Graduate School of the University of Florida, and
the National Science Foundation made this work possible.
in


PREFACE
"Tom he said . the trouble about arguments
is, they ain't nothing but theories, after all, and
theories don't prove nothing, they only give you a
place to rest on, a spell, when you are tuckered out
butting around and around trying to find out something
there ain't no way to find out. "
Huckleberry Finn in
"Tom Sawyer Abroad"
by Mark Twain


TABLE OF CONTENTS
ACKNOWLEDGMENT iii
PREFACE iv
ABSTRACT vi
INTRODUCTION 1
RESULTS 11
DISCUSSION 45
EXPERIMENTAL 57
LIST OF REFERENCES 70
BIOGRAPHICAL SKETCH 73
v


Abstract of Dissertation Presented to the
Graduate Council of the University of Florida in Partial
Fulfillment of the Requirements for the Degree of Doctor of Philosophy
(4, 5-c)FUROTROPYLIDENE --
A TEN-PI-ELECTRON CARBENE
By
Thomas Howard Ledford
August, 1973
Chairman: Professor William M. Jones, Department of Chemistry
(4, 5-c)Furotropylidene has the required structure and the required
number of pi-electrons to belong to the class of aromatic carbenes, a
group of carbenes that show predominantly singlet behavior and react
preferentially with electron-poor olefins. Contrary to this expectation,
(4, 5-c) f urotropylidene appears to behave as a triplet above about
40 C. and adds to ordinary olefins. It also has the unusual property
of undergoing the first step of carbene-carbene rearrangement at low
temperatures. The second step of rearrangement, opening of the
intermediate cyclopropene to the rearranged carbene, is not detected.
Possible rearrangement, though not disproved, is shown not to be the
predominant reaction path such as is seen in certain slightly destabi
lized aromatic carbenes.
vi


INTRODUCTION
It has been established that incorporating a vacant orbital of a
carbene into a ring containing conjugated double bonds can, when the
resulting system obeys the Huckel "4n + 2" rule, result in establish
ment of so-called "aromatic" carbene systems that have unusual
1,2, 3,4
reactivity patterns. These conditions are satisfied when the
number of double bonds conjugated with the vacant orbital of the
carbene is an odd number. (See Figure 1.)
Examples of such aromatic carbenes include the 2-pi electron
4
system diphenylcyclopropenylidene (1), the 6-pi-electron system,
1, 2
cycloheptatrienylidene (2), and the 10-pi-electron carbene derived
5
from the 1,6 -methanof 11) annulene ring system (3). (See Figure 2. )
1


2
Aromatic carbenes display behavior patterns that are signifi
cantly different from those shown by other carbenes. The delocali
zation of charge density from the conjugated double bond system into
the vacant orbital of an aromatic carbene can be expected to increase
the nucleophilicity of the carbene. Also the carbene orbitals can be
expected to split into two different energy levels, affording the possi
bility of a stabilized singlet state. (See Figure 3.)
(Figure 3)
Perhaps the most well known of these aromatic carbenes is
1 2
cycloheptatrienylidene (2). This carbene shows the properties one
might expect of a stabilized singlet with increased nucleophilic
character. It prefers to react with electron-deficient, rather than
electron-rich, olefins. For example, in a Hammett study with sub
stituted styrenes, cycloheptatrienylidene showed a reaction rate con
stant of +1. 05. This compares with reaction rate constants of -0.619
7, 8
for dichlorocarbene and -0. 38 for carbethoxycarbene. Not only is
the sign of the reaction rate constant significant, but there is also
significance in its larger absolute value, an indication that cyclohepta
trienylidene is more discriminating than other carbenes; i, e. more
stable. Consistent with the hypothesized stabilization of its singlet
state, cycloheptatrienylidene reacts with acceptor olefins to form
9
cyclopropanes in which the olefin stereochemistry is preserved.
(Figure 4.)


3
(Figure 4)
Among the substituted cycloheptatrienylidenes that have been
prepared and studied, the following annelated compounds have shown
some interesting new departures in cycloheptatrienylidene chemistry.
(Figure 5.)
Carbenes (4) and (5) have been generated under conditions that
allow observation of their low-temperature esr spectra. Both have
triplet ground states and react with electron-rich olefins such as 2-
butene to form cyclopropane adducts. ^ Evidently both (4) and
(5) behave much like diphenylcarbene. Annelation has, in these two
cases, changed the cycloheptatrienylidene so significantly that a
singlet ground state is impossible. Carbenes (6), (7), and (8) show
even more dramatic effects of annelation upon cycloheptatrienylidene.
All three of these undergo carbene-carbene rearrangement at low to
13 14 15
moderate temperatures according to the following equations.
(Figure 6.)
The ground states for these carbenes are unknown, but it is
assumed that the rearrangements, at least, proceed through a singlet
16, 17
state. The nature of the intermediate or transition state leading
to this kind of carbene-carbene rearrangement has been somewhat
controversial. There is recent convincing evidence that such re
arrangements proceed via a cyclopropene intermediate such as shown


4
(Figure 5)


5
(Figure 6)


6
15
m Figure 7. In this example, the intermediate cyclopropene (9)
appears to have been trapped by a Diels-Alder reaction with each of
several dienes. The intermediate (9) has also been approached from
another source as shown in Figure 7.
18
(Figure 7)
Monoannelation is said to substantially decrease the stability of
19
the tropyl cation. Since carbene stability is thought to parallel
cation stability, and since monoannelation should have little effect
upon the stability of the intermediate cyclopropene, monoannelation is


7
thought to cause a destabilization of the carbene relative to the cyclo-
propene intermediate, thus increasing the probability of rearrange-
20
ment. Following this line of reasoning further, one could expect to
anticipate rearrangements in other carbenes by an analysis of aroma
ticity and cation stability relative to the tropyl system.
The subject of this study is the carbene (4, 5~c)furotropylidene
(11) shown in Figure 8. This carbene should be expected to show at
least some aromatic character, since it does satisfy the Huckel 4n + 2
(Figure 8)
rule (n = 2), having 10 pi-electrons. The structure is not actually a
simple annelated cycloheptatrienylidene in one sense, because it lacks
a double bond analogous to the one between positions 4 and 5 in cyclo
heptatrienylidene.
The question of whether aromatic character can be expected in
carbene (11) cannot be answered a priori. In fact, the whole concept
2 122
of aromaticity in troponoid ketones has been attacked by Bertelli;
but the concept seems so useful in explaining the behavior of troponoid-
derived carbenes that its continued use seems justified for the time
being. The following analysis, though it is mitigated by Bertelli's
argument, has been used to arrive at estimates of relative aroma-
23
ticities in the following series of ketones.
As delocalization of electrons increases in the ring systems, the
bond order of the exocyclic C = 0 groups will decrease. This will


8
(13) (14)
(Figure 9)
parallel the increasing contribution of the dipolar form of the
*f -
carbonyl group C-O, thus paralleling the ability of the ring system to
stabilize positive charge at the carbonyl carbon atom. This trend
should be in the same direction as cation stability, thus in the same
direction as carbene stability.
A measure of C = 0 bond order can be obtained by a study of the
carbonyl absorption positions in the infrared spectra of the ketones in
this series. It has been shown that, for geometrically similarly
disposed C = 0 groups, there is good correlation between the frequency
of absorption and the calculated bond order; i. e. as bond order of the
carbonyl group increases, the higher will be the absorption frequency.
As the aromaticity in the series of ketones increases, the bond order
of the C = 0 groups should decrease, showing a lower infrared absorp
tion frequency. The ketone (4, 5-c)furotropone (14), having a C = 0
absorption at 1599 cm. is therefore less aromatic than benztropone
(13), having its C = 0 absorption at 1590 cm. ^ In turn, benztropone
(13) is less aromatic than tropone, since the carbonyl frequency of


9
tropone (12) is 1582 cm. By this criterion furotropone (14) has
more delocalization than a cross-conjugated cycloheptadienone because
all its bands appear at lower frequencies than the carbonyl band of
, 1 23
the dienone (15) shown in Figure 10 (ca. 1635 cm. ).
(Figure 10)
The inference that furotropylidene (11) should have less
aromatic character than cycloheptatrienylidene (2) suggests that
furotropylidene, like other slightly destabilized aromatic carbenes (6),
(7), and (8), might be expected to undergo carbene-carbene rearrange
ment. The examination of a hypothetical reaction pathway of a hypo
thetical reaction pathway (Figure 11) suggests a possible complication.
Although the carbene (11) should be destabilized relative to the
(11)
(Figure 11)
cyclopropene (16), the product (17) from opening the cyclopropene
should give some caution. The rearranged carbene (17) has a carbene
center attached to an isober *an skeleton. Although isobenzofuran
is a 10-pi system, it appare does not show the stabilization


10
associated with other aromatic systems. The parent hydrocarbon,
24
isobenzofuran, has been prepared for the first time only recently.
It polymerizes readily in solution at moderate temperatures. The
reaction pathway in Figure 11 suggests that, for the first time, one of
the destabilized, partially aromatic carbenes might be headed into a
rearrangement pathway in which product stability is quite low. This
is in contrast to the highly stabilized aromatic products of carbene
rearrangements presented on page 4. The effect of this point will
become apparent as the results of this study are presented.


RESULTS
The carbene (4, 5-c)furotropylidene (11) was prepared in all
cases either by pyrolysis or photolysis of the sodium salt of the
tosylhydrazone of (4, 5-c)furotropone (18). The synthetic scheme for

(18)
(11)
(Figure 12)
4- N2
producing the required ketone was originally developed by Cook and
23
Forbes. Some modifications of their procedures were used in pre
paring the ketone for this study. For example, commercially avail
able furan-3, 4-dicarboxylic acid was converted to its diacyl
(Figure 13)
chloride (19) by the action of thionyl chloride in the presence of a
catalytic amount of N, N-dimethylformamide. The acid chloride (19)
was never purified and characterized. Its presence was inferred from


12
its reaction with methanol to afford a quantitative yield of the known
dimethyl ester (20), previously characterized and reported by Cook
23
and Forbes. Using the procedures of Cook and Forbes, the reduc
tion of the dimethyl ester was carried out using lithium aluminum
hydride, but the 76 percent yields reportedly attainable did not result.
Direct reduction of the crude diacyl chloride (19) did afford the di
alcohol (21) in yields of about 7 0 percent. The di-alcohol was treated
o
/^x:oc|
LIAIH.
!4^
o
COCI
(19)
(21)
'CH2OH
*ch2oh
(Figure 14)
with activated managanese dioxide to effect oxidation of one of the
alcohol groups to the aldehyde stage. Again the yields reported in
23
the literature did not result. The reaction usually produced only
about 50 percent of the maximum amount of 3-hydroxymethyl-furan-
4-carboxaldehyde (22), accompanied by about half of the unreacted
di-alcohol (determined by proton resonance spectroscopy). This
situation was made usable by the fact that lead tetra-acetate oxidation
of this crude mixture of di-alcohol and mono-aldehyde afforded the
(21) + MnOz
di-aldehyde (23) in
yields of about 24 percent based on di-alcohol.


13
The 3, 4-furandicarboxaldehyde (23) was condensed with acetone
using the procedure of Cook and Forbes to give exactly the reported
23
yield of 38 percent.
(Figure 16)
Conversion of furotropone into its tosylhydrazone was best
carried out by treatment of the ketone (14) with tosylhydrazine in
tetrahydrofuran containing a trace of anhydrous phosphoric acid. The
reaction worked best when the reactants were merely allowed to stand
together at room temperature for five to seven days. This procedure
gave the tosylhydrazone (24) in 65-70 percent conversion.
=D
(Figure 17)
f
A solution of the tosylhydrazone in tetrahydrofuran was treated
with sodium hydride to produce the sodium salt of the tosylhydrazone
(18). The weight of the sodium salt produced suggests from the
stoichiometry of the reaction that one mole of tetrahydrofuran is
included in the salt as bound solvent. All yields in reactions of this
sodium salt have been adjusted to reflect this effect.


14
/
NcP

s^W Ar
N
N
(Figure 18)
(18)
II
Thermal decomposition of the sodium salt of (4, 5-c)furotropone
tosylhydrazone (18) in the presence of benzene at 188 C. led to
formation of the formal C-H insertion product (25) in 43 percent
isolated yield. The structure of (25) was assigned primarily on the
basis of its spectral properties. At tau 2.71 and 2. 72 there were two
singlets, assigned to the furan hydrogens and to the benzene hydro
gens, respectively. The total of both peaks was seven hydrogens.
The vinyl hydrogens (Ha) appeared at 3. 5-3. 9 tau as a doublet, split
by 11.5 Hz. through coupling to (Hb). Each peak of this doublet
showed a slight splitting (ca. 1 Hz. ) attributable to allylic coupling
to the tertiary hydrogen (Hc). The vinyl hydrogens (Hb) appeared as
a doublet of doublets at tau 4. 33-4. 6. In this pattern the coupling
(11.5 Hz. ) between vinylic protons and the coupling (5-5. 3 Hz. )
between (H^) and (Hc) were both easily discernible. The tertiary
hydrogen (H ) appeared at tau 5. 64. It was primarily a triplet pattern
showing some superimposed allylic splitting. The infrared spectrum
indicated the monosubstituted benzene structure by its absorptions at
762 cm. ~ and 700 cm. *


15
(25)
(Figure 19)


16
The proton magnetic resonance spectrum of the crude reaction
mixture showed only the benzene C-H insertion product (25). No
evidence of a cycloheptatriene structure was present. Careful
examination of the reaction mixture by analytical thin-layer chroma
tography failed to show any biphenyl in the sample.
In a competition reaction allowing the carbene equal access to
benzene and d^-benzene, essentially equal amounts of deuterated and
non-deuterated products were produced as determined by both mass
spectroscopy and by 100 MHz. proton magnetic resonance.
An effort to prepare the product of C-H insertion into cyclo
hexane failed because of low yields. The carbene (11) undergoes
reaction with olefins in dioxane solution without taking dioxane into the
reaction mixture. These observations suggest that the benzene C-H
insertion reaction probably does not result from direct insertion, but
through an intermediate that will be discussed in a later section of
this report.
Attempted addition of the carbene (11) to the double bond in
cyclohexene resulted in a mixture that could not be separated cleanly
enough to allow characterization of any of the products. The proton
magnetic resonance spectrum of the crude product did suggest that
some addition to the double bond had occurred., The presence of other
products in the reaction mixture suggests that (4, 5-c)furotropylidene
is not incapable of C-H insertion, but one is left to speculate about
whether the products arise by direct reaction of the carbene or by
secondary processes.
Decomposition of the tosylhydrazone salt in a refluxing solution
of styrene in dioxane (b. p. 101 C. ) was successful in producing a


17
phenylcyclopropane (26) that could be separated and characterized.
Yields as high as 50 percent were produced in solutions that were
quite dilute (1. 5-3 percent styrene). Little, if any, dioxane was
attacked by the carbene. The major side-reaction was production of
considerable amounts of polystyrene. The 100 MHz. magnetic
resonance spectrum of the phenylcyclopropane (26) showed a sharp
singlet at tau 2. 86 with a correct integral for the five phenyl hydrogens.
There were two small singlets (total 2H for both) representing the
furan hydrogens, nonequivalent in this molecule, at tau 2. 96 and
3.01. The vinylic hydrogens (Ha) and (Ha>) appeared as two doublets
in the region from 4. 0 to 4. 33 tau. Each of the doublets was split by
12 Hz. through coupling to the hydrogens (H^) and (H^(). The value of
this coupling between cis olefinic hydrogens suggests that they are
connected to a seven-membered ring. The hydrogens (H^) and
(H^i) appear as two doublets at 5. 25 to 5. 95 tau, again spaced by
about 12 Hz. ; but each peak in these doublets is split very slightly
again (about 2 Hz. ), suggesting coupling across the ring between (H^)
and (H^,), This coupling is to be expected because these hydrogens
(non-equivalent because of the phenyl group) are situated for W-form
coupling. Although the furan hydrogens are also situated for W-form
coupling, and their chemical shift difference is ca. 12 Hz. the cou
pling between them is only barely discernible. It is interesting to
note that the facing pairs of hydrogens on the seven-membered ring
and in the furan system show decreasing chemical shift differences
with increasing distance from the symmetry-disturbing phenyl group.
The cyclopropyl hydrogens in the phenylcyclopropane (26) present the
expected ABX pattern. The (Hc) hydrogen (X) appears in the 7. 53-7. 85


18
PROTON MAGNETIC RESONANCE SPECTRUM OF PRODUCT
(26)
(Figure 20)


19
T
*1 1" 'I -f-
PROTON MAGNETIC RESONANCE SPECTRUM OF PRODUCT
(26)
ENLARGED VIEWS OF ABX PORTION
T
(Figure 21)


20
tau area as two doublets that show overlap between the two central
peaks. The geminal cyclopropyl hydrogens (AB pair) appear as the
expected pair of overlapping quartets in the region 8.7-9. 0 tau. The
spacing between the midpoints of the two quartets (1/2 abs. value of
+ Jgy) allows easy calculation of the predicted spacing between
lines 9 and 12 in the X portion of the spectrum. The predicted
spacing between lines 9 and 12 (15. 6 Hz. ) was observed and permitted
assignment of lines 9 and 12 as the two outside lines in the X portion
2 6
of the spectrum. The value of JAB = 5. 4 Hz. was directly
measurable from the spectrum.
The infrared spectrum of (26) shows absorptions near 700 cm.-^
and 750 cm. consistent with the mono-substituted benzene
structure. Absorptions at 860 cm. and 1028 cm. offer confirma
tory evidence of the cyclopropane ring indicated by the absorption at
-1 27
3060 cm.
Pyrolytic decomposition of the tosylhydrazone salt (17) in the
presence of 1-butene gave the expected ethylcyclopropane (27) in
about 50 percent isolated yield. The cyclopropane was accompanied
by three minor by-products that were never identified. The proton
magnetic resonance spectrum of (27) showed a two-hydrogen singlet at
2. 95 tau for the furan hydrogens. The vinylic protons (Ha) and (Hai)
that showed a pair of doublets in the phenylcyclopropane (26) appeared
in this ethylcyclopropane as an overlapped pair of doublets split by
11.5 Hz. at tau 3. 87-4. 3. The other pair of vinylic hydrogens (H^)
and (H^i) appeared as a pair of separated doublets at 5. 25-5. 8 tau
showing the same W-form coupling observed in the phenylcyclopropane
(26). It is interesting to observe the smaller symmetry disturbance


21
PROTON MAGNETIC RESONANCE SPECTRUM OF PRODUCT (27)
(18)
/
H
CHpCH^
(Figure 22)


22
produced by the ethyl group in (27) compared with the larger effect
of the phenyl group in (26). Whereas the furan hydrogens were re
solvable in (26), they were not resolvable in (27). Further evidence
of lower disturbance of symmetry is provided by the fact that the pair
of doublets representing the vinylic hydrogens (H ) and (H ,) are over-
lapped in (27), but well separated in (26). The remainder of the
spectrum of the ethylcyclopropane (27) was a complex eight-hydrogen
signal in the region of 8. 3-9. 5 tau that included the cyclopropyl
hydrogens and the hydrogens on the ethyl group.
Thermal decomposition of the tosylhydrazone salt (17) in the
presence of isobutene gave a remarkably clean reaction producing the
dimethylcyclopropane (28) in 28 percent yield. The structure was
assigned primarily on the basis of the proton magnetic resonance
spectrum. This molecule provides an excellent example of the pro
found effects of molecular symmetry on nuclear magnetic resonance.
A plane of symmetry can be drawn through the dimethylcyclopropane
(28). This plane includes the plane of the cyclopropyl ring and bisects
the plane of the fused furotropyl ring system. This symmetry results
in magnetic equivalence of the furan hydrogens and both sets of vinyl
hydrogens in the seven-membered ring. This results in a simplified
spectrum for the compound. A two-hydrogen singlet for the furan
hydrogens appeared at 2. 83 tau. Instead of the more complex vinyl
absorptions observed in the styrene adduct (26) and in the 1-butene
adduct (27) a simple AB pattern appeared. A doublet centered at 3.81
tau showed a two-hydrogen signal for the (H ) pair. Another doublet
centered at 5. 09 tau was presented by the (H^) pair of hydrogens. The
coupling between (Ha) and (H^) was 11. 5 Hz. about the same value


23
PROTON MAGNETIC RESONANCE SPECTRUM OF PRODUCT (28)
(17) +
H
H
\ A
CC
/ V
(Figure 23)


24
observed in other compounds in this series. The two methyl groups
produced the expected six-hydrogen singlet at 8. 9 tau, accompanied
by a nearby singlet for the two equivalent cyclopropyl hydrogens at
9. 2 tau.
The profound effects of changes in symmetry in spirocyclo-
propanes such as (26), (27), and (28) provide an excellent basis for
assignment of stereochemical configurations in cis- and trans-1,2-
disubstituted spirocyclopropanes by nuclear magnetic resonance.
Trans 1,2-disubstituted spirocyclopropanes (see Figure 24) can be
expected to have equivalent sets of furan hydrogens and vinylic
hydrogens facing each other across the ring. This is because rotation
symmetry
axis
about the twofold axis of symmetry shown in the drawing makes
these sets of hydrogens equivalent. On the other hand, cis-1, 2-
disubstituted spirocyclopropanes can be expected to show the same
kind of complex pattern observed for the vinyl hydrogens as was seen
in the monosubstituted spirocyclopropanes (26) and (27), resulting
from the non-equivalency of facing pairs of hydrogens on the opposite
sides of the seven-membered ring. A model for cis-disubstituted
spirocyclopropanes of this type has been prepared by Krajca from the
14
reaction of 4, 5-benzotropylidene with cyclohexene. This compound
(29) shows a nuclear magnetic resonance pattern in the vinyl region


25
that is essentially identical to the pattern shown by the phenylcyclo-
propane (26). A similar vinylic absorption pattern has been used to
(Figure 25)
assign stereochemical configurations in a series of spirocyclopro-
panes derived from the reactions of 4, 4-dimethylcyclohexadienylidene
with various olefins. This is shown in Figure 26. Both cis- and
trans-1,2-disubstituted spirocyclopropanes of this type were prepared.
(Figure 26)
Both isomers showed the expected effect of symmetry differences upon
the nuclear magnetic resonance spectra in the vinylic region.
With the above-described basis for making stereochemical
assignments in 1, 2-disubstituted spirocyclopropanes, it is possible to
study the stereospecificity of the reaction of furotropylidene (11) with
olefins. The stereospecificity test is widely used as a chemical
28,29
test for distinguishing between singlet and triplet states in carbenes.
Stereospecific addition; i. e. ,
addition to olefins to produce cyclopro-


26
panes in which olefin stereochemistry is preserved, is characteristic
of singlet carbenes. Non-stereospecific addition, in which olefin
stereochemistry is not preserved, is characteristic of triplet
carbenes.
A stereochemical study was undertaken using cis- and trans-2-
butenes as acceptor olefins for the carbene (11). Thermal decompo
sition of the tosylhydrazone salt in the presence of cis-2-butene at
118-120 C, and in the presence of trans-2-butene at the same tem
perature produced two crude reaction mixtures that were virtually
identical in their proton magnetic resonance spectra. Gas chromato
graphic examination of the crude reaction mixtures using a 100-foot
capillary column coated with Ucon LB-550 showed at least 11 com
ponents in the reaction mixtures. Most of the chromatographic peaks
were in the same quantitative relation to each other in both mixtures.
Separation of the main peak on a preparative gas chromatographic
instrument, though it gave a less-perfect separation than the capillary
instrument, did allow some narrowing in the choice of the significant
peaks in the chromatograms prepared on the capillary instrument,
since this fraction was shown by nuclear magnetic resonance to con
tain the major components present in the crude product. The signifi
cant area turned out to be a group of two smaller peaks and one major
peak that were not even well separated on the capillary instrument.
Quantitative differences were seen in the relation of the two smaller
peaks when comparing samples prepared by thermal reaction with the
cis and trans olefins, but the significance of this difference between
these two smaller peaks may be trivial because of the following obser
vations: 1. The proton magnetic resonance spectra (vide infra) of


27
both reaction mixtures were identical. Both crude reaction mixtures
appeared to be predominantly the trans-spirocyclopropane (vide infra).
2. There was no indication of the presence of the cis-spirocyclopro-
pane in either sample to the limit of detection by the proton magnetic
resonance spectra. 3. Thermal reaction of the tosylhydrazone salt
with trans-2-butene is most likely to produce the more stable trans-
spirocyclopropane if product isomerization is taking place. A photo
chemical decomposition of the salt in the presence of cis-2-butene is
most likely to produce the cis-spirocyclopropane, because of expected
lower probability of thermal cis-trans isomerization at the milder
temperatures, ca. 50 C. used. A comparison of the capillary
chromatograms of these two reactions showed the same quantitative
relation among the three peaks in this significant area. Apparently
the major peak is the trans-spirocyclopropane (vide infra). The two
minor peaks were never identifiable for the reasons of small sample
size and difficulty of purification. The proton magnetic resonance
spectra suggest that these are probably mainly C-H insertion products.
The attainment of the same product mixture from carbene reactions
with a pair of isomeric cis-and trans-olefins is the criterion for com
plete loss of stereospecificity in the reaction.
The failure to isolate any of the cis spirocyclopr opane from the
reactions with the 2-butenes and to demonstrate the stability of the cis-
isomer to reaction conditions does leave the experiment open to the
criticism that the cis-isomer is possibly being formed, then is decom
posing to either the trans-isomer or to some other product. This
possibility is impossible to exclude rigorously in the present case,
but some inferences for the stability of the cis-isomer can be drawn


28
from a study of known model compounds. Cyclopropanes of the type
(30) are subject to a cleavage of the cyclopropyl ring followed by
(Figure 27)
isomerization to an indane derivative. The substituted cyclopropane
(30a) undergoes isomerization at 130C. but the unsubstituted cyclo
propane (30b) is stable at 150 C. Similarly, one should expect an
enhanced rate of isomerization in the vinyl-substituted spirocyclo-
propane (31) (Figure 28) because of stabilization of radical inter
mediate (32). The isomerization is slow at 100 C. since the cyclo
propane can be isolated as the main product from reaction mixtures
exposed to that temperature for 0. 5 hr. (vide infra). This suggests
that cis-dialkyl-spirocyclopropanes would require substantially
higher temperatures before isomerization to the trans isomer would
occur at a significant rate.
(Figure 28)


29
Isolation and characterization of the trans spirocyclopropane
produced from the reaction of carbene (11) with the cis- and trans-2-
butenes proved to be as difficult as the foregoing discussion would
suggest. Reaction of trans-2-butene by decomposition of the sodium
salt at 115C. produced a crude reaction mixture, the proton mag
netic resonance spectrum of which suggested that the main component
(18) +
(Figure 29)
was the trans 1, 2-dimethylcyclopropane (34) contaminated with C-H
insertion products. Preparative layer chromatography on silica gel
plates did not improve the appearance of the spectrum very much
until the main band was collected and re-chromatographed on silica
gel plates using very low sample loading. This allowed separation
into three bands, the major one of which gave a spectrum suggesting
a fairly pure sample of the trans-adduct (34). Because of small
sample size, neither of the two minor components was identified. The
yield of the trans adduct (34) appears to be in the neighborhood of
25 percent, but extensive handling of small samples makes this
number unreliable. The assignment of the structure (34) rests pri
marily on the proton magnetic resonance spectrum. There is the
usual sharp singlet at 2. 9 tau for the furan hydrogens. From the
discussion on pages 17, 18, and 19 one would expect the AB pattern
that is observed in the vinylic region, produced by the hydrogens on


30
£ Y y:.'-r
(Figure 30)


31
the seven-membered ring. One of the AB doublets is centered at 3. 8
tau, the other at about 5. 3 tau, with a coupling of 11.5 Hz. At 8. 65
to 8. 9 tau there are two peaks whose relative intensity suggests they
are coupled to the cyclopropyl hydrogens that appear slightly upfield.
There is a third sharp peak just downfield of these cyclopropyl
hydrogens at about 8. 93 tau, the shape and intensity of which leave
its interpretation open to question. It is probably a spurious peak
due to the presence of some impurity, but it could also be the result
of so-called "virtual coupling" through the cyclopropyl hydrogens.
The integration curve is not much help in deciding, since the effect
of this peak on the total is not very great. The best integral does
result from considering it to be a spurious peak, though. The spacing
of this suspicious peak from the closest of the other two is, whether
fortuitous or not, equal to the spacing between the other two and equal
to one of the spacing patterns seen in the signal for the cyclopropyl
hydrogens whose multiplet appears at 9. 05 to 9. 5 tau. The integration
curve for the cyclopropyl hydrogens appears to fall just a little bit
short of the required amount, but some of this signal may be buried
under the "suspicious" peak already discussed. To judge from this
spectrum, there is very little, if any, of the cis-spirocyclopropane
present in the sample.
An overview of the results of the stereochemical study with the
2-butenes suggests that a study with another olefin, one that would
hopefully give a cleaner reaction, would reinforce the argument for
the loss of stereospecificity in addition reactions of this carbene.
Accordingly a study was carried out using trans-deuteriostyrene as an
acceptor for the carbene. From the experience gained with the non-


32
deuterated styrene reaction it was known that this reaction (shown in
Figure 20) can be used to produce rather pure samples of the phenyl-
cyclopropane.
The required deuterated styrene was prepared by the stereo
specific addition of dicyclohexylborane to phenylacetylene followed by
30
hydrolysis with deuterioacetic acid to free the styrene. Formal
addition of the carbene to this olefin was carried out by pyrolysis
of the tosylhydrazone salt in a dilute solution of the olefin in boiling
dioxane (b. p. 101 C. ). The resulting phenylcyclopropane was
separated by preparative layer chromatography. Use of d^-benzene
as a solvent allowed observation of the geminal cyclopropyl hydrogens
by 100 MHz. proton magnetic resonance spectroscopy as two doublets
appearing at 8. 7-9. 2 tau. One of the doublets was split by 8. 5 Hz. ;
the other, by 7. 0 Hz. By double irradiation to decouple the neighboring
cyclopropyl hydrogen (H^) from the geminal pair, the four signals
were caused to collapse to two signals having a separation of about
12 Hz. Integration of the four signals (before decoupling) and the two
signals (after decoupling) showed the presence of an equal mixture
of the two possible isomers.
Though the formation of an equal mixture of the two possible
deuterio phenylcyclopropanes in this study suggests non-stereospecific
addition of the carbene to the olefin, the result is not conclusive unless
the possibility of olefin isomerization before reaction and the possi
bility of product isomerization after reaction are excluded. The
olefin was determined to be stereochemically stable under the reaction
conditions by a control experiment. The stability of the product is not
so easily proved. Separation of the two stereoisomeric products is not


33
PROTON MAGNETIC RESONANCE SPECTRUM OF PRODUCT (26a)
SHOWING SIMPLIFICATION OF ABX
(Figure 31)


34
possible, so a direct test for isomerization under reaction conditions
is not possible. The best remaining option is to conduct the reaction
at a temperature at which product isomerization is highly unlikely.
One can also draw inferences about the thermal stability and the
photochemical stability of the phenylcyclopropane adduct by examina
tion of model compounds (vide infra).
The reaction with trans-deuteriostyrene was repeated by decom
posing the sodium salt of the tosylhydrazone photolytically at about
45 C. This procedure also produced an equal amount of the two
possible stereoisomers. Though it might have been desirable to
have carried out the photolysis at even lower temperatures, the
properties of this carbene are such that it does not add readily to
olefins at low temperatures. This point will be discussed further in
connection with reactions of this carbene with butadiene. The styrene
did not isomerize under photolysis.
The photolytic and thermal stability of the phenylcyclopropane
(26a) can be inferred from the following data: 1. The vinylcyclopro-
pane (31) (see Figure 28) requires temperatures greater than 100C.
for an appreciable rate of ring-opening, followed by closure to the
cyclopentene (33). 2. The same vinylcyclopropane was determined
(vide infra) to be photolytically stable under reaction conditions. 3.
The somewhat similar 1-phenylspiro(2. 6)nona-4, 6, 8-triene (35)
shown in Figure 32 requires temperatures greater than 75C. for
, 31
isomerization to the 8-phenylbicyclo(5. 2. 0)nona- 1, 3, 5-triene (36),
but its isomerization is aided by the formation of a new stable com
pound of a type that cannot be formed from (26). 4. The vinylcyclo-
o 31
propane (37) rearranges to (38) at 50-75 C. On the other hand, the


35
butadiene adduct (39) is stable enough to be isolated by preparative
gas chromatography.^^
75-1 00
->
c6h5
(37)
ch3
(Figure 32)
Pyrolysis of the tosylhydrazone salt (18) in the presence of 1, 3-
butadiene at 118C. produces almost exclusively the 1,4-addition
product (33) (55 percent yield) shown in Figure 33. It has been hypoth
esized that triplet carbenes might react with 1, 3-dienes in the 1, 4-
addition mode. Few carbenes, if any, actually do add in this manner


36
by direct reaction. Most adducts arising from a formal 1, 4-
addition are products from the thermal isomerization of initially
formed 1, 2-addition products such as (3 1). That proved to be true
in this case also. Thermal decomposition of the tosylhydrazone salt
in 1, 3-butadiene at 100C. for short reaction times (0.5 hr. or less)
produced the 1,2 adduct (31). Heating of the vinylcyclopropane (31)
(18)
ToT 5
(Figure 33)
at 120 C. for 0. 5 hr. caused complete conversion to the isomeric
cyclopentene (33).
Structural assignment of the 1, 4-addition product (33) was based
on the following spectral data. In the proton magnetic resonance
spectrum there is the expected two-hydrogen singlet at 2. 82 tau for
the furan hydrogens. Since this molecule has the same kind of
symmetry as the dimethylcyclopropane (28) shown in Figure 22, one
can predict the same kind of AB pattern for the vinyl hydrogens (Ha)
and (H^) in the seven-membered ring. This expected four-line AB
pattern is observed in (33). One of the doublets in the AB pattern is
centered at 3. 9 tau and is split by 11. 5-12 Hz. The other doublet is
centered at 4. 57 tau (representing the (H^) hydrogens), but the left
half of the doublet has a partially superimposed peak from the vinylic
hydrogens in the cyclopentene ring (Hc). The integral for the lower-


37
* m _ t t _ w T > t y 1 m
PROTON MAGNETIC RESONANCE SPECTRUM OF PRODUCT (33)
(Figure 34)


38
field doublet is two hydrogens. The integral for the upper-field
doublet containing the signal for the cyclopentene olefinic hydrogens
indicates a total of four hydrogens. The remainder of the spectrum
is a sharp singlet at 7. 49 tau with a correct integral for the four
allylic hydrogens (H^). The lack of discernible splitting of the
allylic hydrogens is consistent with the reported 0. 5 Hz. allylic
33
splitting in cyclopentene itself. The high symmetry of the 1, 4-
adduct (33) gives rise to some doubt as to whether the C=C bond in the
cyclopentene ring should even be infrared active at all. Nevertheless,
there is a weak absorption at 1618 cm. that does fit the known
pattern for C = C stretch in five-membered rings (cyclobutene, 1566
-1 -1 -1 34
cm. ; cyclopentene, 1611 cm. ; cyclohexene, 1649 cm. ).
Structural assignment of the 1, 2-addition product with butadiene
was based on the following information. The furan hydrogens appeared
as a two-hydrogen singlet at 2. 9 tau. The vinyl region showed
clearly the results of the symmetry-disturbing exocyclic vinyl group.
The pattern for the (H ) and (H ,) hydrogens was a partially over-
lapping pair of doublets showing the same 11.5 Hz. coupling between
the AB pair in the seven-membered ring that has been observed in
(26) and (27). This four-line signal for the (H ) and(Ha,) hydrogens
was about 3. 9-4.2 tau. Another four-line signal for the (H^) and (H^i)
hydrogens appeared at about 5. 1-5.65 tau. Once again, since these
two hydrogens are nonequivalent, the W-form coupling of ca. 2 Hz.
was observed in addition to the coupling with the (Ha) and (Hai)
hydrogens. The vinylic hydrogens belonging to the exocyclic vinyl
group appeared between the two sets of signals for the AB pair in the
seven-membered ring. The (H ^) signal appeared from about 4.2 to


39

i ,,1 T~i ¡ i... .1, p.-i ... ir -
PROTON MAGNETIC RESONANCE SPECTRUM OF PRODUCT (31)
(31)
(Figure 35)


40
*1 > +"' 1 --4-1-- r-i, r V T h
PROTON MAGNETIC RESONANCE SPECTRUM OF PRODUCT (31)
SHOWING ENLARGEMENT OF ABX PORTION
(Figure 36)


41
4. 45 tau with primarily a four-line pattern. The (H2) and (H3)
hydrogens were at 4. 75-5. 0 tau presenting a complex pattern that had
so much fine structure that direct measurement of the coupling
constants was not possible. Use of a 100-MHz, spectrometer made
it possible to resolve each set of vinylic hydrogens, both the AB
pair and the exocyclic vinyl hydrogens, sufficiently to allow an accu
rate integration for each signal. All of the integrals were satisfac
tory, The remainder of the spectrum presented the expected ABX
pattern for the cyclopropyl hydrogens. Direct measurement of
was 5. 0 Hz. The AB portion of the spectrum (for the vicinal cyclo
propyl hydrogens) was at 8. 6-9. 0 tau. The X portion was at about
8. 15-8. 5 tau. The AB signal allowed easy recognition of the expected
pair of overlapping quartets. The X signal gave an integral that was
slightly lower than the correct value because some of the lines were
buried in instrument noise. Four of the lines were visible, but only
two of them were very strong. The spectrum also showed a sharp
singlet at about 8. 6 tau from a contaminating inhibitor (2, 6-di-tert,
butyl-4-methyl phenol) picked up during exposure of the sample to a
commercial grade of tetrahydrofuran. Elemental analysis was made
impossible because of the presence of the inhibitor, since it was
difficult to separate from the sample. The problem was sur
mountable by the ready conversion of the 1,2-adduct to the 1, 4-
adduct (33), which was easy to separate from the inhibitor and to
provide in pure form for elemental analysis. The exocyclic vinyl
O C
group in (31) was shown by infrared.
Decomposition of the tosylhydrazone salt by photolysis at low
temperatures in the presence of 1, 3-butadiene caused a remarkable


42
change in the character of reaction with this olefin. At temperatures
of -60 to -30 C. it produces the product (40), shown in Figure 37,
in about 40 percent yield as the only hydrocarbon product identifiable.
The structure of (40) was identified by the striking similarities in its
spectra with the spectra of a number of similar compounds recently
15
prepared and elucidated in detail by Coburn. In the proton mag
netic resonance spectrum the furan hydrogens produced a two-hydrogen
singlet at 2. 83 tau. The vinylic hydrogens (H&) produced an AB
pattern centered near 4. 0 tau split by 10 Hz. The other vinylic
hydrogens (H^) produce a poorly resolved peak at 4.47 tau. The
allylic hydrogens appear as a broadened peak at 7. 52 tau. The
cyclopropyl hydrogen (He) appears as a doublet at about 7. 85 tau,
coupled by about 5 Hz. to the other cyclopropyl hydrogen (H^) which
appears upfield as a multiplet at 9. 15-9. 45 tau.
Photolysis of the tosylhydrazone salt at intermediate tempera
tures (ca. 40 C.) produced a mixture of (40) and the 1,2-addition
product (31) from reaction with butadiene. The ratio was about
45:55. None of the 1, 4-adduct (33) was produced.
In control experiments the 1,2-adduct (31) was shown to be
stable to photolysis; therefore, it is not the source of the product (40).
The product (40) was shown to be thermally stable for at least 20
minutes at 140 C. since it could be purified by preparative gas
chromatography.
To see if normal carbene behavior could be elicited at low
temperatures, an effort was made to add the carbene to trans-2-
butene by photolysis of the tosylhydrazone salt at -50 C. Normal
carbene addition to the olefin did not occur, as shown by the proton


43
PROTON MAGNETIC RESONANCE SPECTRUM OF PRODUCT (40)
-50
(18) -f CH2~CHCH=CH2 >
(40)
(Figure 37)


44
magnetic resonance spectrum of the crude product. The friable
appearance of the product suggested that it was at least partly
polymeric.
In experiments designed to allow equal amounts of olefin
acceptors to compete for the carbene (11), the following relative rate
data were obtained:
OLEFIN RELATIVE RATE
1 -butene 0. 8
isobutene 1. 0
1, 3-butadiene 9. 0
(Table 1)
One experiment was done to attempt to observe a signal in the
proton magnetic resonance spectrum indicating the operation of the
chemically induced dynamic nuclear polarization (CIDNP) phenom-
3 6
enon. Such an observation would be indicative of the presence of a
triplet carbene. Thermal decomposition of the tosylhydrazone salt in
solution in an nmr sample tube containing a mixture of approximately
20 percent cyclohexene in d^-dimethyl sulfoxide failed to show the
CIDNP phenomenon. This could be attributable to the low solubility
of the tosylhydrazone salt in this medium, indicated by the failure to
observe the presence of the salt in the spectrum of the solution.


DISCUSSION
Thermolysis or photolysis of tosylhydrazone salts of tropone
and substituted tropones in solution have been found to give at least
five different kinds of reactive species (Figure 38). Unsubstituted
1 2, 9
tropone (12) shows chemistry of only the singlet carbene (I).
Mono-annelated tropones (13) and (41) show some chemistry expected
of the singlet carbene (I), but in general, their chemical behavior
is dominated by the bicycloheptatriene (III) and the rearranged
singlet and triplet aryl carbenes (IV) and (V). ^ The di-annelated
tropone (42) shows only the chemistry of the bicycloheptatriene (III)
and the aryl carbene, presumably singlet (IV) and triplet (V). The
di-annelated and tri-annelated tropones (43) and (44) show typical
diaryl carbene chemistry. They have been shown to have triplet
ground states, but their chemistry is dominated by the singlet. ^
The reasons for these differences can be qualitatively rationalized
in terms of the expected relative energies of the different intermediates.
Carbene stabilities are thought to run parallel to cation stabili
ties. Mono-annelation, known to de-stabilize the tropyl cation, should
not be expected to have significant effect on the stability of the inter
mediate cyclopropene (III). Mono-annelation should then decrease the
stability of the carbene relative to the cyclopropene intermediate,
2 0
making the rearrangement easier. The di-annelated species (43) and
the tri-annelated species (44), by incorporating into the fused benzene
systems the double bond that must suffer attack in order for
45


46

(12)
A,
B,
D =
H
(13)
A,
D
= H;
B = fused benzene ring
(41)
A
= fu
s ed
Denzene ring; B,
D =
H
(42)
A,
B
= fus
ed benzene ring;
D =
H
(43)
A,
D
= fus
ed benzene ring;
B =
H
(44)
A,
B,
D =
fused benzene ring
(Figure 38)
W Q


47
rearrangement to occur, reduce the probability of rearrangement by
increasing the relative energy of the intermediate cyclopropene
because of loss of benzenoid aromaticity. The di-annelated species
(42) does not require as much loss of aromaticity to form the cyclo
propene (III), so it undergoes rearrangement easily. Many carbenes
that are formed in their singlet states react in their singlet states,
because the singlet is so reactive that reaction occurs before colli-
sional deactivation to triplet, if that is the ground state, can occur.
Equilibration between a reactive singlet and a relatively unreactive
triplet can also cause the same effect.
The present carbene (11) fits this overall scheme, but as a
result of its unusual structure, it seems to have a unique place in the
scheme. In the first place, unlike any of the other carbenes studied,
under certain conditions (above about 40 C. ) its chemistry is appar
ently dominated by the triplet.
The complete loss of stereospecificity in reactions of (4,5-c)furo-
tropylidene is consistent with triplet behavior. The nonstereospecific
addition of a carbene in solution is now well established as a criterion
for interpreting the reaction in terms of a two-step reaction; i. e. via
triplet. The present stereospecificity studies must be taken with the
37
caveat of Gaspar and Hammond in mind that "Nonstereospecific
addition cannot be taken as a proof that an attacking species is a
triplet unless it has also been shown that under some other conditions
a species of the same composition can give stereospecific addition. "
Closs, in a more recent view, asserts that non stereospecific reac
tions can always be interpreted as proceeding via the two-step mech-
29
anism; i. e. via triplet.


48
The relative reactivities of (4, 5-c)furotropylidene in reactions
with olefins also fit the triplet pattern. It is well accepted that con
jugated dienes, such as 1, 3-butadiene, show a high relative rate of
reaction with triplets because of allylic stabilization of the di-radical
intermediate (Figure 39) in the two-step reaction. The common use
of butadiene as a "triplet scavenger" to improve stereospecificity of
VR
K.
(Figure 39)
carbene reactions by selectively draining off triplet illustrates this
. 38
principle. The relative rates found in this present study also fit
the relative rate pattern for the rate of radical addition vs. abstraction
39
with the same olefins.
Interpreting the reaction of (4, 5-c)furotropylidene with benzene
in terms of triplet chemistry is aided by consideration of some related
reports in the literature. Bis(carbomethoxy)carbene has been gener
ated by photolysis of the corresponding diazo compound under two
32
sets of conditions. Direct photolysis produces a carbene that reacts
in the singlet state as shown by the stereospecificity of its reactions
with olefins. Photosensitized decomposition produces a carbene that
reacts in the triplet state as shown by the loss of stereospecificity in
its reactions with olefins. The same carbene, prepared by each of
the two methods, was allowed to react with benzene. Direct photolysis
of methyldiazomalonate in benzene gave the cycloheptatriene (45 ) and


49
the C-H insertion product (46) in a ratio of 2. 7 to 1. 0. The photo
sensitized reaction gave the same two compounds in a ratio of 1.6 to
(Figure 40)
1. 0. The increased amount of the phenylmalonate (49) when the
carbene is prepared in the triplet state is consistent with the inter
mediacy of the di-radical, which can either close to the norcaradiene
related to the cycloheptatriene, or undergo hydrogen shift to form the
phenylmalonate. Increased triplet character in the attacking carbene
increases the amount of the C-H insertion product. If the slow step
of the reaction is attack of triplet carbene upon a benzene double
bond, the absence of a deuterium isotope effect is to be expected.
This was demonstrated in the present study with (4, 5-c)furotropylidene.
Still, there are hazards in interpreting the insertion of furo-
tropylidene into the C-H bonds of benzene as necessarily a triplet
behavior. A di-radical intermediate such as that shown in Figure 40
could arise from another path. Consider, for example, the six-
membered carbocyclic carbene, 4, 4-dimethylcyclohexadienylidene.
It apparently reacts with olefins in the singlet state in solution. It
reacts with benzene to produce a spironorcaradiene (47) shown in
Figure 41. This spironorcaradiene isomerizes at 100C. to produce
the intermediate (48) that is very much like the di-radical intermediate


50
that could arise from triplet attack upon the benzene double bond.
Here is apparently a singlet pathway to the di-radical intermediate.
(Figure 41)
None of the analogous norcaradiene was detected in the furotropylidene
case, even when the reaction was carried out by photolysis at room
temperature; but the possibility of that intermediate is very real be
cause of the complexity of the mixture that was produced in the reac
tion. The absence of a deuterium isotope effect would also be
expected from the singlet pathway.
Although no one piece of evidence in this report can be said to
rigorously prove that (4, 5-c)furotropylidene is behaving as a triplet
at temperatures above 40C., certainly the mass of evidence taken
as a whole looks fairly convincing. One thing is certain--the cyclo-
propene intermediate (type III, Figure 38) dominates at lower tempera
tures. This is shown by the trapping of the cyclopropene intermediate
(16) (see Figure 11) by the Diels-Alder reaction with butadiene to form
the adduct (40) shown in Figure 37. The cyclopropene seems likely
to have formed from the singlet state of the carbene, since the car-
bene is almost certainly initially formed in the singlet state, and since
intramolecular reactions seem to be favored for carbenes in the


51
i n i /
singlet state. For example, direct irradiation of aliphatic
alpha-diazoketones produces a predominance of the photochemical
Wolff rearrangement; but photosensitized irradiation, which should
increase triplet formation, produces an increased amount of cyclo-
17
propanes, suggesting normal intermolecular carbene reactions.
Formation of the cyclopropene intermediate (16) is a particu
larly surprising result, since the (4, 5-c)furotropylidene (11) has not
shown any evidence of rearrangement to the isobenzofuran skeleton
as might have been expected (Figure 11). This rearrangement, if it
does occur, might be impossible to detect with certainty because of
the high reactivity of the isobenzofuran molecule. It polymerizes
24
rapidly in solution. While one cannot say with certainty that none
of the cyclopropene opens to the isobenzofuranyl carbene, the fact
that yields of up to 50 percent of formal furotropylidene addition
products are formed does allow one to say that the rearrangement is
not the overwhelmingly predominant process such as is observed
with the annelated cycloheptatrienylidenes (13), (41), and (42) in
Figure 38. Perhaps the ring-opening of the cyclopropene intermediate
(16) to the isobenzofuranyl carbene is precluded because not enough
aromaticity is gained in that direction.
Why does triplet chemistry predominate in the reactions of
furotropylidene at moderate to higher temperatures? The apparent
ease of crossing from singlet to triplet suggests that these two elec
tronic states are at very similar energy levels in this carbene. The
effect of temperature in changing the character of the reactions of this
carbene has a few interesting parallels in the literature.


52
Closs has reported a case in which there may be a temperature
40
effect upon a singlet-triplet equilibrium. Diphenyl carbene, known
to have a triplet ground state, was produced by irradiation of di-
phenyldiazomethane in the presence of olefins. In reactions with cis-
and trans-2-butenes, cyclopropanes account for no more than 10 per
cent of the hydrocarbon products. Hydrogen abstraction was the main
reaction pathway. At -10C. the cis-and trans 1, 2-dimethyl-3, 3-
diphenylcyclopropanes were formed in a ratio of 3. 2 from the cis-2-
butene. The corresponding ratio from the trans olefin was 0. 04.
Lower temperatures caused increased stereospecificity. At -66C.
the product ratio from the cis -2-butene was 9. 0. At a given tem
perature the product ratio was found to be independent of the butene
concentration over a range of 150-fold dilution with cyclohexane. The
presence of oxygen failed to change the isomer ratio of products.
Closs postulated the following scheme (Figure 42) as a possible ex
planation of his observations. He suggested that intersystem crossing
is much faster than any other reaction in the system and that the
reverse crossing is also very fast so that both singlet and triplet are
effectively in equilibrium. The relative rates of the singlet (kag) and
the triplet (k ) addition steps and the position of the singlet-triplet
equilibrium both determine the fraction of stereospecific singlet-state
addition. Since diphenylmethylene is known to have a triplet ground
state, the rate of crossing to the triplet (k^) must be greater than the
rate of triplet crossing to the singlet (k ; therefore, in view of the
observed product ratios, the rate of singlet addition (k ) must be
much greater than the rate of triplet addition (k&t). If the difference
in the free energies of activation for the two addition reactions is


53
larger than the free energy difference between the two electronic
states, the temperature difference could be explained on this basis
alone. It is not possible to determine whether a temperature effect
upon the position of singlet-triplet equilibrium is being observed, but
this is a possibility.
(Figure 42)
Thermal effects upon the population of electronic states are
known in certain photochemically produced noncarbene species. An
41
example is a study of pyrene-d1Q in a polymethylmethacrylate matrix.
The triplet yield plus the fluorescence yield was near unity at -196C.
As the temperature was raised, two effects were observed. First,
the triplet yield increased with increasing temperature, suggesting a
temper ature-dependent proc es s that produces increasing intersystem


54
crossing from vibrationally excited singlet to second triplet state
(^2). The second effect observed was a falling off of the sum of
triplet yield and fluorescence yield from the expected value of unity
as temperature increased. This suggested a thermally dependent
radiationless transition from the first singlet state to the ground
state. The energy of activation for the temperature-dependent com
ponent of the intersystem-crossing process was determined to be
about 2. 6 kcal. per mole. The energy of activation for the radiation
less transition from singlet to ground state was about 0, 9 kcal per
mole.
A somewhat similar study of 1, 12 benzperylene has shown that,
since the second excited singlet of this molecule lies only about
1300 cm. (3,7 kcal. per mole) above the first excited singlet, there
is significant thermal population of the second excited singlet state
at 2 3C. 42
Whether furotropylidene is showing a similar thermal effect
upon population of electronic states is not possible to determine so
long as the electronic states themselves cannot be observed except
through their chemistry. This is because the relative rates of re
action of the electronic species with their trapping agents are
unknown.
It is possible to draw several speculative schemes that could fit
the presently known facts about (4, 5-c)furotropylidene. Some of
these are shown in abbreviated form in Figure 43. It seems reason
able to assume that the cyclopropene is lower in energy than the
initially formed singlet carbene. The relative energies of the triplet
and singlet states shown in Figure 43 can only be the subject of


55
(Figure 43)


56
speculation from the present data. It is interesting to consider the
question as to whether equilibria exist between the species in Figure
39, but there is no experimental basis for a determination of this
question. A hypothetical experiment can be devised to answer this
question. If one can show that there is X percent formation of cyclo-
propene under a given set of conditions and that there is more than
(100-X) percent of carbene addition observed under the same condi
tions in the absence of a cyclopropene trap, one could reasonably
conclude that an equilibrium between cyclopropene and singlet carbene
does exist. Such an experiment seems to call for extraordinarily
high yields in these carbene reactions that are unlikely to be attain
able. In all of these schemes it seems reasonable that singlet
chemistry is not observed via intermolecular olefin trapping, since
the intramolecular reaction to form the cyclopropene would be ex
pected to be much faster than the intermolecular reaction.
It is interesting to speculate that perhaps triplet chemistry
predominates at higher temperatures because the singlet, through
its aromatic character, is relatively less reactive than triplet, and
therefore has a sufficiently long lifetime to allow intersystem crossing
to occur before singlet reaction occurs. An equilibration between
singlet and triplet, with the triplet the more reactive of the pair,
would also fit the data.
Perhaps the study of minor reaction products of (4, 5-c)furotro-
pylidene would shed additional light on these matters, but the separa
tion and purification of such large molecules formed in such low yields
presents formidable experimental difficulties.


EXPERIMENTAL
General. Melting points were taken in a Thomas -Hoover
Unimelt apparatus and are uncorrected. Elemental analyses were
performed by Atlantic Microlab, Incorporated, Atlanta, Georgia.
Accurate mass measurements were provided by Dr. R. W. King,
using the MS-30 high-resolution mass spectrometer equipped with
automatic data system, at the University of Florida. Infrared spectra
were recorded on a Beckman IR-10 spectrophotometer. In all cases
where the liquid film technique was not used, the KBr pellet technique
was used. Nuclear magnetic resonance spectra were determined on
a Varian A-60A high-resolution spectrometer, or in some cases, a
Varian XL-100 instrument. Chemical shifts are reported in tau
values from internal tetramethylsilane standard. Low resolution
mass spectra were determined on a Hitachi RMU-6E mass
spectrometer.
Analytical thin-layer chromatography was done on 2 in. x 8 in.
plates coated in these laboratories with 0. 25 mm. layers of E. Merck
HF-254 silica gel; preparative work was conducted on 8 in. x 8 in.
plates coated with 1. 0 to 1.5 mm. layers of HP-254 silica gel. Com
ponents were visualized by their quenching of fluorescence under
ultraviolet light. Analytical gas chromatography was accomplished
with a Varian Aerograph Series 1200 ame ionization instrument using
a 100-ft. capillary column coated with Ucon LB-550. Analytical
results were obtained by planimetric measurement and by peak height
times peak-width-at-half-height measurement.


58
All chemicals are reagent grade used as supplied unless other
wise stated. The furan-3, 4-dicarboxylic acid was used as supplied
by Aldrich Chemical Company, Milwaukee, Wisconsin. Solvents
were dried by passage through a column of either freshly re-activated
Linde Molecular Sieve (4A) or Woelm basic alumina, activity grade 0,
followed by storage over calcium hydride under a nitrogen atmosphere.
3, 4-Di(hydroxymethyl)furan. This compound has been reported
23
as the product of the reduction of dimethyl-3, 4-furandicarboxylate.
The reported yield of 76 percent did not result from use of the pub
lished procedure. The following procedure gave 72 percent conver
sion based on the diacid. A mixture of 31.2 g. (0. 2 moles) 3, 4-
furandicarboxylic acid, 47.2 g. (0.4 moles) thionyl chloride, 200 ml.
benzene, and 1 ml. N, N-dimethylformamide was heated at reflux for
1 hr. The reaction is essentially complete when all of the solid has
dissolved. The benzene and excess thionyl chloride were removed in
vacuum by rotary evaporator. The crude diacyl chloride, formed
in essentially quantitative yield, was reduced directly without purifi
cation using the following procedure. The crude acid chloride was
dissolved in ca. 300 ml. tetrahydrofuran. This solution was dripped
into a stirred suspension of 30 g. lithium aluminum hydride in 800 ml.
dry tetrahydrofuran. The mixture was stirred at room temperature
overnight, then refluxed 8 hr. The reaction mixture was cooled. The
excess hydride was destroyed by addition of about 300 ml. of 5 percent
sodium hydroxide solution that had been saturated with sodium
chloride. The ether layer was separated by decanting from the white
granular slurry. This white residue was washed several times with
diethyl ether. The washings were corrbined with the first (THF)


59
extract, washed with brine, dried with anhydrous MgSO^ and filtered.
Removal of the solvent on a rotary evaporator using aspirator vacuum
gave 26. 4 g. of crude 3, 4-dihydroxymethylfuran. The product was
identified by the correspondence of its spectral properties with the
23
values reported in the literature.
3, 4-Furandicarboxaldehyde. This compound was prepared from
3, 4-di(hydroxymethyl)furan in two steps by the procedure of Cook and
2 3
Forbes. The first step, partial oxidation of the di-alcohol with
activated manganese dioxide, gave yields of about 50 percent instead
of the reported 80 percent. The best yields of di aldehyde were ob
tained by lead tetra-acetate oxidation of the crude 3 -hydroxymethyl-
furan-4-carboxaldehyde containing about 50 percent of unreacted
glycol, rather than by separation and purification of the mono
aldehyde. This procedure allowed the lead tetraacetate to oxidize,
not only the mono-aldehyde in the mixture, but also the glycol that
had not been oxidized by the manganese dioxide. This required use
of about 50 percent more lead tetraacetate than would have been
required for oxidation of an equal weight of 3-hydroxymethylfuran-4-
carboxaldehyde to the dialdehyde. This procedure gave about 25 per
cent conversion of the glycol to 3, 4-furandicarboxaldehyde. The
produce was identified by the correspondence of its spectral properties
and melting point with the values reported in the literature by Cook
and Forbes. ^
(4, 5-c)Furotropone. This compound was prepared by condensa
tion of 3, 4-furandicarboxaldehyde with acetone using the procedure of
23
Cook and Forbes. The yield and the physical and spectral properties
of the product were exactly as reported.


60
(4, 5-c)Furotropone tosylhydrazone. A solution of 2. 0 g.
(0. 014 moles) p-toluenesulfonylhydrazine and a trace of phosphoric
acid in 20 ml. of dry tetrahydrofuran was allowed to stand in a
stoppered flask for three to seven days at room temperature. The
solution was diluted with one volume of chloroform and allowed to
stand in a refrigerator cabinet (ca. 5-7C.) for 0. 5 to 1 hr. The
resulting slurry of crystals was poured onto a Buchner filter. The
collected yellow crystals were washed with fresh chloroform on the
filter. The combined wash solvent and mother liquor were eluted
from a column of silica gel (4. 5x15 cm. ) using methylene chloride.
The first (yellow) fraction was collected and evaporated to dryness.
The residue was washed with chloroform and filtered. The resulting
second crop of yellow crystals when combined with the first crop on
the filter gave a total of 2. 9 g. (66 percent conversion) of the ketone
tosylhydrazone, m. p. 214-215C. w. decomposition.
Anal. Caled for C jqN203S: C, 61.13;H, 4. 49; N, 8.91.
Found: C, 60. 97; H, 4. 54; N, 8.85.
- 1
The spectral data were: ir (KBr, cm. ) 3190, 1640, 1595,
1395, 1325, 1 162, 1052, 930, 885, 830, 762, 680. nmr (d6-DMSO)
2, 1 to 4. 13 (complex pattern, total 10H), 7.62 (singlet, 3H).
(4, 5-c)furotropone tosylhydrazone, sodium salt. A solution of
3. 9 g. furotropone tosylhydrazone in 100 ml. dry tetrahydrofuran was
stirred under dry nitrogen while 0. 5 g. sodium hydride (washed with
pentane) was added. After 0. 5 to 1.0 hr. at room temperature, 50-75
ml. pentane was added to the reaction mixture. The resulting slurry
of yellow solid was filtered in a dry nitrogen atmosphere (dry box) to
recover 5.2 g. of the sodium- salt.


61
Decomposition of tosylhydrazone salt in presence of benzene.
(4, 5-c)Furotroponetosylhydrazone sodium salt (0. 3 g. 0. 7 mmole)
was stirred with 50 ml. benzene in a sealed Fischer-Porter Aerosol
Compatibility Test Tube (containing an atmosphere of dry nitrogen)
and heated in an oil bath kept at 118C. After 1 hr. the tube was
cooled and opened. The dark brown slurry was taken from the tube
and filtered through a sintered glass funnel. The solid filter cake
weighed 0. 24 g. The filtrate, upon evaporation of the benzene, left
a residue of 0. 14 g. This crude residue was chromatographed on
preparative silica gel plates developed with hexane containing 5-10
percent benzene. The leading band of the chromatogram was col
lected, stripped from the adsorbent with ethanol, and recovered by
evaporating the filtered solution. This resulted in collection of 0. 063
g. of the benzene insertion product (25), m. p. 75-77 C.
Anal. Caled for C 15H1zO: C, 86. 49; H, 5.82. Found: C, 86. 38
H, 5.85.
The spectral data were: ir (KBr, cm ) 1595, 1490, 1450,
1 123, 1040, 872, 852, 800, 797, 762, 700; nmr (CDC13) 2. 71 and 2. 72
(two singlets, total 7H), 3.7 (complex, 2H), 4.5 (complex, 2H), 5.64
(complex, 1H); mass spectrum (70 eV) 208 (molecular ion), 131, 77.
Decomposition of tosylhydrazone salt in equimolar benzene-d^-
benzene. A repeat of the above preparation in the presence of an
equimolar mixture of benzene and hexadeuterated benzene produced
a 50:50 mixture of the benzene insertion product and the deuterated
benzene insertion product as determined by nmr (100 MHz. ) and by
mass spectroscopy.


62
Decomposition of tosylhydrazone salt in presence of styrene. A
solution of 0. 42 g. (4 mmoles) styrene in 15 ml. dry dioxane was
heated to 100 C. in a flask equipped with thermometer, stirring bar,
and an inlet for dry nitrogen. Dry solid tosylhydrazone salt (0. 33 g. ,
0. 8 mmoles) was added to the solution all at once. After 0. 3 hr. the
reaction mixture was quickly cooled in an ice bath as stirring was
continued. The crude brown slurry in the flask was removed and
filtered, then treated on a rotary evaporator to remove the dioxane
and as much styrene as possible. The resulting residue was dis
solved in chloroform and streaked on a preparative silica gel plate.
Development of the plate in a mixture of hexane and chloroform gave
0. 07 g. of somewhat impure spiro adduct in the major band. This
material was purified by repetition of the silica gel chromatography
using hexane as the solvent for development of the plate. This gave
0.06 g. of the oily liquid phenylspirocyclopropane (26), conversion
32 percent.
Anal. Caled for C^H^O; C, 87. 13; H, 6.03. Found: C,
86. 81; H, 6. 01.
The spectral data were: ir (film, cmT^) 3130, 3080, 3060,
3020, 2995, 1662, 1600, 1540, 1495, 1450, 1410, 1210, 1 125, 1047,
980, 875, 855, 815, 790, 698; nmr (CC14) 2.86 (singlet, 5H), 2.96
and 3. 01 (two singlets, total 2H), 7. 55-7. 82 (complex, 1H), 8. 5-8. 76
(complex, 2H); mass spectrum (70eV) 234 (molecular ion), 2 16, 205,
191, 130, 128.
Thermal decomposition of tosylhydrazone salt in presence of
trans-deuteriostyrene. The above preparation was repeated using
trans-deuteriostyrene in place of styrene. Examination of the nmr


63
spectrum showed that the product consisted of equal parts of the cis
and trans cyclopropanes. The spectrum showed a simplified ABX
pattern as described in the text of this report.
Photolytic decomposition of tosylhydrazone salt in presence of
trans-deuteriostyrene. A solution prepared as in the experiment
above was irradiated in a sealed tube (magnetically stirred) with two
Sears-Roebuck sunlamps at a distance of approximately 8-10 inches.
During the reaction and the workup the product was not exposed to
temperatures exceeding 50 C. The resulting phenylcyclopropane
consisted of equal parts of the cis and trans products as shown by
nmr.
Test of the thermal and photolytic stability of trans-deuterio-
styrene. A small sample of trans-deuteriostyrene in an nmr sample
tube was heated in a steam cone for 0. 5 hr. The nmr spectrum was
unchanged by the heating. The sample was also unchanged after it
was irradiated by two Sears Roebuck sunlamps for 0. 75 hr.
Decomposition of tosylhydrazone salt in presence of 1-butene.
The salt (0. Z g, 0. 48 mmoles) was heated with 5 g. 1-butene (liquid)
that had been distilled into a Fisher Porter Aerosol Compatibility
Test Tube. The tube was kept in an oil bath at 110 C. for 1 hr. The
excess 1-butene was then released. The crude residue was slurried
with benzene and filtered through a sintered glass filter. The solid
filter cake weighed 0. 14 g. The crude filtrate left a residue of 0. 05 g.
after evaporation of the benzene. This residue (about 90 percent
pure) afforded the ethyl spirocyclopropane (27) after purification by
preparative vapor phase chromatography on an 8 ft. x 1/4 in. column
packed with 60/80 mesh Anakrom ABS coated with 20 percent w/w
SE-30.


64
Anal. High resolution mass spectroscopy (70 eV): Caled for
C13H14O: 186. 1044. Found: 186. 1036.
The spectral data were: ir (liquid film, cm. 3145, 3070,
3035, 3000, 2975, 2940, 2880, 1670, 1540, 1470, 1460, 1132, 1050,
980, 880, 850, 810; nmr (CCl^) s.95 (singlet, 2H), 3.87-4.3 (over
lapping doublets, total 2H), 5.25-5.8 (complex, 2H), 8. 3-9. 5 (com
plex, 8H); mass spectrum (70 eV) 186 (molecular ion), 17 1 (C^H^O),
158. 07 (Cj jHjqO), 157. 06 (ChH90), 144. 05 (C 10H8O), 130.04
Decomposition of tosylhydrazone salt in presence of isobutene.
The salt (0. 3 g. 0. 7 mmoles) was heated with ca. 4 g. liquid iso
butene in a sealed Fisher-Porter Aerosol Compatibility Test Tube in
an oil bath at 1 12C. for 1-1.5 hr. The excess isobutene was then
released to cool the contents of the tube. The crude residue that
remained was slurried in benzene and filtered. The solid filter cake
weighed 0. 2 g. The filtrate, after evaporation of the benzene,
weighed 0. 038 g. Purification of this residue by taking the leading
band on a thin-layer plate (silica gel) developed in hexane gave
0. 017 g. of the purified dimethyl spirocyclopropane (28). The high
purity of the crude product, as shown by its nmr spectrum, suggests
that a large loss of material occurred during handling that was not
attributable merely to purification.
Anal, High resolution mass spectroscopy (70 eV): Caled for
C 13H14: 186.1044. Found: 186.1060.
The spectral data were: ir (liquid film, cm. *) 3055, 3030,
2980, 1770, 1725, 1540, 1440, 1365, 1 130, 1 1 10, 1050, 880, 825;
nmr (CC14) 2. 83 (singlet, 2H), 3. 7-3. 9 (doublet, 2H), 4. 9-5.2


65
(doublet, 2H), 8. 9 (singlet, 6H), 9. 2 (singlet, 2H0; mass spectrum
(70 eV) 186. 10 (molecular ion), 185. 10 (C^H^O) 172. 08
(c i2H ii). 158. 07 (CnH10O), 157. 06 (C j jHgO), 144. 05 (C 10HgO).
Thermal decomposition of tosylhydrazone salt in presence of
cis- and trans-2-butenes. The same pyrolysis technique described
above was used to decompose samples of the tosylhydrazone salt in
the presence of cis and trans-2-butenes. The resulting crude re
action mixtures had essentially identical nmr spectra and gas chro
matograms (capillary column, Ucon LB-550). Pyrolysis of a 0. 3-g.
sample (0.72 mmoles) of the salt with 15 ml. liquid trans-2-butene
at 118C. produced a crude product weighing 0. 09 g. Careful
preparative layer chromatography (silica gel adsorbent, hexane
solvent) of this material at low plate loadings gave 0. 03 g. of trans-
dimethylspirocyclopropane (34), 23 percent conversion.
Anal. High resolution mass spectroscopy (70 eV): Caled for
C 1 3H 14' 186- 1044- Found: 186. 1052.
The spectral data were: ir (liquid film, cm. ^) 3030, 3000,
2960, 2935, 2855, 1665, 1540, 1455, 1387, 1 130, 1088, 1050, 880,
810; nmr (CC14) 2.88 (singlet, 2H), 3.9 (doublet, 2H), 5.3 (doublet,
2H), 8. 75-9. 0 (three sharp peaks, total 6H), 9. 0-9. 5 (complex, 2H);
mass spectrum (70 eV) 186. 10 (molecular ion), 171.08 (C^Hj^O),
158. 07 (CnH10O), 157. 06 (CnH90), 144. 06 (C } 0HgO), 128.06
(C 10h8)-
Photolysis of tosylhydrazone salt in presence of cis-2-butene.
The photolytic decomposition of 0, 33 g. tosylhydrazone salt with 12 g.
cis-2-butene was carried out by irradiating the stirred slurry in a
sealed tube for 1 hr. using two Sears-Roebuck sunlamps at a distance


66
of about 10-12 inches. This procedure produced a crude product
mixture that gave an nmr spectrum and gas chromatogram that were
essentially identical to those produced by the thermal decomposition
of the salt in the presence of cis- and trans-2-butenes described
above.
Photolysis of tosylhydrazone salt in presence of trans-2-butene
at low temperature. Photolytic decomposition of 0.4 g. tosylhydra
zone salt by irradiation for 1 hr. with a Hanovia 55 0-watt mercury
lamp at a temperature of -30C. produced a crude reaction mixture
that contained no cyclopropane (34) as determined by nmr.
Determination of relative rates of reaction with various olefins.
Relative rates of reaction with various olefins were determined using
the pyrolysis method in a sealed tube as previously described. The
temperature of the oil bath was kept at 118C. for all runs. In each
run a comparison of product formation from each of two olefins was
done. Each olefin was present in equimolar amounts, measured by
condensing equal volumes of the gaseous olefins into the reaction
tube by use of a mercury-filled gas buret. The product ratios were
determined by capillary column gas chromatography as described
under the General heading of this section. The results are presented
in Table I, page 31.
Pyrolysis with 1, 3-butadiene at 110C. Furotropone tosylhy
drazone salt (0.25 g. 0. 6 mmoles) was heated with ca. 20 ml. liquid
1, 3-butadiene in a sealed Fisher-Porter Aerosol Compatibility Test
Tube in an oil bath kept at 110C. for 4 hr. Excess butadiene was
vented to the atmosphere after the tube was removed from the bath
and opened. The residue that remained in the tube was slurried in


67
benzene and filtered through sintered glass. The clear amber ben
zene solution was streaked on a preparative layer plate (silica gel)
that was developed with hexane. The leading band of material gave
0. 06 g. of the 1, 4-adduct of butadiene (33), 55 percent yield. A
small band of material following the 1, 4-adduct was too small for
identi fication.
Anal. Caled for C13H120: C, 84. 75; H, 6.57. Found: C,
84. 49; H, 6. 65.
The spectral data were: ir (liquid film, cm. ^) 3060, 3020,
2930, 2850, 1618, 1540, 1440, 1340, 1 132, 1052, 948, 882, 848,
800, 670; nmr (CCl^) 2.82 (singlet, 2H0, 3.8-4. 7 (two doublets with
overlapping signal, total 6H), 7.5 (singlet, 4H); mass spectrum
(70 eV) 184 (molecular ion), 169, 155, 130, 129, 128, 54.
Pyrolysis with 1, 3-butadiene at 100 C. The tosylhydrazone
salt (0. 36 g. 0.86 mmoles) was pyrolyzed with 1, 3-butadiene by the
above-described method using an oil bath temperature of 100 C. and
reaction time of 0. 5 hr. Similar workup and chromatography showed
only a very weak leading band corresponding to the 1, 4-adduct (33)
(0. 01 g. ), followed by a second band that afforded 0. 025 g. of the 1, 2-
adduct, the vinyl cyclopropane (31). A yield figure is not given in
this reaction because the short reaction time and low temperature
probably did not decompose all of the sodium salt.
Anal. Analysis was done by thermal isomerization of the 1,2-
adduct to the known 1, 4-adduct by heating it at 130 C. for 0. 5 hr.
The spectral data were: ir (liquid film, cm. ^) 3140, 3090,
3010, 1542, 1217, 1132, 1052, 1000, 910, 880, 813, 790; nmr (CC14)
3. 0 (singlet, sH), 4-5. 7 (complex, 7H), 8. 2-9. 1 (ABX pattern, 3H).
An impurity gave a singlet at 8. 64.


68
Photolysis of tosylhydrazone salt with 1, 3-butadiene at low
temperature. The tosylhydrazone salt (0. 4 g. 0. 98 mmoles) was
photolyzed in a stirred reactor at -40 to -50 C. using the Hanovia
550-watt lamp for 2 hr. Workup, including thin-layer chromatog
raphy, as described before afforded 0. 07 g. of the Diels-Alder adduct
(40), 39 percent conversion.
Anal. High resolution mass spectroscopy (70 eV): Caled for
C13H120: 184. 0887. Found: 184.0880.
The spectral data were: ir (liquid film, cm. ^), 3040, 2960,
2880, 2840, 1630, 1430, 1280, 1220, 1050, 1 110, 1025, 892, 860,
780, 740; nmr (CC14) 2.83 (singlet, 2H), 4.0 (doublet, 2H), 4.47
(broad, 211), 7. 52 (broad, 4H), 7. 85 (doublet, 1H), 9.15-9.45
(multiplet, 1H); mass spectrum (70 eV) 184.0887 ( molecular ion),
182. 073 (C 13H1qO), 169. 065 (C12H90), 168. 057 (C 12HgO), 165.070
(C j ^HpO).
Photolytic stability of vinylcyclopropane (31). A sample of the
vinylcyclopropane (31) was irradiated with two Sears-Roebuck sun
lamps for 0. 5-0. 75 hr. It was unchanged after irradiation.
Photolysis of tosylhydrazone salt with 1, 3-butadiene at 40 C. A
small-scale photolysis (ca. 25 mg. salt) was run in the presence of
1, 3-butadiene at 40 C, The product ratio was determined by a gas
chromatographic analysis (see General heading) of the crude product,
followed by another similar analysis after removal of all 1, 2-adduct
by thin-layer chromatography. The result showed that the Diels-Alder
adduct (40) and the vinylcyclopropane (31) were present in a 45:55
ratio with none of the 1, 4-adduct (33) present.


69
CIDNP Experiment, A saturated solution of the tosylhydrazone
salt in an nmr tube containing a solution of ca. 20 percent cyclohexene
in d^-DMSO was heated in the variable temperature probe of the
Varian A-60A at 120 C. for 10 min. No change in the spectrum
was detected before, during, and after heating.


LIST OF REFERENCES
1. C, L. Ennis, Ph. D. Dissertation, University of Florida,
March, 1968.
2. W. M. Jones and C. Lawrence Ennis, J. Am. Chem. Soc.,
9_1, 6391 (1969).
3. R. Gleiter and R. Hoffmann, J. Am. Chem. Soc., 90,
5457 (1968).
4. W. M. Jones, M. E. Stowe, E. E. Wells, Jr., and
E. W. Lester, J. Am. Chem. Soc. 90, 1849 (1968).
5. P. H. Gebert, Ph. D. Dissertation, University of Florida,
March, 1972.
6. L. W. Christensen, E. E. Waali, and W. M. Jones, J.
Am. Chem. Soc., 94, 21 18 (1972).
7. D. Seyferth, J. Y. -P. Mui, and R. Damrauer, J. Am.
Chem. Soc., 90, 6182 (1968).
8. J. E. Baldwin and R. A. Smith, J. Am. Chem. Soc. 89,
1886 (1967).
9. W. M. Jones, Burrell N. Hamon, Robert C. Joines, and
C. L. Ennis, Tetrahedron Lett., 3909 (1969).
10. I. Moritani et al. Tetrahedron Lett., 373 (1966).
1 1. I, Moritani et al. J. Am. Chem. Soc. 89, 1259 (1967).
12.S. I. Murahashi, I. Moritani, and M. Nishino, J. Am.
Chem. Soc., 89, 1257 (1967).
13. K. E. Krajca, Tsutomu Mitsuhasni, andW. M. Jones,
J. Am. Chem. Soc., 94, 3661 (1972).
14. K. E. Krajca, Ph. D. Dissertation, University of Florida,
August, 1972.
15. Thomas Coburn, Ph.D. Dissertation, University of Florida,
August, 1973.
70


71
16. P. S. Skell, Accounts of Chemical Research, 6, 97 (1973).
17. Maitland Jones, Jr. and Wataru Ando, J. Am. Chem, Soc. ,
90, 2200(1968). ~
18. W. M. Jones and J. P. Mykytka, unpublished results, 1973.
19. A. Streitwieser, Jr. "Molecular Orbital Theory for Organic
Chemists, John Wiley and Sons, New York, N. Y. 1961, p.357.
20. W. M. Jones et al. J. Am. Chem. Soc., 95, 826 (1973).
21.Domenick J. Bertelli and Thomas G. Andrews, Jr. J. Am.
Chem. Soc., 91, 5280 (1969).
22. Domenick J. Bertelli, Thomas G. Andrews, Jr. and Phillip O.
Crews, J, Am. Chem. Soc. 91, 5286 (1969).
23. M. J. Cook and E. J. Forbes, Tetrahedron, 24, 4501 (1968)
and references cited therein.
24. Ronald N. Warrener, J. Am. Chem. Soc,, 93, 2346 (1971).
25. O. L. Chapman, J. Am. Chem. Soc., 85, 2014 (1963).
26. C. N. Banwell, in "Nuclear Magnetic Resonance for Organic
Chemists," D. W. Mathieson, Ed., Academic Press, New York,
N. Y. 1967, p. 85.
27. Maitland Jones, Jr. Arnold M. Harrison, and Kenneth R.
Rettig, J. Am. Chem. Soc., 91, 7462 (1969).
28. P. S. Skell and R. C. Woodworth, J. Am. Chem. Soc. 78,
4496 (1956).
29. G. L. Closs, in "Topics in Stereochemistry, Vol. 3, E. L.
Eliel and N. L. Allinger, Eds. Interscience Publishers, New
York, N. Y. 1968, p. 226.
30. George Zweifel, G. M. Clark, and N. L. Polston, J. Am. Chem.
Soc., 93, 3395(1971).
31. E. E. WaaliandW. M. Jones, J. Am. Chem. Soc., in press.
32. Maitland Jones, Jr., Wataru Ando, Michael E. Hendrick,
Anthony Kulczychi, Jr. Peter M. Howley, Karl F. Hummel,
and Donald S. Malament, J. Am. Chem. Soc., 94, 7469 (1972).
33. K. B. Wiberg and B. J. Nist, J. Am. Chem. Soc. 83, 1226
(1961).
34. L. J. Bellamy, "Advances in Infrared Group Frequencies,"
Meuthen and Co. Ltd. London, 1968, p. 24.


72
35. L. J. Bellamy, "The I. R. Spectra of Complex Molecules,"
John Wiley and Sons, New York, N. Y. 1954, p. 31.
36. Harold R. Ward, in "Free Radicals," J. K. Kochi, Ed., John
Wiley and Sons, New York, N. Y. 1973, p. 239.
37. Peter P. Gasper and George S. Hammond, in "Carbene
Chemistry," Wolfgang Kirmse, Ed., Academic Press, New
York, N. Y. 1964, p. 270.
38. W. J. Baron et al. in "Carbenes," Vol. 1, Maitland Jones,
Jr. and Robert A. Moss, Eds. John Wiley and Sons, New
York, N. Y. 1973, p. 81.
39. K. U, Ingold, in "Free Radicals, J. K. Kochi, Ed. John
Wiley and Sons, New York, N. Y. 1973, p. 92.
40. G. L. Closs, in "Topics in Stereochemistry, Vol. 3, E. L.
Eliel and N. L. Allinger, Eds. Interscience Publishers, New
York, N. Y. 1968, p. 224.
41. J. L. Kropp, W. R. Dawson, and M. W. Windsor, J. Phys.
Chem. 73, 1752(1969). '
42. W. R. Dawson and J. L. Kropp, J. Phys. Chem., 73, 1752
(1969).


BIOGRAPHICAL SKETCH
Thomas Howard Ledford was born August 24, 1942, in Macon,
Georgia, to Mr, and Mrs, Howard William Ledford. He was gradu
ated from Swainsboro High School, Swainsboro, Georgia, in I960
and entered the University of Georgia as a four-year General Motors
Scholar that September. While there he was elected to Phi Beta
Kappa and received the Merck Award and the American Institute of
Chemists Award. He obtained the degree of Bachelor of Science in
Chemistry in June, 1964. The period 1965- 1968 was spent in indus
trial research in organic chemistry with Tennessee Eastman
Company, Kingsport, Tennessee. In 1968 he enrolled in the Graduate
School of the University of Florida with a Woodrow Wilson National
Fellowship. He was also a Graduate School Fellow during his
graduate study. He is a member of the American Chemical Society
and Phi Beta Kappa.
Mr. Ledford is married to the former Joan McDaniel of Oneonta,
Alabama. He will be working for the Esso Research Laboratories
of Exxon, U.S.A., in Baton Rouge, Louisiana.
73


I certify that I have read this study and that in my opinion it con
forms to acceptable standards of scholarly presentation and is fully ade
quate, in scope and quality, as a dissertation for the degree of Doctor
of Philosophy,
William M. J
Professor of
I certify that I have read this study and that in my opinion it con
forms to acceptable standards of scholarly presentation and is fully ade
quate, in scope and quality, as a dissertation for the degree of Doctor
of Philosophy,
a.
Merle A. Battiste
Professor of Chemistry
I certify that I have read this study and that in my opinion it con
forms to acceptable standards of scholarly presentation and is fully ade
quate, in scope and quality, as a dissertation for the degree of Doctor
of Philosophy.
/I
George B, Butler
Professor of Chemistry
I certify that I have read this study and that in my opinion it con
forms to acceptable standards of scholarly presentation and is fully ade
quate, in scope and quality, as a dissertation for the degree of Doctor
of Philosophy,
Aw; fefc"
Roge^/G. Bates
Professor of Chemistry


I certify that I have read this study and that in my opinion it con
forms to acceptable standards of scholarly presentation and is fully ade
quate, in scope and quality, as a dissertation for the degree of Doctor
of Philosophy.
Richard H. Hammer
Associate Professor of Pharmaceu
tical Chemistry
This dissertation was submitted to the Department of Chemistry in the
College of Arts and Sciences and to the Graduate Council, and was ac
cepted as partial fulfillment of the requirements for the degree of Doc
tor of Philosophy.
August, 1973
Dean, Graduate School






UNIVERSITY OF FLORIDA
3 1262 08556 7443


Full Text
xml version 1.0 encoding UTF-8
REPORT xmlns http:www.fcla.edudlsmddaitss xmlns:xsi http:www.w3.org2001XMLSchema-instance xsi:schemaLocation http:www.fcla.edudlsmddaitssdaitssReport.xsd
INGEST IEID EVFJDNEI7_DDPKXH INGEST_TIME 2011-10-17T20:47:06Z PACKAGE AA00004930_00001
AGREEMENT_INFO ACCOUNT UF PROJECT UFDC
FILES


-•* -

(4, 5-c)FUROTROPY LIDENE - -
A TEN-PI-ELECTRON CARBENE
By
THOMAS HOWARD LEDFORD
A DISSERTATION PRESENTED TO THE GRADUATE COUNCIL OF
THE UNIVERSITY OF FLORIDA
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE
DEGREE OF DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
1973

DEDICATION
This work is dedicated to the past for my parents, to the
present for my wife, and to the future for my children.

ACKNOWLEDGMENT
I would like to express my sincere gratitude to Professor W. M.
Jones and all the members of my supervisory committee for their
scholarly guidance during the preparation of this work. A special
debt is owed to Dr. R. W. King of the University of Florida who
good-naturedly suffered all of my questions about molecular spec¬
troscopy. It is such men as these who keep teaching in its honored
place among the professions.
The financial aid of the Woodrow Wilson National Fellowship
Foundation, the Graduate School of the University of Florida, and
the National Science Foundation made this work possible.
in

PREFACE
"Tom he said . . . the trouble about arguments
is, they ain't nothing but theories, after all, and
theories don't prove nothing, they only give you a
place to rest on, a spell, when you are tuckered out
butting around and around trying to find out something
there ain't no way to find out, "
Huckleberry Finn in
"Tom Sawyer Abroad"
by Mark Twain

TABLE OF CONTENTS
ACKNOWLEDGMENT iii
PREFACE iv
ABSTRACT vi
INTRODUCTION 1
RESULTS 11
DISCUSSION 45
EXPERIMENTAL 57
LIST OF REFERENCES 70
BIOGRAPHICAL SKETCH 73
v

Abstract of Dissertation Presented to the
Graduate Council of the University of Florida in Partial
Fulfillment of the Requirements for the Degree of Doctor of Philosophy
(4, 5-c)FUROTROPYLIDENE --
A TEN-PI-ELECTRON CARBENE
By
Thomas Howard Ledford
August, 1973
Chairman: Professor William M. Jones, Department of Chemistry
(4, 5-c)Furotropylidene has the required structure and the required
number of pi-electrons to belong to the class of aromatic carbenes, a
group of carbenes that show predominantly singlet behavior and react
preferentially with electron-poor olefins. Contrary to this expectation,
(4, 5-c) f urotropylidene appears to behave as a triplet above about
40° C. and adds to ordinary olefins. It also has the unusual property
of undergoing the first step of carbene-carbene rearrangement at low
temperatures. The second step of rearrangement, opening of the
intermediate cyclopropene to the rearranged carbene, is not detected.
Possible rearrangement, though not disproved, is shown not to be the
predominant reaction path such as is seen in certain slightly destabi¬
lized aromatic carbenes.
vi

INTRODUCTION
It has been established that incorporating a vacant orbital of a
carbene into a ring containing conjugated double bonds can, when the
resulting system obeys the Huckel "4n + 2" rule, result in establish¬
ment of so-called "aromatic" carbene systems that have unusual
1,2, 3,4
reactivity patterns. These conditions are satisfied when the
number of double bonds conjugated with the vacant orbital of the
carbene is an odd number. (See Figure 1.)
Examples of such aromatic carbenes include the 2-pi - electron
4
system diphenylcyclopropenylidene (1), the 6-pi-electron system,
1, 2
cycloheptatrienylidene (2), and the 10-pi-electron carbene derived
5
from the 1,6 -methanof 11) annulene ring system (3). (See Figure 2. )
1

2
Aromatic carbenes display behavior patterns that are signifi¬
cantly different from those shown by other carbenes. The delocali¬
zation of charge density from the conjugated double bond system into
the vacant orbital of an aromatic carbene can be expected to increase
the nucleophilicity of the carbene. Also the carbene orbitals can be
expected to split into two different energy levels, affording the possi¬
bility of a stabilized singlet state. (See Figure 3.)
(Figure 3)
Perhaps the most well known of these aromatic carbenes is
1 2
cycloheptatrienylidene (2). ’ This carbene shows the properties one
might expect of a stabilized singlet with increased nucleophilic
character. It prefers to react with electron-deficient, rather than
electron-rich, olefins. For example, in a Hammett study with sub¬
stituted styrenes, cycloheptatrienylidene showed a reaction rate con¬
stant of +1. 05. This compares with reaction rate constants of -0.619
7, 8
for dichlorocarbene and -0. 38 for carbethoxycarbene. Not only is
the sign of the reaction rate constant significant, but there is also
significance in its larger absolute value, an indication that cyclohepta¬
trienylidene is more discriminating than other carbenes; i, e. , more
stable. Consistent with the hypothesized stabilization of its singlet
state, cycloheptatrienylidene reacts with acceptor olefins to form
9
cyclopropanes in which the olefin stereochemistry is preserved.
(Figure 4.)

3
(Figure 4)
Among the substituted cycloheptatrienylidenes that have been
prepared and studied, the following annelated compounds have shown
some interesting new departures in cycloheptatrienylidene chemistry.
(Figure 5.)
Carbenes (4) and (5) have been generated under conditions that
allow observation of their low-temperature esr spectra. Both have
triplet ground states and react with electron-rich olefins such as 2-
butene to form cyclopropane adducts. ^ Evidently both (4) and
(5) behave much like diphenylcarbene. Annelation has, in these two
cases, changed the cycloheptatrienylidene so significantly that a
singlet ground state is impossible. Carbenes (6), (7), and (8) show
even more dramatic effects of annelation upon cycloheptatrienylidene.
All three of these undergo carbene-carbene rearrangement at low to
13 14 15
moderate temperatures according to the following equations. ’ ’
(Figure 6.)
The ground states for these carbenes are unknown, but it is
assumed that the rearrangements, at least, proceed through a singlet
16, 17
state. The nature of the intermediate or transition state leading
to this kind of carbene-carbene rearrangement has been somewhat
controversial. There is recent convincing evidence that such re¬
arrangements proceed via a cyclopropene intermediate such as shown

4
(Figure 5)

5
(Figure 6)

6
15
m Figure 7. In this example, the intermediate cyclopropene (9)
appears to have been trapped by a Diels-Alder reaction with each of
several dienes. The intermediate (9) has also been approached from
another source as shown in Figure 7.
18
(Figure 7)
Monoannelation is said to substantially decrease the stability of
19
the tropyl cation. Since carbene stability is thought to parallel
cation stability, and since monoannelation should have little effect
upon the stability of the intermediate cyclopropene, monoannelation is

7
thought to cause a destabilization of the carbene relative to the cyclo-
propene intermediate, thus increasing the probability of rearrange-
20
ment. Following this line of reasoning further, one could expect to
anticipate rearrangements in other carbenes by an analysis of aroma¬
ticity and cation stability relative to the tropyl system.
The subject of this study is the carbene (4, 5~c)furotropylidene
(11) shown in Figure 8. This carbene should be expected to show at
least some aromatic character, since it does satisfy the Huckel 4n + 2
(Figure 8)
rule (n = 2), having 10 pi-electrons. The structure is not actually a
simple annelated cycloheptatrienylidene in one sense, because it lacks
a double bond analogous to the one between positions 4 and 5 in cyclo¬
heptatrienylidene.
The question of whether aromatic character can be expected in
carbene (11) cannot be answered a priori. In fact, the whole concept
2 122
of aromaticity in troponoid ketones has been attacked by Bertelli; ’
but the concept seems so useful in explaining the behavior of troponoid-
derived carbenes that its continued use seems justified for the time
being. The following analysis, though it is mitigated by Bertelli's
argument, has been used to arrive at estimates of relative aroma-
23
ticities in the following series of ketones.
As delocalization of electrons increases in the ring systems, the
bond order of the exocyclic C = 0 groups will decrease. This will

8
(13) (14)
(Figure 9)
parallel the increasing contribution of the dipolar form of the
*f -
carbonyl group C-O, thus paralleling the ability of the ring system to
stabilize positive charge at the carbonyl carbon atom. This trend
should be in the same direction as cation stability, thus in the same
direction as carbene stability.
A measure of C = 0 bond order can be obtained by a study of the
carbonyl absorption positions in the infrared spectra of the ketones in
this series. It has been shown that, for geometrically similarly
disposed C = 0 groups, there is good correlation between the frequency
of absorption and the calculated bond order; i. e. , as bond order of the
carbonyl group increases, the higher will be the absorption frequency.
As the aromaticity in the series of ketones increases, the bond order
of the C = 0 groups should decrease, showing a lower infrared absorp¬
tion frequency. The ketone (4, 5-c)furotropone (14), having a C = 0
absorption at 1599 cm. , * is therefore less aromatic than benztropone
(13), having its C = 0 absorption at 1590 cm. ^ In turn, benztropone
(13) is less aromatic than tropone, since the carbonyl frequency of

9
tropone (12) is 1582 cm. By this criterion furotropone (14) has
more delocalization than a cross-conjugated cycloheptadienone because
all its bands appear at lower frequencies than the carbonyl band of
, , 23
the dienone (15) shown in Figure 10 (ca. 1635 cm. ).
(Figure 10)
The inference that furotropylidene (11) should have less
aromatic character than cycloheptatrienylidene (2) suggests that
furotropylidene, like other slightly destabilized aromatic carbenes (6),
(7), and (8), might be expected to undergo carbene-carbene rearrange¬
ment. The examination of a hypothetical reaction pathway of a hypo¬
thetical reaction pathway (Figure 11) suggests a possible complication.
Although the carbene (11) should be destabilized relative to the
(11)
(Figure 11)
cyclopropene (16), the product (17) from opening the cyclopropene
should give some caution. The rearranged carbene (17) has a carbene
center attached to an isoben: ran skeleton. Although isobenzofuran
is a 10-pi system, it appare does not show the stabilization

10
associated with other aromatic systems. The parent hydrocarbon,
24
isobenzofuran, has been prepared for the first time only recently.
It polymerizes readily in solution at moderate temperatures. The
reaction pathway in Figure 11 suggests that, for the first time, one of
the destabilized, partially aromatic carbenes might be headed into a
rearrangement pathway in which product stability is quite low. This
is in contrast to the highly stabilized aromatic products of carbene
rearrangements presented on page 4. The effect of this point will
become apparent as the results of this sttidy are presented.

RESULTS
The carbene (4, 5-c)furotropylidene (11) was prepared in all
cases either by pyrolysis or photolysis of the sodium salt of the
tosylhydrazone of (4, 5-c)furotropone (18). The synthetic scheme for
©
(18)
(11)
(Figure 12)
4- N2
producing the required ketone was originally developed by Cook and
23
Forbes. Some modifications of their procedures were used in pre¬
paring the ketone for this study. For example, commercially avail¬
able furan-3, 4-dicarboxylic acid was converted to its diacyl
(Figure 13)
chloride (19) by the action of thionyl chloride in the presence of a
catalytic amount of N, N-dimethylformamide. The acid chloride (19)
was never purified and characterized. Its presence was inferred from

12
its reaction with methanol to afford a quantitative yield of the known
dimethyl ester (20), previously characterized and reported by Cook
23
and Forbes. Using the procedures of Cook and Forbes, the reduc¬
tion of the dimethyl ester was carried out using lithium aluminum
hydride, but the 76 percent yields reportedly attainable did not result.
Direct reduction of the crude diacyl chloride (19) did afford the di¬
alcohol (21) in yields of about 7 0 percent. The di-alcohol was treated
o
/^x:oc|
LIAIH.
!d—
o
‘COCI
(19)
(21)
'CH2OH
*ch2oh
(Figure 14)
with activated managanese dioxide to effect oxidation of one of the
alcohol groups to the aldehyde stage. Again the yields reported in
23
the literature did not result. The reaction usually produced only
about 50 percent of the maximum amount of 3-hydroxymethyl-furan-
4-carboxaldehyde (22), accompanied by about half of the unreacted
di-alcohol (determined by proton resonance spectroscopy). This
situation was made usable by the fact that lead tetra-acetate oxidation
of this crude mixture of di-alcohol and mono-aldehyde afforded the
(21) + MnOz
di-aldehyde (23) in
yields of about 24 percent based on di-alcohol.

13
The 3, 4-furandicarboxaldehyde (23) was condensed with acetone
using the procedure of Cook and Forbes to give exactly the reported
23
yield of 38 percent.
(Figure 16)
Conversion of furotropone into its tosylhydrazone was best
carried out by treatment of the ketone (14) with tosylhydrazine in
tetrahydrofuran containing a trace of anhydrous phosphoric acid. The
reaction worked best when the reactants were merely allowed to stand
together at room temperature for five to seven days. This procedure
gave the tosylhydrazone (24) in 65-70 percent conversion.
=D
(Figure 17)
f
A solution of the tosylhydrazone in tetrahydrofuran was treated
with sodium hydride to produce the sodium salt of the tosylhydrazone
(18). The weight of the sodium salt produced suggests from the
stoichiometry of the reaction that one mole of tetrahydrofuran is
included in the salt as bound solvent. All yields in reactions of this
sodium salt have been adjusted to reflect this effect.

14
/
NcP
ei
s^W— Ar
N
N
(Figure 18)
(18)
II
Thermal decomposition of the sodium salt of (4, 5-c)furotropone
tosylhydrazone (18) in the presence of benzene at 188° C. led to
formation of the formal C-H insertion product (25) in 43 percent
isolated yield. The structure of (25) was assigned primarily on the
basis of its spectral properties. At tau 2.71 and 2. 72 there were two
singlets, assigned to the furan hydrogens and to the benzene hydro¬
gens, respectively. The total of both peaks was seven hydrogens.
The vinyl hydrogens (Ha) appeared at 3. 5-3. 9 tau as a doublet, split
by 11.5 Hz. through coupling to (Hb). Each peak of this doublet
showed a slight splitting (ca. 1 Hz. ) attributable to allylic coupling
to the tertiary hydrogen (Hc). The vinyl hydrogens (Hb) appeared as
a doublet of doublets at tau 4. 33-4. 6. In this pattern the coupling
(11.5 Hz. ) between vinylic protons and the coupling (5-5. 3 Hz. )
between (H^) and (Hc) were both easily discernible. The tertiary
hydrogen (H ) appeared at tau 5. 64. It was primarily a triplet pattern
showing some superimposed allylic splitting. The infrared spectrum
indicated the monosubstituted benzene structure by its absorptions at
762 cm. ~ * and 700 cm. *

15
(25)
(Figure 19)

16
The proton magnetic resonance spectrum of the crude reaction
mixture showed only the benzene C-H insertion product (25). No
evidence of a cycloheptatriene structure was present. Careful
examination of the reaction mixture by analytical thin-layer chroma¬
tography failed to show any biphenyl in the sample.
In a competition reaction allowing the carbene equal access to
benzene and d^-benzene, essentially equal amounts of deuterated and
non-deuterated products were produced as determined by both mass
spectroscopy and by 100 MHz. proton magnetic resonance.
An effort to prepare the product of C-H insertion into cyclo¬
hexane failed because of low yields. The carbene (11) undergoes
reaction with olefins in dioxane solution without taking dioxane into the
reaction mixture. These observations suggest that the benzene C-H
insertion reaction probably does not result from direct insertion, but
through an intermediate that will be discussed in a later section of
this report.
Attempted addition of the carbene (11) to the double bond in
cyclohexene resulted in a mixture that could not be separated cleanly
enough to allow characterization of any of the products. The proton
magnetic resonance spectrum of the crude product did suggest that
some addition to the double bond had occurred., The presence of other
products in the reaction mixture suggests that (4, 5-c)furotropylidene
is not incapable of C-H insertion, but one is left to speculate about
whether the products arise by direct reaction of the carbene or by
secondary processes.
Decomposition of the tosylhydrazone salt in a refluxing solution
of styrene in dioxane (b. p. 101° C. ) was successful in producing a

17
phenylcyclopropane (26) that could be separated and characterized.
Yields as high as 50 percent were produced in solutions that were
quite dilute (1. 5-3 percent styrene). Little, if any, dioxane was
attacked by the carbene. The major side-reaction was production of
considerable amounts of polystyrene. The 100 MHz. magnetic
resonance spectrum of the phenylcyclopropane (26) showed a sharp
singlet at tau 2. 86 with a correct integral for the five phenyl hydrogens.
There were two small singlets (total 2H for both) representing the
furan hydrogens, nonequivalent in this molecule, at tau 2. 96 and
3.01. The vinylic hydrogens (Ha) and (Ha>) appeared as two doublets
in the region from 4. 0 to 4. 33 tau. Each of the doublets was split by
12 Hz. through coupling to the hydrogens (H^) and (H^(). The value of
this coupling between cis olefinic hydrogens suggests that they are
connected to a seven-membered ring. The hydrogens (H^) and
(H^i) appear as two doublets at 5. 25 to 5. 95 tau, again spaced by
about 12 Hz. ; but each peak in these doublets is split very slightly
again (about 2 Hz. ), suggesting coupling across the ring between (H^)
and (H^,), This coupling is to be expected because these hydrogens
(non-equivalent because of the phenyl group) are situated for W-form
coupling. Although the furan hydrogens are also situated for W-form
coupling, and their chemical shift difference is ca. 12 Hz. , the cou¬
pling between them is only barely discernible. It is interesting to
note that the facing pairs of hydrogens on the seven-membered ring
and in the furan system show decreasing chemical shift differences
with increasing distance from the symmetry-disturbing phenyl group.
The cyclopropyl hydrogens in the phenylcyclopropane (26) present the
expected ABX pattern. The (Hc) hydrogen (X) appears in the 7. 53-7. 85

18
PROTON MAGNETIC RESONANCE SPECTRUM OF PRODUCT
(26)
(Figure 20)

19
T
T
PROTON MAGNETIC RESONANCE SPECTRUM OF PRODUCT
(26)
ENLARGED VIEWS OF ABX PORTION
T
T-* 1 h 1 J—r
"i :—i— ——r
±
(Figure 21)

20
tau area as two doublets that show overlap between the two central
peaks. The geminal cyclopropyl hydrogens (AB pair) appear as the
expected pair of overlapping quartets in the region 8.7-9. 0 tau. The
spacing between the midpoints of the two quartets (1/2 abs. value of
+ Jgy) allows easy calculation of the predicted spacing between
lines 9 and 12 in the X portion of the spectrum. The predicted
spacing between lines 9 and 12 (15. 6 Hz. ) was observed and permitted
assignment of lines 9 and 12 as the two outside lines in the X portion
2 6
of the spectrum. The value of JAB = 5. 4 Hz. was directly
measurable from the spectrum.
The infrared spectrum of (26) shows absorptions near 700 cm.-^
and 750 cm. , consistent with the mono-substituted benzene
structure. Absorptions at 860 cm. * and 1028 cm. * offer confirma¬
tory evidence of the cyclopropane ring indicated by the absorption at
-1 27
3060 cm.
Pyrolytic decomposition of the tosylhydrazone salt (17) in the
presence of 1-butene gave the expected ethylcyclopropane (27) in
about 50 percent isolated yield. The cyclopropane was accompanied
by three minor by-products that were never identified. The proton
magnetic resonance spectrum of (27) showed a two-hydrogen singlet at
2. 95 tau for the furan hydrogens. The vinylic protons (Ha) and (Hai)
that showed a pair of doublets in the phenylcyclopropane (26) appeared
in this ethylcyclopropane as an overlapped pair of doublets split by
11.5 Hz. at tau 3. 87-4. 3. The other pair of vinylic hydrogens (H^)
and (H^i) appeared as a pair of separated doublets at 5. 25-5. 8 tau
showing the same W-form coupling observed in the phenylcyclopropane
(26). It is interesting to observe the smaller symmetry disturbance

21
—yrr-^1-.. ,: :. .:.v i^
PROTON MAGNETIC RESONANCE SPECTRUM OF PRODUCT (27)
(18)
/
H
CHp—CH^
(Figure 22)

22
produced by the ethyl group in (27) compared with the larger effect
of the phenyl group in (26). Whereas the furan hydrogens were re¬
solvable in (26), they were not resolvable in (27). Further evidence
of lower disturbance of symmetry is provided by the fact that the pair
of doublets representing the vinylic hydrogens (H ) and (H ,) are over-
lapped in (27), but well separated in (26). The remainder of the
spectrum of the ethylcyclopropane (27) was a complex eight-hydrogen
signal in the region of 8. 3-9. 5 tau that included the cyclopropyl
hydrogens and the hydrogens on the ethyl group.
Thermal decomposition of the tosylhydrazone salt (17) in the
presence of isobutene gave a remarkably clean reaction producing the
dimethylcyclopropane (28) in 28 percent yield. The structure was
assigned primarily on the basis of the proton magnetic resonance
spectrum. This molecule provides an excellent example of the pro¬
found effects of molecular symmetry on nuclear magnetic resonance.
A plane of symmetry can be drawn through the dimethylcyclopropane
(28). This plane includes the plane of the cyclopropyl ring and bisects
the plane of the fused furotropyl ring system. This symmetry results
in magnetic equivalence of the furan hydrogens and both sets of vinyl
hydrogens in the seven-membered ring. This results in a simplified
spectrum for the compound. A two-hydrogen singlet for the furan
hydrogens appeared at 2. 83 tau. Instead of the more complex vinyl
absorptions observed in the styrene adduct (26) and in the 1-butene
adduct (27) a simple AB pattern appeared. A doublet centered at 3.81
tau showed a two-hydrogen signal for the (H ) pair. Another doublet
centered at 5. 09 tau was presented by the (H^) pair of hydrogens. The
coupling between (Ha) and (H^) was 11. 5 Hz. , about the same value

23
PROTON MAGNETIC RESONANCE SPECTRUM OF PRODUCT (28)
(17) +
H
H
WcA
/ v
(Figure 23)

24
observed in other compounds in this series. The two methyl groups
produced the expected six-hydrogen singlet at 8. 9 tau, accompanied
by a nearby singlet for the two equivalent cyclopropyl hydrogens at
9. 2 tau.
The profound effects of changes in symmetry in spirocyclo-
propanes such as (26), (27), and (28) provide an excellent basis for
assignment of stereochemical configurations in cis- and trans-1,2-
disubstituted spirocyclopropanes by nuclear magnetic resonance.
Trans - 1,2-disubstituted spirocyclopropanes (see Figure 24) can be
expected to have equivalent sets of furan hydrogens and vinylic
hydrogens facing each other across the ring. This is because rotation
symmetry
axis
about the twofold axis of symmetry shown in the drawing makes
these sets of hydrogens equivalent. On the other hand, cis-1, 2-
disubstituted spirocyclopropanes can be expected to show the same
kind of complex pattern observed for the vinyl hydrogens as was seen
in the monosubstituted spirocyclopropanes (26) and (27), resulting
from the non-equivalency of facing pairs of hydrogens on the opposite
sides of the seven-membered ring. A model for cis-disubstituted
spirocyclopropanes of this type has been prepared by Krajca from the
14
reaction of 4, 5-benzotropylidene with cyclohexene. This compound
(29) shows a nuclear magnetic resonance pattern in the vinyl region

25
that is essentially identical to the pattern shown by the phenylcyclo-
propane (26). A similar vinylic absorption pattern has been used to
(Figure 25)
assign stereochemical configurations in a series of spirocyclopro-
panes derived from the reactions of 4, 4-dimethylcyclohexadienylidene
with various olefins. This is shown in Figure 26. Both cis- and
trans-1,2-disubstituted spirocyclopropanes of this type were prepared.
(Figure 26)
Both isomers showed the expected effect of symmetry differences upon
the nuclear magnetic resonance spectra in the vinylic region.
With the above-described basis for making stereochemical
assignments in 1, 2-disubstituted spirocyclopropanes, it is possible to
study the stereospecificity of the reaction of furotropylidene (11) with
olefins. The stereospecificity test is widely used as a chemical
28,29
test for distinguishing between singlet and triplet states in carbenes.
Stereospecific addition; i. e. ,
addition to olefins to produce cyclopro-

26
panes in which olefin stereochemistry is preserved, is characteristic
of singlet carbenes. Non-stereospecific addition, in which olefin
stereochemistry is not preserved, is characteristic of triplet
carbenes.
A stereochemical study was undertaken using cis- and trans-2-
butenes as acceptor olefins for the carbene (11). Thermal decompo¬
sition of the tosylhydrazone salt in the presence of cis-2-butene at
118-120° C, and in the presence of trans-2-butene at the same tem¬
perature produced two crude reaction mixtures that were virtually
identical in their proton magnetic resonance spectra. Gas chromato¬
graphic examination of the crude reaction mixtures using a 100-foot
capillary column coated with Ucon LB-550 showed at least 11 com¬
ponents in the reaction mixtures. Most of the chromatographic peaks
were in the same quantitative relation to each other in both mixtures.
Separation of the main peak on a preparative gas chromatographic
instrument, though it gave a less-perfect separation than the capillary
instrument, did allow some narrowing in the choice of the significant
peaks in the chromatograms prepared on the capillary instrument,
since this fraction was shown by nuclear magnetic resonance to con¬
tain the major components present in the crude product. The signifi¬
cant area turned out to be a group of two smaller peaks and one major
peak that were not even well separated on the capillary instrument.
Quantitative differences were seen in the relation of the two smaller
peaks when comparing samples prepared by thermal reaction with the
cis and trans olefins, but the significance of this difference between
these two smaller peaks may be trivial because of the following obser¬
vations: 1. The proton magnetic resonance spectra (vide infra) of

27
both reaction mixtures were identical. Both crude reaction mixtures
appeared to be predominantly the trans-spirocyclopropane (vide infra).
2. There was no indication of the presence of the cis-spirocyclopro-
pane in either sample to the limit of detection by the proton magnetic
resonance spectra. 3. Thermal reaction of the tosylhydrazone salt
with trans-2-butene is most likely to produce the more stable trans-
spirocyclopropane if product isomerization is taking place. A photo¬
chemical decomposition of the salt in the presence of cis-2-butene is
most likely to produce the cis-spirocyclopropane, because of expected
lower probability of thermal cis-trans isomerization at the milder
temperatures, ca. 50° C. , used. A comparison of the capillary
chromatograms of these two reactions showed the same quantitative
relation among the three peaks in this significant area. Apparently
the major peak is the trans-spirocyclopropane (vide infra). The two
minor peaks were never identifiable for the reasons of small sample
size and difficulty of purification. The proton magnetic resonance
spectra suggest that these are probably mainly C-H insertion products.
The attainment of the same product mixture from carbene reactions
with a pair of isomeric cis-and trans-olefins is the criterion for com¬
plete loss of stereospecificity in the reaction.
The failure to isolate any of the cis - spirocyclopr opane from the
reactions with the 2-butenes and to demonstrate the stability of the cis-
isomer to reaction conditions does leave the experiment open to the
criticism that the cis-isomer is possibly being formed, then is decom¬
posing to either the trans-isomer or to some other product. This
possibility is impossible to exclude rigorously in the present case,
but some inferences for the stability of the cis-isomer can be drawn

from a study of known model compounds. Cyclopropanes of the type
(30) are subject to a cleavage of the cyclopropyl ring followed by
28
cx
.R
30: a. R = C02CH,
b. R = H
R
(30 a, b)
(Figure 27)
isomerization to an indane derivative. The substituted cyclopropane
(30a) undergoes isomerization at 130°C. , but the unsubstituted cyclo¬
propane (30b) is stable at 150° C. Similarly, one should expect an
enhanced rate of isomerization in the vinyl-substituted spirocyclo-
propane (31) (Figure 28) because of stabilization of radical inter¬
mediate (32). The isomerization is slow at 100° C. , since the cyclo¬
propane can be isolated as the main product from reaction mixtures
exposed to that temperature for 0. 5 hr. (vide infra). This suggests
that cis-dialkyl-spirocyclopropanes would require substantially
higher temperatures before isomerization to the trans isomer would
occur at a significant rate.
‘O'
(33)
(31)
(32)
(Figure 28)

29
Isolation and characterization of the trans - spirocyclopropane
produced from the reaction of carbene (11) with the cis- and trans-2-
butenes proved to be as difficult as the foregoing discussion would
suggest. Reaction of trans-2-butene by decomposition of the sodium
salt at 115°C. produced a crude reaction mixture, the proton mag¬
netic resonance spectrum of which suggested that the main component
(18) +
(Figure 29)
was the trans - 1, 2-dimethylcyclopropane (34) contaminated with C-H
insertion products. Preparative layer chromatography on silica gel
plates did not improve the appearance of the spectrum very much
until the main band was collected and re-chromatographed on silica
gel plates using very low sample loading. This allowed separation
into three bands, the major one of which gave a spectrum suggesting
a fairly pure sample of the trans-adduct (34). Because of small
sample size, neither of the two minor components was identified. The
yield of the trans adduct (34) appears to be in the neighborhood of
25 percent, but extensive handling of small samples makes this
number unreliable. The assignment of the structure (34) rests pri¬
marily on the proton magnetic resonance spectrum. There is the
usual sharp singlet at 2. 9 tau for the furan hydrogens. From the
discussion on pages 17, 18, and 19 one would expect the AB pattern
that is observed in the vinylic region, produced by the hydrogens on

30
-■■■■■■ ’£ --'Y '■1 TTT~';~~
PROTON MAGNETIC RESONANCE SPECTRUM OF PRODUCT (34)
(Figure 30)

31
the seven-membered ring. One of the AB doublets is centered at 3. 8
tau, the other at about 5. 3 tau, with a coupling of 11.5 Hz. At 8. 65
to 8. 9 tau there are two peaks whose relative intensity suggests they
are coupled to the cyclopropyl hydrogens that appear slightly upfield.
There is a third sharp peak just downfield of these cyclopropyl
hydrogens at about 8. 93 tau, the shape and intensity of which leave
its interpretation open to question. It is probably a spurious peak
due to the presence of some impurity, but it could also be the result
of so-called "virtual coupling" through the cyclopropyl hydrogens.
The integration curve is not much help in deciding, since the effect
of this peak on the total is not very great. The best integral does
result from considering it to be a spurious peak, though. The spacing
of this suspicious peak from the closest of the other two is, whether
fortuitous or not, equal to the spacing between the other two and equal
to one of the spacing patterns seen in the signal for the cyclopropyl
hydrogens whose multiplet appears at 9. 05 to 9. 5 tau. The integration
curve for the cyclopropyl hydrogens appears to fall just a little bit
short of the required amount, but some of this signal may be buried
under the "suspicious" peak already discussed. To judge from this
spectrum, there is very little, if any, of the cis-spirocyclopropane
present in the sample.
An overview of the results of the stereochemical study with the
2-butenes suggests that a study with another olefin, one that would
hopefully give a cleaner reaction, would reinforce the argument for
the loss of stereospecificity in addition reactions of this carbene.
Accordingly a study was carried out using trans-deuteriostyrene as an
acceptor for the carbene. From the experience gained with the non-

32
deuterated styrene reaction it was known that this reaction (shown in
Figure 20) can be used to produce rather pure samples of the phenyl-
cyclopropane.
The required deuterated styrene was prepared by the stereo¬
specific addition of dicyclohexylborane to phenylacetylene followed by
30
hydrolysis with deuterioacetic acid to free the styrene. Formal
addition of the carbene to this olefin was carried out by pyrolysis
of the tosylhydrazone salt in a dilute solution of the olefin in boiling
dioxane (b. p. 101° C. ). The resulting phenylcyclopropane was
separated by preparative layer chromatography. Use of d^-benzene
as a solvent allowed observation of the geminal cyclopropyl hydrogens
by 100 MHz. proton magnetic resonance spectroscopy as two doublets
appearing at 8. 7-9. 2 tau. One of the doublets was split by 8. 5 Hz. ;
the other, by 7. 0 Hz. By double irradiation to decouple the neighboring
cyclopropyl hydrogen (H^) from the geminal pair, the four signals
were caused to collapse to two signals having a separation of about
12 Hz. Integration of the four signals (before decoupling) and the two
signals (after decoupling) showed the presence of an equal mixture
of the two possible isomers.
Though the formation of an equal mixture of the two possible
deuterio phenylcyclopropanes in this study suggests non-stereospecific
addition of the carbene to the olefin, the result is not conclusive unless
the possibility of olefin isomerization before reaction and the possi¬
bility of product isomerization after reaction are excluded. The
olefin was determined to be stereochemically stable under the reaction
conditions by a control experiment. The stability of the product is not
so easily proved. Separation of the two stereoisomeric products is not

33
PROTON MAGNETIC RESONANCE SPECTRUM OF PRODUCT (26a)
SHOWING SIMPLIFICATION OF ABX
(Figure 31)

34
possible, so a direct test for isomerization under reaction conditions
is not possible. The best remaining option is to conduct the reaction
at a temperature at which product isomerization is highly unlikely.
One can also draw inferences about the thermal stability and the
photochemical stability of the phenylcyclopropane adduct by examina¬
tion of model compounds (vide infra).
The reaction with trans-deuteriostyrene was repeated by decom¬
posing the sodium salt of the tosylhydrazone photolytically at about
45° C. This procedure also produced an equal amount of the two
possible stereoisomers. Though it might have been desirable to
have carried out the photolysis at even lower temperatures, the
properties of this carbene are such that it does not add readily to
olefins at low temperatures. This point will be discussed further in
connection with reactions of this carbene with butadiene. The styrene
did not isomerize under photolysis.
The photolytic and thermal stability of the phenylcyclopropane
(26a) can be inferred from the following data: 1. The vinylcyclopro-
pane (31) (see Figure 28) requires temperatures greater than 100°C.
for an appreciable rate of ring-opening, followed by closure to the
cyclopentene (33). 2. The same vinylcyclopropane was determined
(vide infra) to be photolytically stable under reaction conditions. 3.
The somewhat similar 1-phenylspiro(2. 6)nona-4, 6, 8-triene (35)
shown in Figure 32 requires temperatures greater than 75°C. for
, 31
isomerization to the 8-phenylbicyclo(5. 2. 0)nona- 1, 3, 5-triene (36),
but its isomerization is aided by the formation of a new stable com¬
pound of a type that cannot be formed from (26). 4. The vinylcyclo-
o 31
propane (37) rearranges to (38) at 50-75 C. On the other hand, the

35
butadiene adduct (39) is stable enough to be isolated by preparative
gas chromatography.^
75-1 00°
->
c6h5
(37)
ch3
(Figure 32)
Pyrolysis of the tosylhydrazone salt (18) in the presence of 1, 3-
butadiene at 118°C. produces almost exclusively the 1,4-addition
product (33) (55 percent yield) shown in Figure 33. It has been hypoth¬
esized that triplet carbenes might react with 1, 3-dienes in the 1, 4-
addition mode. Few carbenes, if any, actually do add in this manner

36
by direct reaction. Most adducts arising from a formal 1, 4-
addition are products from the thermal isomerization of initially
formed 1, 2-addition products such as (3 1). That proved to be true
in this case also. Thermal decomposition of the tosylhydrazone salt
in 1, 3-butadiene at 100°C. for short reaction times (0.5 hr. or less)
produced the 1,2 adduct (31). Heating of the vinylcyclopropane (31)
(18)
iooa >
(Figure 33)
at 120° C. for 0. 5 hr. caused complete conversion to the isomeric
cyclopentene (33).
Structural assignment of the 1, 4-addition product (33) was based
on the following spectral data. In the proton magnetic resonance
spectrum there is the expected two-hydrogen singlet at 2. 82 tau for
the furan hydrogens. Since this molecule has the same kind of
symmetry as the dimethylcyclopropane (28) shown in Figure 22, one
can predict the same kind of AB pattern for the vinyl hydrogens (Ha)
and (H^) in the seven-membered ring. This expected four-line AB
pattern is observed in (33). One of the doublets in the AB pattern is
centered at 3. 9 tau and is split by 11. 5-12 Hz. The other doublet is
centered at 4. 57 tau (representing the (H^) hydrogens), but the left
half of the doublet has a partially superimposed peak from the vinylic
hydrogens in the cyclopentene ring (Hc). The integral for the lower-

37
»• , , , j , , , - , »• WT »0 X -1 M
PROTON MAGNETIC RESONANCE SPECTRUM OF PRODUCT (33)
(Figure 34)

38
field doublet is two hydrogens. The integral for the upper-field
doublet containing the signal for the cyclopentene olefinic hydrogens
indicates a total of four hydrogens. The remainder of the spectrum
is a sharp singlet at 7. 49 tau with a correct integral for the four
allylic hydrogens (H^). The lack of discernible splitting of the
allylic hydrogens is consistent with the reported 0. 5 Hz. allylic
33
splitting in cyclopentene itself. The high symmetry of the 1, 4-
adduct (33) gives rise to some doubt as to whether the C=C bond in the
cyclopentene ring should even be infrared active at all. Nevertheless,
there is a weak absorption at 1618 cm. * that does fit the known
pattern for C = C stretch in five-membered rings (cyclobutene, 1566
-1 -1 , -1 34
cm. ; cyclopentene, 1611 cm. ; cyclohexene, 1649 cm. ).
Structural assignment of the 1, 2-addition product with butadiene
was based on the following information. The furan hydrogens appeared
as a two-hydrogen singlet at 2. 9 tau. The vinyl region showed
clearly the results of the symmetry-disturbing exocyclic vinyl group.
The pattern for the (H ) and (H ,) hydrogens was a partially over-
lapping pair of doublets showing the same 11.5 Hz. coupling between
the AB pair in the seven-membered ring that has been observed in
(26) and (27). This four-line signal for the (H ) and(Ha,) hydrogens
was about 3. 9-4.2 tau. Another four-line signal for the (H^) and (H^i)
hydrogens appeared at about 5. 1-5.65 tau. Once again, since these
two hydrogens are nonequivalent, the W-form coupling of ca. 2 Hz.
was observed in addition to the coupling with the (Ha) and (Hai)
hydrogens. The vinylic hydrogens belonging to the exocyclic vinyl
group appeared between the two sets of signals for the AB pair in the
seven-membered ring. The (H^) signal appeared from about 4.2 to

39
I
- ■ - - I‘ t ^ 1 T.-X.„n ■ ,f l-7 JL . ,. 1, . T
PROTON MAGNETIC RESONANCE SPECTRUM OF PRODUCT (31)
(31)
(Figure 35)

40
rpz
i
■ *1 > f—'' ■ -,-J ¡ r-J—, y —T h
PROTON MAGNETIC RESONANCE SPECTRUM OF PRODUCT (31)
SHOWING ENLARGEMENT OF ABX PORTION
(Figure 36)

41
4. 45 tau with primarily a four-line pattern. The (H2) and (H3)
hydrogens were at 4. 75-5. 0 tau presenting a complex pattern that had
so much fine structure that direct measurement of the coupling
constants was not possible. Use of a 100-MHz, spectrometer made
it possible to resolve each set of vinylic hydrogens, both the AB
pair and the exocyclic vinyl hydrogens, sufficiently to allow an accu¬
rate integration for each signal. All of the integrals were satisfac¬
tory, The remainder of the spectrum presented the expected ABX
pattern for the cyclopropyl hydrogens. Direct measurement of
was 5. 0 Hz. The AB portion of the spectrum (for the vicinal cyclo¬
propyl hydrogens) was at 8. 6-9. 0 tau. The X portion was at about
8. 15-8. 5 tau. The AB signal allowed easy recognition of the expected
pair of overlapping quartets. The X signal gave an integral that was
slightly lower than the correct value because some of the lines were
buried in instrument noise. Four of the lines were visible, but only
two of them were very strong. The spectrum also showed a sharp
singlet at about 8. 6 tau from a contaminating inhibitor (2, 6-di-tert,
butyl-4-methyl phenol) picked up during exposure of the sample to a
commercial grade of tetrahydrofuran. Elemental analysis was made
impossible because of the presence of the inhibitor, since it was
difficult to separate from the sample. The problem was sur¬
mountable by the ready conversion of the 1,2-adduct to the 1,4-
adduct (33), which was easy to separate from the inhibitor and to
provide in pure form for elemental analysis. The exocyclic vinyl
group in (31) was shown by infrared. DD
Decomposition of the tosylhydrazone salt by photolysis at low
temperatures in the presence of 1, 3-butadiene caused a remarkable

42
change in the character of reaction with this olefin. At temperatures
of -60° to -30° C. it produces the product (40), shown in Figure 37,
in about 40 percent yield as the only hydrocarbon product identifiable.
The structure of (40) was identified by the striking similarities in its
spectra with the spectra of a number of similar compounds recently
15
prepared and elucidated in detail by Coburn. In the proton mag¬
netic resonance spectrum the furan hydrogens produced a two-hydrogen
singlet at 2. 83 tau. The vinylic hydrogens (Ha) produced an AB
pattern centered near 4. 0 tau split by 10 Hz. The other vinylic
hydrogens (H^) produce a poorly resolved peak at 4.47 tau. The
allylic hydrogens appear as a broadened peak at 7. 52 tau. The
cyclopropyl hydrogen (Hg) appears as a doublet at about 7. 85 tau,
coupled by about 5 Hz. to the other cyclopropyl hydrogen (H^) which
appears upfield as a multiplet at 9. 15-9. 45 tau.
Photolysis of the tosylhydrazone salt at intermediate tempera¬
tures (ca. 40° C.) produced a mixture of (40) and the 1,2-addition
product (31) from reaction with butadiene. The ratio was about
45:55. None of the 1, 4-adduct (33) was produced.
In control experiments the 1, 2-adduct (31) was shown to be
stable to photolysis; therefore, it is not the source of the product (40).
The product (40) was shown to be thermally stable for at least 20
minutes at 140° C. , since it could be purified by preparative gas
chromatography.
To see if normal carbene behavior could be elicited at low
temperatures, an effort was made to add the carbene to trans-2-
butene by photolysis of the tosylhydrazone salt at -50° C. Normal
carbene addition to the olefin did not occur, as shown by the proton

43
" —v y- ■■’■■■■ ■?—■-—v— r
PROTON MAGNETIC RESONANCE SPECTRUM OF PRODUCT (40)
-50°
(18) -f CH2~CH—CH=CH2 >
(40)
(Figure 37)

44
magnetic resonance spectrum of the crude product. The friable
appearance of the product suggested that it was at least partly
polymeric.
In experiments designed to allow equal amounts of olefin
acceptors to compete for the carbene (11), the following relative rate
data were obtained:
OLEFIN RELATIVE RATE
1 -butene 0. 8
isobutene 1. 0
1, 3-butadiene 9. 0
(Table 1)
One experiment was done to attempt to observe a signal in the
proton magnetic resonance spectrum indicating the operation of the
chemically induced dynamic nuclear polarization (CIDNP) phenom-
3 6
enon. Such an observation would be indicative of the presence of a
triplet carbene. Thermal decomposition of the tosylhydrazone salt in
solution in an nmr sample tube containing a mixture of approximately
20 percent cyclohexene in d^-dimethyl sulfoxide failed to show the
CIDNP phenomenon. This could be attributable to the low solubility
of the tosylhydrazone salt in this medium, indicated by the failure to
observe the presence of the salt in the spectrum of the solution.

DISCUSSION
Thermolysis or photolysis of tosylhydrazone salts of tropone
and substituted tropones in solution have been found to give at least
five different kinds of reactive species (Figure 38). Unsubstituted
1 2, 9
tropone (12) shows chemistry of only the singlet carbene (I).
Mono-annelated tropones (13) and (41) show some chemistry expected
of the singlet carbene (I), but in general, their chemical behavior
is dominated by the bicycloheptatriene (III) and the rearranged
singlet and triplet aryl carbenes (IV) and (V). ^ The di-annelated
tropone (42) shows only the chemistry of the bicycloheptatriene (III)
and the aryl carbene, presumably singlet (IV) and triplet (V). ^ The
di-annelated and tri-annelated tropones (43) and (44) show typical
diaryl carbene chemistry. They have been shown to have triplet
ground states, but their chemistry is dominated by the singlet. ^
The reasons for these differences can be qualitatively rationalized
in terms of the expected relative energies of the different intermediates.
Carbene stabilities are thought to run parallel to cation stabili¬
ties. Mono-annelation, known to de-stabilize the tropyl cation, should
not be expected to have significant effect on the stability of the inter¬
mediate cyclopropene (III). Mono-annelation should then decrease the
stability of the carbene relative to the cyclopropene intermediate,
2 0
making the rearrangement easier. The di-annelated species (43) and
the tri-annelated species (44), by incorporating into the fused benzene
systems the double bond that must suffer attack in order for
45

46
✓
<6
(12)
A,
B,
D = H
(13)
A,
D
= H; B = fused benzene ring
(41)
A
= fu
sed benzene ring; B,
D =
H
(42)
A,
B
= fused benzene ring;
D =
H
(43)
A,
D
= fused benzene ring;
B =
H
(44)
A,
B,
D = fused benzene ring
(Figure 38)
i=\ a

47
rearrangement to occur, reduce the probability of rearrangement by
increasing the relative energy of the intermediate cyclopropene
because of loss of benzenoid aromaticity. The di-annelated species
(42) does not require as much loss of aromaticity to form the cyclo¬
propene (III), so it undergoes rearrangement easily. Many carbenes
that are formed in their singlet states react in their singlet states,
because the singlet is so reactive that reaction occurs before colli-
sional deactivation to triplet, if that is the ground state, can occur.
Equilibration between a reactive singlet and a relatively unreactive
triplet can also cause the same effect.
The present carbene (11) fits this overall scheme, but as a
result of its unusual structure, it seems to have a unique place in the
scheme. In the first place, unlike any of the other carbenes studied,
under certain conditions (above about 40° C. ) its chemistry is appar¬
ently dominated by the triplet.
The complete loss of stereospecificity in reactions of (4, 5-c)furo-
tropylidene is consistent with triplet behavior. The nonstereospecific
addition of a carbene in solution is now well established as a criterion
for interpreting the reaction in terms of a two-step reaction; i. e. , via
triplet. The present stereospecificity studies must be taken with the
37
caveat of Gaspar and Hammond in mind that "Nonstereospecific
addition cannot be taken as a proof that an attacking species is a
triplet unless it has also been shown that under some other conditions
a species of the same composition can give stereospecific addition. "
Closs, in a more recent view, asserts that non stereospecific reac¬
tions can always be interpreted as proceeding via the two-step mech-
29
anism; i. e. , via triplet.

48
The relative reactivities of (4, 5-c)furotropylidene in reactions
with olefins also fit the triplet pattern. It is well accepted that con¬
jugated dienes, such as 1, 3-butadiene, show a high relative rate of
reaction with triplets because of allylic stabilization of the di-radical
intermediate (Figure 39) in the two-step reaction. The common use
of butadiene as a "triplet scavenger" to improve stereospecificity of
VR
K-
(Figure 39)
carbene reactions by selectively draining off triplet illustrates this
. . , 38
principle. The relative rates found in this present study also fit
the relative rate pattern for the rate of radical addition vs. abstraction
39
with the same olefins.
Interpreting the reaction of (4, 5-c)furotropylidene with benzene
in terms of triplet chemistry is aided by consideration of some related
reports in the literature. Bis(carbomethoxy)carbene has been gener¬
ated by photolysis of the corresponding diazo compound under two
32
sets of conditions. Direct photolysis produces a carbene that reacts
in the singlet state as shown by the stereospecificity of its reactions
with olefins. Photosensitized decomposition produces a carbene that
reacts in the triplet state as shown by the loss of stereospecificity in
its reactions with olefins. The same carbene, prepared by each of
the two methods, was allowed to react with benzene. Direct photolysis
of methyldiazomalonate in benzene gave the cycloheptatriene (45 ) and

49
the C-H insertion product (46) in a ratio of 2. 7 to 1. 0. The photo¬
sensitized reaction gave the same two compounds in a ratio of 1.6 to
(Figure 40)
1. 0. The increased amount of the phenylmalonate (49) when the
carbene is prepared in the triplet state is consistent with the inter¬
mediacy of the di-radical, which can either close to the norcaradiene
related to the cycloheptatriene, or undergo hydrogen shift to form the
phenylmalonate. Increased triplet character in the attacking carbene
increases the amount of the C-H insertion product. If the slow step
of the reaction is attack of triplet carbene upon a benzene double
bond, the absence of a deuterium isotope effect is to be expected.
This was demonstrated in the present study with (4, 5-c)furotropylidene.
Still, there are hazards in interpreting the insertion of furo-
tropylidene into the C-H bonds of benzene as necessarily a triplet
behavior. A di-radical intermediate such as that shown in Figure 40
could arise from another path. Consider, for example, the six-
membered carbocyclic carbene, 4, 4-dimethylcyclohexadienylidene.
It apparently reacts with olefins in the singlet state in solution. It
reacts with benzene to produce a spironorcaradiene (47) shown in
Figure 41, This spironorcaradiene isomerizes at 100°C. to produce
the intermediate (48) that is very much like the di-radical intermediate

50
that could arise from triplet attack upon the benzene double bond.
Here is apparently a singlet pathway to the di-radical intermediate.
(Figure 41)
None of the analogous norcaradiene was detected in the furotropylidene
case, even when the reaction was carried out by photolysis at room
temperature; but the possibility of that intermediate is very real be¬
cause of the complexity of the mixture that was produced in the reac¬
tion. The absence of a deuterium isotope effect would also be
expected from the singlet pathway.
Although no one piece of evidence in this report can be said to
rigorously prove that (4, 5-c)furotropylidene is behaving as a triplet
at temperatures above 40°C., certainly the mass of evidence taken
as a whole looks fairly convincing. One thing is certain--the cyclo-
propene intermediate (type III, Figure 38) dominates at lower tempera¬
tures. This is shown by the trapping of the cyclopropene intermediate
(16) (see Figure 11) by the Diels-Alder reaction with butadiene to form
the adduct (40) shown in Figure 37. The cyclopropene seems likely
to have formed from the singlet state of the carbene, since the car-
bene is almost certainly initially formed in the singlet state, and since
intramolecular reactions seem to be favored for carbenes in the

51
i n i /
singlet state. ’ For example, direct irradiation of aliphatic
alpha-diazoketones produces a predominance of the photochemical
Wolff rearrangement; but photosensitized irradiation, which should
increase triplet formation, produces an increased amount of cyclo-
17
propanes, suggesting normal intermolecular carbene reactions.
Formation of the cyclopropene intermediate (16) is a particu¬
larly surprising result, since the (4, 5-c)furotropylidene (11) has not
shown any evidence of rearrangement to the isobenzofuran skeleton
as might have been expected (Figure 11). This rearrangement, if it
does occur, might be impossible to detect with certainty because of
the high reactivity of the isobenzofuran molecule. It polymerizes
24
rapidly in solution. While one cannot say with certainty that none
of the cyclopropene opens to the isobenzofuranyl carbene, the fact
that yields of up to 50 percent of formal furotropylidene addition
products are formed does allow one to say that the rearrangement is
not the overwhelmingly predominant process such as is observed
with the annelated cycloheptatrienylidenes (13), (41), and (42) in
Figure 38. Perhaps the ring-opening of the cyclopropene intermediate
(16) to the isobenzofuranyl carbene is precluded because not enough
aromaticity is gained in that direction.
Why does triplet chemistry predominate in the reactions of
furotropylidene at moderate to higher temperatures? The apparent
ease of crossing from singlet to triplet suggests that these two elec¬
tronic states are at very similar energy levels in this carbene. The
effect of temperature in changing the character of the reactions of this
carbene has a few interesting parallels in the literature.

52
Closs has reported a case in which there may be a temperature
40
effect upon a singlet-triplet equilibrium. Diphenyl carbene, known
to have a triplet ground state, was produced by irradiation of di-
phenyldiazomethane in the presence of olefins. In reactions with cis-
and trans-2-butenes, cyclopropanes account for no more than 10 per¬
cent of the hydrocarbon products. Hydrogen abstraction was the main
reaction pathway. At -10°C. the cis-and trans - 1, 2-dimethyl-3, 3-
diphenylcyclopropanes were formed in a ratio of 3. 2 from the cis-2-
butene. The corresponding ratio from the trans olefin was 0. 04.
Lower temperatures caused increased stereospecificity. At -66°C.
the product ratio from the cis -2-butene was 9. 0. At a given tem¬
perature the product ratio was found to be independent of the butene
concentration over a range of 150-fold dilution with cyclohexane. The
presence of oxygen failed to change the isomer ratio of products.
Closs postulated the following scheme (Figure 42) as a possible ex¬
planation of his observations. He suggested that intersystem crossing
is much faster than any other reaction in the system and that the
reverse crossing is also very fast so that both singlet and triplet are
effectively in equilibrium. The relative rates of the singlet (kag) and
the triplet (k ) addition steps and the position of the singlet-triplet
equilibrium both determine the fraction of stereospecific singlet-state
addition. Since diphenylmethylene is known to have a triplet ground
state, the rate of crossing to the triplet (k^) must be greater than the
rate of triplet crossing to the singlet (k ; therefore, in view of the
observed product ratios, the rate of singlet addition (k ) must be
much greater than the rate of triplet addition (k&t). If the difference
in the free energies of activation for the two addition reactions is

53
larger than the free energy difference between the two electronic
states, the temperature difference could be explained on this basis
alone. It is not possible to determine whether a temperature effect
upon the position of singlet-triplet equilibrium is being observed, but
this is a possibility.
(Figure 42)
Thermal effects upon the population of electronic states are
known in certain photochemically produced noncarbene species. An
41
example is a study of pyrene-d1Q in a polymethylmethacrylate matrix.
The triplet yield plus the fluorescence yield was near unity at -196°C.
As the temperature was raised, two effects were observed. First,
the triplet yield increased with increasing temperature, suggesting a
temper ature-dependent process that produces increasing intersystem

54
crossing from vibrationally excited singlet to second triplet state
(^2). The second effect observed was a falling off of the sum of
triplet yield and fluorescence yield from the expected value of unity
as temperature increased. This suggested a thermally dependent
radiationless transition from the first singlet state to the ground
state. The energy of activation for the temperature-dependent com¬
ponent of the intersystem-crossing process was determined to be
about 2. 6 kcal. per mole. The energy of activation for the radiation¬
less transition from singlet to ground state was about 0, 9 kcal per
mole.
A somewhat similar study of 1, 12 benzperylene has shown that,
since the second excited singlet of this molecule lies only about
1300 cm. ^ (3,7 kcal. per mole) above the first excited singlet, there
is significant thermal population of the second excited singlet state
at 2 3°C. 42
Whether furotropylidene is showing a similar thermal effect
upon population of electronic states is not possible to determine so
long as the electronic states themselves cannot be observed except
through their chemistry. This is because the relative rates of re¬
action of the electronic species with their trapping agents are
unknown.
It is possible to draw several speculative schemes that could fit
the presently known facts about (4, 5-c)furotropylidene. Some of
these are shown in abbreviated form in Figure 43. It seems reason¬
able to assume that the cyclopropene is lower in energy than the
initially formed singlet carbene. The relative energies of the triplet
and singlet states shown in Figure 43 can only be the subject of

55
11
(Figure 43)

56
speculation from the present data. It is interesting to consider the
question as to whether equilibria exist between the species in Figure
39, but there is no experimental basis for a determination of this
question. A hypothetical experiment can be devised to answer this
question. If one can show that there is X percent formation of cyclo-
propene under a given set of conditions and that there is more than
(100-X) percent of carbene addition observed under the same condi¬
tions in the absence of a cyclopropene trap, one could reasonably
conclude that an equilibrium between cyclopropene and singlet carbene
does exist. Such an experiment seems to call for extraordinarily
high yields in these carbene reactions that are unlikely to be attain¬
able. In all of these schemes it seems reasonable that singlet
chemistry is not observed via intermolecular olefin trapping, since
the intramolecular reaction to form the cyclopropene would be ex¬
pected to be much faster than the intermolecular reaction.
It is interesting to speculate that perhaps triplet chemistry
predominates at higher temperatures because the singlet, through
its aromatic character, is relatively less reactive than triplet, and
therefore has a sufficiently long lifetime to allow intersystem crossing
to occur before singlet reaction occurs. An equilibration between
singlet and triplet, with the triplet the more reactive of the pair,
would also fit the data.
Perhaps the study of minor reaction products of (4, 5-c)furotro-
pylidene would shed additional light on these matters, but the separa¬
tion and purification of such large molecules formed in such low yields
presents formidable experimental difficulties.

EXPERIMENTAL
General. Melting points were taken in a Thomas -Hoover
Unimelt apparatus and are uncorrected. Elemental analyses were
performed by Atlantic Microlab, Incorporated, Atlanta, Georgia.
Accurate mass measurements were provided by Dr. R. W. King,
using the MS-30 high-resolution mass spectrometer equipped with
automatic data system, at the University of Florida. Infrared spectra
were recorded on a Beckman IR-10 spectrophotometer. In all cases
where the liquid film technique was not used, the KBr pellet technique
was used. Nuclear magnetic resonance spectra were determined on
a Varian A-60A high-resolution spectrometer, or in some cases, a
Varian XL-100 instrument. Chemical shifts are reported in tau
values from internal tetramethylsilane standard. Low resolution
mass spectra were determined on a Hitachi RMU-6E mass
spectrometer.
Analytical thin-layer chromatography was done on 2 in. x 8 in.
plates coated in these laboratories with 0. 25 mm. layers of E. Merck
HF-254 silica gel; preparative work was conducted on 8 in. x 8 in.
plates coated with 1. 0 to 1.5 mm. layers of HP-254 silica gel. Com¬
ponents were visualized by their quenching of fluorescence under
ultraviolet light. Analytical gas chromatography was accomplished
with a Varian Aerograph Series 1200 ñame ionization instrument using
a 100-ft. capillary column coated with Ucon LB-550. Analytical
results were obtained by planimetric measurement and by peak height
times peak-width-at-half-height measurement.

58
All chemicals are reagent grade used as supplied unless other¬
wise stated. The furan-3, 4-dicarboxylic acid was used as supplied
by Aldrich Chemical Company, Milwaukee, Wisconsin. Solvents
were dried by passage through a column of either freshly re-activated
Linde Molecular Sieve (4A) or Woelm basic alumina, activity grade 0,
followed by storage over calcium hydride under a nitrogen atmosphere.
3, 4-Di(hydroxymethyl)furan. This compound has been reported
23
as the product of the reduction of dimethyl-3, 4-furandicarboxylate.
The reported yield of 76 percent did not result from use of the pub¬
lished procedure. The following procedure gave 72 percent conver¬
sion based on the diacid. A mixture of 31.2 g. (0. 2 moles) 3, 4-
furandicarboxylic acid, 47.2 g. (0.4 moles) thionyl chloride, 200 ml.
benzene, and 1 ml. N, N-dimethylformamide was heated at reflux for
1 hr. The reaction is essentially complete when all of the solid has
dissolved. The benzene and excess thionyl chloride were removed in
vacuum by rotary evaporator. The crude diacyl chloride, formed
in essentially quantitative yield, was reduced directly without purifi¬
cation using the following procedure. The crude acid chloride was
dissolved in ca. 300 ml. tetrahydrofuran. This solution was dripped
into a stirred suspension of 30 g. lithium aluminum hydride in 800 ml.
dry tetrahydrofuran. The mixture was stirred at room temperature
overnight, then refluxed 8 hr. The reaction mixture was cooled. The
excess hydride was destroyed by addition of about 300 ml. of 5 percent
sodium hydroxide solution that had been saturated with sodium
chloride. The ether layer was separated by decanting from the white
granular slurry. This white residue was washed several times with
diethyl ether. The washings were combined with the first (THF)

59
extract, washed with brine, dried with anhydrous MgSO^ and filtered.
Removal of the solvent on a rotary evaporator using aspirator vacuum
gave 26. 4 g. of crude 3, 4-dihydroxymethylfuran. The product was
identified by the correspondence of its spectral properties with the
23
values reported in the literature.
3, 4-Furandicarboxaldehyde. This compound was prepared from
3, 4-di(hydroxymethyl)furan in two steps by the procedure of Cook and
2 3
Forbes. The first step, partial oxidation of the di-alcohol with
activated manganese dioxide, gave yields of about 50 percent instead
of the reported 80 percent. The best yields of di aldehyde were ob¬
tained by lead tetra-acetate oxidation of the crude 3 -hydroxymethyl-
furan-4-carboxaldehyde containing about 50 percent of unreacted
glycol, rather than by separation and purification of the mono¬
aldehyde. This procedure allowed the lead tetraacetate to oxidize,
not only the mono-aldehyde in the mixture, but also the glycol that
had not been oxidized by the manganese dioxide. This required use
of about 50 percent more lead tetraacetate than would have been
required for oxidation of an equal weight of 3-hydroxymethylfuran-4-
carboxaldehyde to the dialdehyde. This procedure gave about 25 per¬
cent conversion of the glycol to 3, 4-furandicarboxaldehyde. The
produce was identified by the correspondence of its spectral properties
and melting point with the values reported in the literature by Cook
and Forbes. ^
(4, 5-c)Furotropone. This compound was prepared by condensa¬
tion of 3, 4-furandicarboxaldehyde with acetone using the procedure of
23
Cook and Forbes. The yield and the physical and spectral properties
of the product were exactly as reported.

60
(4, 5-c)Furotropone tosylhydrazone. A solution of 2. 0 g.
(0. 014 moles) p-toluenesulfonylhydrazine and a trace of phosphoric
acid in 20 ml. of dry tetrahydrofuran was allowed to stand in a
stoppered flask for three to seven days at room temperature. The
solution was diluted with one volume of chloroform and allowed to
stand in a refrigerator cabinet (ca. 5-7°C.) for 0. 5 to 1 hr. The
resulting slurry of crystals was poured onto a Buchner filter. The
collected yellow crystals were washed with fresh chloroform on the
filter. The combined wash solvent and mother liquor were eluted
from a column of silica gel (4. 5x15 cm. ) using methylene chloride.
The first (yellow) fraction was collected and evaporated to dryness.
The residue was washed with chloroform and filtered. The resulting
second crop of yellow crystals when combined with the first crop on
the filter gave a total of 2. 9 g. (66 percent conversion) of the ketone
tosylhydrazone, m. p. 214-215°C. w. decomposition.
Anal. Caled for C jqN203S: C, 61.13;H, 4. 49; N, 8.91.
Found: C, 60. 97; H, 4. 54; N, 8.85.
- 1
The spectral data were: ir (KBr, cm. ) 3190, 1640, 1595,
1395, 1325, 1 162, 1052, 930, 885, 830, 762, 680. nmr (d6-DMSO)
2, 1 to 4. 13 (complex pattern, total 10H), 7.62 (singlet, 3H).
(4, 5-c)furotropone tosylhydrazone, sodium salt. A solution of
3. 9 g. furotropone tosylhydrazone in 100 ml. dry tetrahydrofuran was
stirred under dry nitrogen while 0. 5 g. sodium hydride (washed with
pentane) was added. After 0. 5 to 1.0 hr. at room temperature, 50-75
ml. pentane was added to the reaction mixture. The resulting slurry
of yellow solid was filtered in a dry nitrogen atmosphere (dry box) to
recover 5.2 g. of the sodium- salt.

61
Decomposition of tosylhydrazone salt in presence of benzene.
(4, 5-c)Furotroponetosylhydrazone sodium salt (0. 3 g. , 0. 7 mmole)
was stirred with 50 ml. benzene in a sealed Fischer-Porter Aerosol
Compatibility Test Tube (containing an atmosphere of dry nitrogen)
and heated in an oil bath kept at 118°C. After 1 hr. the tube was
cooled and opened. The dark brown slurry was taken from the tube
and filtered through a sintered glass funnel. The solid filter cake
weighed 0. 24 g. The filtrate, upon evaporation of the benzene, left
a residue of 0. 14 g. This crude residue was chromatographed on
preparative silica gel plates developed with hexane containing 5-10
percent benzene. The leading band of the chromatogram was col¬
lected, stripped from the adsorbent with ethanol, and recovered by
evaporating the filtered solution. This resulted in collection of 0. 063
g. of the benzene insertion product (25), m. p. 75-77° C.
Anal. Caled for C 15H1zO: C, 86. 49; H, 5.82. Found: C, 86. 38
H, 5.85.
The spectral data were: ir (KBr, cm ) 1595, 1490, 1450,
1 123, 1040, 872, 852, 800, 797, 762, 700; nmr (CDClj) 2. 71 and 2. 72
(two singlets, total 7H), 3.7 (complex, 2H), 4.5 (complex, 2H), 5.64
(complex, 1H); mass spectrum (70 eV) 208 (molecular ion), 131, 77.
Decomposition of tosylhydrazone salt in equimolar benzene-d^-
benzene. A repeat of the above preparation in the presence of an
equimolar mixture of benzene and hexadeuterated benzene produced
a 50:50 mixture of the benzene insertion product and the deuterated
benzene insertion product as determined by nmr (100 MHz. ) and by
mass spectroscopy.

62
Decomposition of tosylhydrazone salt in presence of styrene. A
solution of 0. 42 g. (4 mmoles) styrene in 15 ml. dry dioxane was
heated to 100° C. in a flask equipped with thermometer, stirring bar,
and an inlet for dry nitrogen. Dry solid tosylhydrazone salt (0. 33 g. ,
0. 8 mmoles) was added to the solution all at once. After 0. 3 hr. the
reaction mixture was quickly cooled in an ice bath as stirring was
continued. The crude brown slurry in the flask was removed and
filtered, then treated on a rotary evaporator to remove the dioxane
and as much styrene as possible. The resulting residue was dis¬
solved in chloroform and streaked on a preparative silica gel plate.
Development of the plate in a mixture of hexane and chloroform gave
0. 07 g. of somewhat impure spiro adduct in the major band. This
material was purified by repetition of the silica gel chromatography
using hexane as the solvent for development of the plate. This gave
0.06 g. of the oily liquid phenylspirocyclopropane (26), conversion
32 percent.
Anal. Caled for C, 87. 13; H, 6.03. Found: C,
86. 81; H, 6. 01.
The spectral data were: ir (film, cmT^) 3130, 3080, 3060,
3020, 2995, 1662, 1600, 1540, 1495, 1450, 1410, 1210, 1 125, 1047,
980, 875, 855, 815, 790, 698; nmr (CC14) 2.86 (singlet, 5H), 2.96
and 3. 01 (two singlets, total 2H), 7. 55-7. 82 (complex, 1H), 8. 5-8. 76
(complex, 2H); mass spectrum (70eV) 234 (molecular ion), 2 16, 205,
191, 130, 128.
Thermal decomposition of tosylhydrazone salt in presence of
trans-deuteriostyrene. The above preparation was repeated using
trans-deuteriostyrene in place of styrene. Examination of the nmr

63
spectrum showed that the product consisted of equal parts of the cis
and trans cyclopropanes. The spectrum showed a simplified ABX
pattern as described in the text of this report.
Photolytic decomposition of tosylhydrazone salt in presence of
trans-deuteriostyrene. A solution prepared as in the experiment
above was irradiated in a sealed tube (magnetically stirred) with two
Sears-Roebuck sunlamps at a distance of approximately 8-10 inches.
During the reaction and the workup the product was not exposed to
temperatures exceeding 50° C. The resulting phenylcyclopropane
consisted of equal parts of the cis and trans products as shown by
nmr.
Test of the thermal and photolytic stability of trans-deuterio-
styrene. A small sample of trans-deuteriostyrene in an nmr sample
tube was heated in a steam cone for 0. 5 hr. The nmr spectrum was
unchanged by the heating. The sample was also unchanged after it
was irradiated by two Sears Roebuck sunlamps for 0. 75 hr.
Decomposition of tosylhydrazone salt in presence of 1-butene.
The salt (0. Z g, , 0. 48 mmoles) was heated with 5 g. 1-butene (liquid)
that had been distilled into a Fisher - Porter Aerosol Compatibility
Test Tube. The tube was kept in an oil bath at 110 C. for 1 hr. The
excess 1-butene was then released. The crude residue was slurried
with benzene and filtered through a sintered glass filter. The solid
filter cake weighed 0. 14 g. The crude filtrate left a residue of 0. 05 g.
after evaporation of the benzene. This residue (about 90 percent
pure) afforded the ethyl spirocyclopropane (27) after purification by
preparative vapor phase chromatography on an 8 ft. x 1/4 in. column
packed with 60/80 mesh Anakrom ABS coated with 20 percent w/w
SE-30.

64
Anal. High resolution mass spectroscopy (70 eV): Caled for
C^H^O: 186. 1044. Found: 186. 1036.
The spectral data were: ir (liquid film, cm. 3145, 3070,
3035, 3000, 2975, 2940, 2880, 1670, 1540, 1470, 1460, 1132, 1050,
980, 880, 850, 810; nmr (CC14) s.95 (singlet, 2H), 3.87-4.3 (over¬
lapping doublets, total 2H), 5.25-5.8 (complex, 2H), 8. 3-9. 5 (com¬
plex, 8H); mass spectrum (70 eV) 186 (molecular ion), 171 (C^H^O),
158. 07 (C j jHjqO), 157. 06 (CnH90), 144. 05 (C 10HgO), 130.04
(c9h6o).
Decomposition of tosylhydrazone salt in presence of isobutene.
The salt (0. 3 g. , 0. 7 mmoles) was heated with ca. 4 g. liquid iso¬
butene in a sealed Fisher-Porter Aerosol Compatibility Test Tube in
an oil bath at 1 12°C. for 1-1.5 hr. The excess isobutene was then
released to cool the contents of the tube. The crude residue that
remained was slurried in benzene and filtered. The solid filter cake
weighed 0. 2 g. The filtrate, after evaporation of the benzene,
weighed 0. 038 g. Purification of this residue by taking the leading
band on a thin-layer plate (silica gel) developed in hexane gave
0. 017 g. of the purified dimethyl spirocyclopropane (28). The high
purity of the crude product, as shown by its nmr spectrum, suggests
that a large loss of material occurred during handling that was not
attributable merely to purification.
Anal. High resolution mass spectroscopy (70 eV): Caled for
C 13H14°: 186.1044. Found: 186.1060.
The spectral data were: ir (liquid film, cm. *) 3055, 3030,
2980, 1770, 1725, 1540, 1440, 1365, 1 130, 1 1 10, 1050, 880, 825;
nmr (CC14) 2. 83 (singlet, 2H), 3. 7-3. 9 (doublet, 2H), 4. 9-5.2

65
(doublet, 2H), 8. 9 (singlet, 6H), 9. 2 (singlet, 2H0; mass spectrum
(70 eV) 186. 10 (molecular ion), 185. 10 (C^H^O), 172. 08
(c i2H ii°). 158. 07 (CnH10O), 157. 06 (C l jHgO), 144. 05 (C 10HgO).
Thermal decomposition of tosylhydrazone salt in presence of
cis- and trans-2-butenes. The same pyrolysis technique described
above was used to decompose samples of the tosylhydrazone salt in
the presence of cis - and trans-2-butenes. The resulting crude re¬
action mixtures had essentially identical nmr spectra and gas chro¬
matograms (capillary column, Ucon LB-550). Pyrolysis of a 0. 3-g.
sample (0.72 mmoles) of the salt with 15 ml. liquid trans-2-butene
at 118°C. produced a crude product weighing 0. 09 g. Careful
preparative layer chromatography (silica gel adsorbent, hexane
solvent) of this material at low plate loadings gave 0. 03 g. of trans-
dimethylspirocyclopropane (34), 23 percent conversion.
Anal, High resolution mass spectroscopy (70 eV): Caled for
C 1 3H 14°' 186- 1044- Found= 186- 1052.
The spectral data were: ir (liquid film, cm. ^) 3030, 3000,
2960, 2935, 2855, 1665, 1540, 1455, 1387, 1 130, 1088, 1050, 880,
810; nmr (CC14) 2.88 (singlet, 2H), 3.9 (doublet, 2H), 5.3 (doublet,
2H), 8. 75-9. 0 (three sharp peaks, total 6H), 9. 0-9. 5 (complex, 2H);
mass spectrum (70 eV) 186. 10 (molecular ion), 171.08 (C^Hj^O),
158. 07 (CnH10O), 157. 06 (CnH90), 144. 06 (C } 0HgO), 128.06
(C 10h8)-
Photolysis of tosylhydrazone salt in presence of cis-2-butene.
The photolytic decomposition of 0, 33 g. tosylhydrazone salt with 12 g.
cis-2-butene was carried out by irradiating the stirred slurry in a
sealed tube for 1 hr. using two Sears-Roebuck sunlamps at a distance

66
of about 10-12 inches. This procedure produced a crude product
mixture that gave an nmr spectrum and gas chromatogram that were
essentially identical to those produced by the thermal decomposition
of the salt in the presence of cis- and trans-2-butenes described
above.
Photolysis of tosylhydrazone salt in presence of trans-2-butene
at low temperature. Photolytic decomposition of 0.4 g. tosylhydra¬
zone salt by irradiation for 1 hr. with a Hanovia 55 0-watt mercury
lamp at a temperature of -30°C. produced a crude reaction mixture
that contained no cyclopropane (34) as determined by nmr.
Determination of relative rates of reaction with various olefins.
Relative rates of reaction with various olefins were determined using
the pyrolysis method in a sealed tube as previously described. The
temperature of the oil bath was kept at 118°C. for all runs. In each
run a comparison of product formation from each of two olefins was
done. Each olefin was present in equimolar amounts, measured by
condensing equal volumes of the gaseous olefins into the reaction
tube by use of a mercury-filled gas buret. The product ratios were
determined by capillary column gas chromatography as described
under the General heading of this section. The results are presented
in Table I, page 31.
Pyrolysis with 1, 3-butadiene at 110°C. Furotropone tosylhy¬
drazone salt (0. 25 g. , 0. 6 mmoles) was heated with ca. 20 ml. liquid
1, 3-butadiene in a sealed Fisher-Porter Aerosol Compatibility Test
Tube in an oil bath kept at 110°C. for 4 hr. Excess butadiene was
vented to the atmosphere after the tube was removed from the bath
and opened. The residue that remained in the tube was slurried in

67
benzene and filtered through sintered glass. The clear amber ben¬
zene solution was streaked on a preparative layer plate (silica gel)
that was developed with hexane. The leading band of material gave
0. 06 g. of the 1, 4-adduct of butadiene (33), 55 percent yield. A
small band of material following the 1, 4-adduct was too small for
identi fication.
Anal. Caled for C13H120: C, 84. 75; H, 6.57. Found: C,
84. 49; H, 6. 65.
The spectral data were: ir (liquid film, cm. ^) 3060, 3020,
2930, 2850, 1618, 1540, 1440, 1340, 1 132, 1052, 948, 882, 848,
800, 670; nmr (CCl^) 2.82 (singlet, 2H0, 3.8-4. 7 (two doublets with
overlapping signal, total 6H), 7.5 (singlet, 4H); mass spectrum
(70 eV) 184 (molecular ion), 169, 155, 130, 129, 128, 54.
Pyrolysis with 1, 3-butadiene at 100° C. The tosylhydrazone
salt (0. 36 g. , 0.86 mmoles) was pyrolyzed with 1, 3-butadiene by the
above-described method using an oil bath temperature of 100° C. and
reaction time of 0. 5 hr. Similar workup and chromatography showed
only a very weak leading band corresponding to the 1, 4-adduct (33)
(0. 01 g. ), followed by a second band that afforded 0. 025 g. of the 1, 2-
adduct, the vinyl cyclopropane (31). A yield figure is not given in
this reaction because the short reaction time and low temperature
probably did not decompose all of the sodium salt.
Anal. Analysis was done by thermal isomerization of the 1,2-
adduct to the known 1, 4-adduct by heating it at 130° C. for 0. 5 hr.
The spectral data were: ir (liquid film, cm. ^) 3140, 3090,
3010, 1542, 1217, 1132, 1052, 1000, 910, 880, 813, 790; nmr (CC14)
3. 0 (singlet, sH), 4-5. 7 (complex, 7H), 8. 2-9. 1 (ABX pattern, 3H).
An impurity gave a singlet at 8. 64.

68
Photolysis of tosylhydrazone salt with 1, 3-butadiene at low
temperature. The tosylhydrazone salt (0. 4 g. , 0. 98 mmoles) was
photolyzed in a stirred reactor at -40° to -50° C. using the Hanovia
550-watt lamp for 2 hr. Workup, including thin-layer chromatog¬
raphy, as described before afforded 0. 07 g. of the Diels-Alder adduct
(40), 39 percent conversion.
Anal. High resolution mass spectroscopy (70 eV): Caled for
C 13H 12°' 184. 0887. Found: 184.0880.
The spectral data were: ir (liquid film, cm. ^), 3040, 2960,
2880, 2840, 1630, 1430, 1280, 1220, 1050, 1 110, 1025, 892, 860,
780, 740; nmr (CC14) 2.83 (singlet, 2H), 4.0 (doublet, 2H), 4.47
(broad, 211), 7. 52 (broad, 4H), 7. 85 (doublet, 1H), 9.15-9.45
(multiplet, 1H); mass spectrum (70 eV) 184.0887 ( molecular ion),
182. 073 (C 13H1qO), 169. 065 (C12H90), 168. 057 (C 12HgO), 165.070
(C j ^HpO).
Photolytic stability of vinylcyclopropane (31). A sample of the
vinylcyclopropane (31) was irradiated with two Sears-Roebuck sun¬
lamps for 0. 5-0. 75 hr. It was unchanged after irradiation.
Photolysis of tosylhydrazone salt with 1, 3-butadiene at 40° C. A
small-scale photolysis (ca. 25 mg. salt) was run in the presence of
1, 3-butadiene at 40° C, The product ratio was determined by a gas
chromatographic analysis (see General heading) of the crude product,
followed by another similar analysis after removal of all 1, 2-adduct
by thin-layer chromatography. The result showed that the Diels-Alder
adduct (40) and the vinylcyclopropane (31) were present in a 45:55
ratio with none of the 1, 4-adduct (33) present.

69
CIDNP Experiment, A saturated solution of the tosylhydrazone
salt in an nmr tube containing a solution of ca. 20 percent cyclohexene
in d^-DMSO was heated in the variable temperature probe of the
Varian A-60A at 120° C. for 10 min. No change in the spectrum
was detected before, during, and after heating.

LIST OF REFERENCES
1. C, L. Ennis, Ph. D. Dissertation, University of Florida,
March, 1968.
2. W. M. Jones and C. Lawrence Ennis, J. Am. Chem. Soc.,
9_1, 6391 (1969).
3. R. Gleiter and R. Hoffmann, J. Am. Chem. Soc., 90,
5457 (1968).
4. W. M. Jones, M. E. Stowe, E. E. Wells, Jr., and
E. W. Lester, J. Am. Chem. Soc. , 90, 1849 (1968).
5. P. H. Gebert, Ph. D. Dissertation, University of Florida,
March, 1972.
6. L. W. Christensen, E. E. Waali, and W. M. Jones, J.
Am. Chem. Soc., 94, 21 18 (1972).
7. D. Seyferth, J. Y. -P. Mui, and R. Damrauer, J. Am.
Chem. Soc., 90, 6182 (1968).
8. J. E. Baldwin and R. A. Smith, J. Am. Chem. Soc. , 89,
1886 (1967).
9. W. M. Jones, Burrell N. Hamon, Robert C. Joines, and
C. L. Ennis, Tetrahedron Lett., 3909 (1969).
10. I. Moritani et al. , Tetrahedron Lett., 373 (1966).
1 1. I, Moritani et al. , J. Am. Chem. Soc. , 89, 1259 (1967).
12.S. I. Murahashi, I. Moritani, and M. Nishino, J. Am.
Chem. Soc., 89, 1257 (1967).
13. K. E. Krajca, Tsutomu Mitsuhasni, andW. M. Jones,
J. Am. Chem. Soc., 94, 3661 (1972).
14. K. E. Krajca, Ph. D. Dissertation, University of Florida,
August, 1972.
15. Thomas Coburn, Ph.D. Dissertation, University of Florida,
August, 1973.
70

71
16. P. S. Skell, Accounts of Chemical Research, 6, 97 (1973).
17. Maitland Jones, Jr. and Wataru Ando, J. Am. Chem, Soc. ,
90, 2200(1968). ~
18. W. M. Jones and J. P. Mykytka, unpublished results, 1973.
19. A. Streitwieser, Jr. , "Molecular Orbital Theory for Organic
Chemists, " John Wiley and Sons, New York, N. Y. , 1961, p.357.
20. W. M. Jones et al. , J. Am. Chem. Soc., 95, 826 (1973).
21.Domenick J. Bertelli and Thomas G. Andrews, Jr. , J. Am.
Chem. Soc., 91, 5280 (1969).
22. Domenick J. Bertelli, Thomas G. Andrews, Jr. and Phillip O.
Crews, J, Am. Chem. Soc. , 91, 5286 (1969).
23. M. J. Cook and E. J. Forbes, Tetrahedron, 24, 4501 (1968)
and references cited therein.
24. Ronald N. Warrener, J, Am. Chem. Soc,, 93, 2346 (1971).
25. O. L. Chapman, J. Am. Chem. Soc., 85, 2014 (1963).
26. C. N. Banwell, in "Nuclear Magnetic Resonance for Organic
Chemists," D. W. Mathieson, Ed., Academic Press, New York,
N. Y. , 1967, p. 85.
27. Maitland Jones, Jr. , Arnold M. Harrison, and Kenneth R.
Rettig, J. Am. Chem. Soc., 91, 7462 (1969).
28. P. S. Skell and R. C. Woodworth, J. Am. Chem. Soc. , 78,
4496 (1956).
29. G. L. Closs, in "Topics in Stereochemistry, " Vol. 3, E. L.
Eliel and N. L. Allinger, Eds. , Interscience Publishers, New
York, N. Y. , 1968, p. 226.
30. George Zweifel, G. M. Clark, and N. L. Polston, J. Am. Chem.
Soc., 93, 3395(1971).
31. E. E. WaaliandW. M. Jones, J. Am. Chem. Soc., in press.
32. Maitland Jones, Jr., Wataru Ando, Michael E. Hendrick,
Anthony Kulczychi, Jr. , Peter M. Howley, Karl F. Hummel,
and Donald S. Malament, J. Am. Chem. Soc., 94, 7469 (1972).
33. K. B. Wiberg and B. J. Nist, J. Am. Chem. Soc. , 83, 1226
(1961).
34. L. J. Bellamy, "Advances in Infrared Group Frequencies,"
Meuthen and Co. , Ltd. , London, 1968, p. 24.

72
35. L. J. Bellamy, "The I. R. Spectra of Complex Molecules,"
John Wiley and Sons, New York, N. Y. , 1954, p. 31.
36. Harold R. Ward, in "Free Radicals," J. K. Kochi, Ed., John
Wiley and Sons, New York, N. Y. , 1973, p. 239.
37. Peter P. Gasper and George S. Hammond, in "Carbene
Chemistry," Wolfgang Kirmse, Ed., Academic Press, New
York, N. Y. , 1964, p. 270.
38. W. J. Baron et al. , in "Carbenes," Vol. 1, Maitland Jones,
Jr. and Robert A. Moss, Eds. , John Wiley and Sons, New
York, N. Y. , 1973, p. 81.
39. K. U, Ingold, in "Free Radicals, " J. K. Kochi, Ed. , John
Wiley and Sons, New York, N. Y. , 1973, p. 92.
40. G. L. Closs, in "Topics in Stereochemistry, " Vol. 3, E. L.
Eliel and N. L. Allinger, Eds. , Interscience Publishers, New
York, N. Y. , 1968, p. 224.
41. J. L. Kropp, W. R. Dawson, and M. W. Windsor, J. Phys.
Chem. , 73, 1752(1969). '
42. W. R. Dawson and J. L. Kropp, J. Phys. Chem., 73, 1752
(1969).

BIOGRAPHICAL SKETCH
Thomas Howard Ledford was born August 24, 1942, in Macon,
Georgia, to Mr, and Mrs, Howard William Ledford. He was gradu¬
ated from Swainsboro High School, Swainsboro, Georgia, in I960
and entered the University of Georgia as a four-year General Motors
Scholar that September. While there he was elected to Phi Beta
Kappa and received the Merck Award and the American Institute of
Chemists Award. He obtained the degree of Bachelor of Science in
Chemistry in June, 1964. The period 1965- 1968 was spent in indus¬
trial research in organic chemistry with Tennessee Eastman
Company, Kingsport, Tennessee. In 1968 he enrolled in the Graduate
School of the University of Florida with a Woodrow Wilson National
Fellowship. He was also a Graduate School Fellow during his
graduate study. He is a member of the American Chemical Society
and Phi Beta Kappa.
Mr. Ledford is married to the former Joan McDaniel of Oneonta,
Alabama. He will be working for the Esso Research Laboratories
of Exxon, U.S.A., in Baton Rouge, Louisiana.
73

I certify that I have read this study and that in my opinion it con¬
forms to acceptable standards of scholarly presentation and is fully ade¬
quate, in scope and quality, as a dissertation for the degree of Doctor
of Philosophy,
William M. J
Professor of
I certify that I have read this study and that in my opinion it con¬
forms to acceptable standards of scholarly presentation and is fully ade¬
quate, in scope and quality, as a dissertation for the degree of Doctor
of Philosophy,
Merle A. Battiste
Professor of Chemistry
I certify that I have read this study and that in my opinion it con¬
forms to acceptable standards of scholarly presentation and is fully ade¬
quate, in scope and quality, as a dissertation for the degree of Doctor
of Philosophy.
/3./3cOül.
George B, Butler
Professor of Chemistry
I certify that I have read this study and that in my opinion it con¬
forms to acceptable standards of scholarly presentation and is fully ade¬
quate, in scope and quality, as a dissertation for the degree of Doctor
of Philosophy,
AW; &Jtr
Roge^/G. Bates
Professor of Chemistry

I certify that I have read this study and that in my opinion it con¬
forms to acceptable standards of scholarly presentation and is fully ade¬
quate, in scope and quality, as a dissertation for the degree of Doctor
of Philosophy.
Richard H. Hammer
Associate Professor of Pharmaceu¬
tical Chemistry
This dissertation was submitted to the Department of Chemistry in the
College of Arts and Sciences and to the Graduate Council, and was ac¬
cepted as partial fulfillment of the requirements for the degree of Doc¬
tor of Philosophy.
August, 1973
Dean, Graduate School

UNIVERSITY OF FLORIDA
3 1262 08556 7443







PAGE 2

Ff)8527523< /,'(1( $ 7(13,(/(&7521 &$5%(1( %\ 7+20$6 +2:$5' /(')25' $ ',66(57$7,21 35(6(17(' 72 7+( *5$'8$7( &281&,/ 2) 7+( 81,9(56,7< 2) )/25,'$ ,1 3$57,$/ )8/),//0(17 2) 7+( 5(48,5(0(176 )25 7+( '(*5(( 2) '2&725 2) 3+,/2623+< 81,9(56,7< 2) )/25,'$

PAGE 3

'(',&$7,21 7KLV ZRUN LV GHGLFDWHG WR WKH SDVW IRU P\ SDUHQWV WR WKH SUHVHQW IRU P\ ZLIH DQG WR WKH IXWXUH IRU P\ FKLOGUHQ

PAGE 4

$&.12:/('*0(17 ZRXOG OLNH WR H[SUHVV P\ VLQFHUH JUDWLWXGH WR 3URIHVVRU : 0 -RQHV DQG DOO WKH PHPEHUV RI P\ VXSHUYLVRU\ FRPPLWWHH IRU WKHLU VFKRODUO\ JXLGDQFH GXULQJ WKH SUHSDUDWLRQ RI WKLV ZRUN $ VSHFLDO GHEW LV RZHG WR 'U 5 : .LQJ RI WKH 8QLYHUVLW\ RI )ORULGD ZKR JRRGQDWXUHGO\ VXIIHUHG DOO RI P\ TXHVWLRQV DERXW PROHFXODU VSHFn WURVFRS\ ,W LV VXFK PHQ DV WKHVH ZKR NHHS WHDFKLQJ LQ LWV KRQRUHG SODFH DPRQJ WKH SURIHVVLRQV 7KH ILQDQFLDO DLG RI WKH :RRGURZ :LOVRQ 1DWLRQDO )HOORZVKLS )RXQGDWLRQ WKH *UDGXDWH 6FKRRO RI WKH 8QLYHUVLW\ RI )ORULGD DQG WKH 1DWLRQDO 6FLHQFH )RXQGDWLRQ PDGH WKLV ZRUN SRVVLEOH LQ

PAGE 5

35()$&( 7RP KH VDLG WKH WURXEOH DERXW DUJXPHQWV LV WKH\ DLQnW QRWKLQJ EXW WKHRULHV DIWHU DOO DQG WKHRULHV GRQnW SURYH QRWKLQJ WKH\ RQO\ JLYH \RX D SODFH WR UHVW RQ D VSHOO ZKHQ \RX DUH WXFNHUHG RXW EXWWLQJ DURXQG DQG DURXQG WU\LQJ WR ILQG RXW VRPHWKLQJ WKHUH DLQnW QR ZD\ WR ILQG RXW +XFNOHEHUU\ )LQQ LQ 7RP 6DZ\HU $EURDG E\ 0DUN 7ZDLQ

PAGE 6

7$%/( 2) &217(176 $&.12:/('*0(17 LLL 35()$&( LY $%675$&7 YL ,1752'8&7,21 5(68/76 ',6&866,21 (;3(5,0(17$/ /,67 2) 5()(5(1&(6 %,2*5$3+,&$/ 6.(7&+ Y

PAGE 7

$EVWUDFW RI 'LVVHUWDWLRQ 3UHVHQWHG WR WKH *UDGXDWH &RXQFLO RI WKH 8QLYHUVLW\ RI )ORULGD LQ 3DUWLDO )XOILOOPHQW RI WKH 5HTXLUHPHQWV IRU WKH 'HJUHH RI 'RFWRU RI 3KLORVRSK\ Ff)8527523
PAGE 8

,1752'8&7,21 ,W KDV EHHQ HVWDEOLVKHG WKDW LQFRUSRUDWLQJ D YDFDQW RUELWDO RI D FDUEHQH LQWR D ULQJ FRQWDLQLQJ FRQMXJDWHG GRXEOH ERQGV FDQ ZKHQ WKH UHVXOWLQJ V\VWHP REH\V WKH +XFNHO Q UXOH UHVXOW LQ HVWDEOLVKn PHQW RI VRFDOOHG DURPDWLF FDUEHQH V\VWHPV WKDW KDYH XQXVXDO UHDFWLYLW\ SDWWHUQV 7KHVH FRQGLWLRQV DUH VDWLVILHG ZKHQ WKH QXPEHU RI GRXEOH ERQGV FRQMXJDWHG ZLWK WKH YDFDQW RUELWDO RI WKH FDUEHQH LV DQ RGG QXPEHU 6HH )LJXUH f ([DPSOHV RI VXFK DURPDWLF FDUEHQHV LQFOXGH WKH SL HOHFWURQ V\VWHP GLSKHQ\OF\FORSURSHQ\OLGHQH f WKH SLHOHFWURQ V\VWHP F\FORKHSWDWULHQ\OLGHQH f DQG WKH SLHOHFWURQ FDUEHQH GHULYHG IURP WKH PHWKDQRI f DQQXOHQH ULQJ V\VWHP f 6HH )LJXUH f

PAGE 9

$URPDWLF FDUEHQHV GLVSOD\ EHKDYLRU SDWWHUQV WKDW DUH VLJQLILn FDQWO\ GLIIHUHQW IURP WKRVH VKRZQ E\ RWKHU FDUEHQHV 7KH GHORFDOLn ]DWLRQ RI FKDUJH GHQVLW\ IURP WKH FRQMXJDWHG GRXEOH ERQG V\VWHP LQWR WKH YDFDQW RUELWDO RI DQ DURPDWLF FDUEHQH FDQ EH H[SHFWHG WR LQFUHDVH WKH QXFOHRSKLOLFLW\ RI WKH FDUEHQH $OVR WKH FDUEHQH RUELWDOV FDQ EH H[SHFWHG WR VSOLW LQWR WZR GLIIHUHQW HQHUJ\ OHYHOV DIIRUGLQJ WKH SRVVLn ELOLW\ RI D VWDELOL]HG VLQJOHW VWDWH 6HH )LJXUH f )LJXUH f 3HUKDSV WKH PRVW ZHOO NQRZQ RI WKHVH DURPDWLF FDUEHQHV LV F\FORKHSWDWULHQ\OLGHQH f f 7KLV FDUEHQH VKRZV WKH SURSHUWLHV RQH PLJKW H[SHFW RI D VWDELOL]HG VLQJOHW ZLWK LQFUHDVHG QXFOHRSKLOLF FKDUDFWHU ,W SUHIHUV WR UHDFW ZLWK HOHFWURQGHILFLHQW UDWKHU WKDQ HOHFWURQULFK ROHILQV )RU H[DPSOH LQ D +DPPHWW VWXG\ ZLWK VXEn VWLWXWHG VW\UHQHV F\FORKHSWDWULHQ\OLGHQH VKRZHG D UHDFWLRQ UDWH FRQn VWDQW RI 7KLV FRPSDUHV ZLWK UHDFWLRQ UDWH FRQVWDQWV RI IRU GLFKORURFDUEHQH DQG IRU FDUEHWKR[\FDUEHQH 1RW RQO\ LV WKH VLJQ RI WKH UHDFWLRQ UDWH FRQVWDQW VLJQLILFDQW EXW WKHUH LV DOVR VLJQLILFDQFH LQ LWV ODUJHU DEVROXWH YDOXH DQ LQGLFDWLRQ WKDW F\FORKHSWDn WULHQ\OLGHQH LV PRUH GLVFULPLQDWLQJ WKDQ RWKHU FDUEHQHV L H PRUH VWDEOH &RQVLVWHQW ZLWK WKH K\SRWKHVL]HG VWDELOL]DWLRQ RI LWV VLQJOHW VWDWH F\FORKHSWDWULHQ\OLGHQH UHDFWV ZLWK DFFHSWRU ROHILQV WR IRUP F\FORSURSDQHV LQ ZKLFK WKH ROHILQ VWHUHRFKHPLVWU\ LV SUHVHUYHG )LJXUH f

PAGE 10

)LJXUH f $PRQJ WKH VXEVWLWXWHG F\FORKHSWDWULHQ\OLGHQHV WKDW KDYH EHHQ SUHSDUHG DQG VWXGLHG WKH IROORZLQJ DQQHODWHG FRPSRXQGV KDYH VKRZQ VRPH LQWHUHVWLQJ QHZ GHSDUWXUHV LQ F\FORKHSWDWULHQ\OLGHQH FKHPLVWU\ )LJXUH f &DUEHQHV f DQG f KDYH EHHQ JHQHUDWHG XQGHU FRQGLWLRQV WKDW DOORZ REVHUYDWLRQ RI WKHLU ORZWHPSHUDWXUH HVU VSHFWUD %RWK KDYH WULSOHW JURXQG VWDWHV DQG UHDFW ZLWK HOHFWURQULFK ROHILQV VXFK DV EXWHQH WR IRUP F\FORSURSDQH DGGXFWV A (YLGHQWO\ ERWK f DQG f EHKDYH PXFK OLNH GLSKHQ\OFDUEHQH $QQHODWLRQ KDV LQ WKHVH WZR FDVHV FKDQJHG WKH F\FORKHSWDWULHQ\OLGHQH VR VLJQLILFDQWO\ WKDW D VLQJOHW JURXQG VWDWH LV LPSRVVLEOH &DUEHQHV f f DQG f VKRZ HYHQ PRUH GUDPDWLF HIIHFWV RI DQQHODWLRQ XSRQ F\FORKHSWDWULHQ\OLGHQH $OO WKUHH RI WKHVH XQGHUJR FDUEHQHFDUEHQH UHDUUDQJHPHQW DW ORZ WR PRGHUDWH WHPSHUDWXUHV DFFRUGLQJ WR WKH IROORZLQJ HTXDWLRQV f f )LJXUH f 7KH JURXQG VWDWHV IRU WKHVH FDUEHQHV DUH XQNQRZQ EXW LW LV DVVXPHG WKDW WKH UHDUUDQJHPHQWV DW OHDVW SURFHHG WKURXJK D VLQJOHW VWDWH 7KH QDWXUH RI WKH LQWHUPHGLDWH RU WUDQVLWLRQ VWDWH OHDGLQJ WR WKLV NLQG RI FDUEHQHFDUEHQH UHDUUDQJHPHQW KDV EHHQ VRPHZKDW FRQWURYHUVLDO 7KHUH LV UHFHQW FRQYLQFLQJ HYLGHQFH WKDW VXFK UHn DUUDQJHPHQWV SURFHHG YLD D F\FORSURSHQH LQWHUPHGLDWH VXFK DV VKRZQ

PAGE 11

)LJXUH f

PAGE 12

)LJXUH f

PAGE 13

P )LJXUH ,Q WKLV H[DPSOH WKH LQWHUPHGLDWH F\FORSURSHQH f DSSHDUV WR KDYH EHHQ WUDSSHG E\ D 'LHOV$OGHU UHDFWLRQ ZLWK HDFK RI VHYHUDO GLHQHV 7KH LQWHUPHGLDWH f KDV DOVR EHHQ DSSURDFKHG IURP DQRWKHU VRXUFH DV VKRZQ LQ )LJXUH )LJXUH f 0RQRDQQHODWLRQ LV VDLG WR VXEVWDQWLDOO\ GHFUHDVH WKH VWDELOLW\ RI WKH WURS\O FDWLRQ 6LQFH FDUEHQH VWDELOLW\ LV WKRXJKW WR SDUDOOHO FDWLRQ VWDELOLW\ DQG VLQFH PRQRDQQHODWLRQ VKRXOG KDYH OLWWOH HIIHFW XSRQ WKH VWDELOLW\ RI WKH LQWHUPHGLDWH F\FORSURSHQH PRQRDQQHODWLRQ LV

PAGE 14

WKRXJKW WR FDXVH D GHVWDELOL]DWLRQ RI WKH FDUEHQH UHODWLYH WR WKH F\FOR SURSHQH LQWHUPHGLDWH WKXV LQFUHDVLQJ WKH SUREDELOLW\ RI UHDUUDQJH PHQW )ROORZLQJ WKLV OLQH RI UHDVRQLQJ IXUWKHU RQH FRXOG H[SHFW WR DQWLFLSDWH UHDUUDQJHPHQWV LQ RWKHU FDUEHQHV E\ DQ DQDO\VLV RI DURPDn WLFLW\ DQG FDWLRQ VWDELOLW\ UHODWLYH WR WKH WURS\O V\VWHP 7KH VXEMHFW RI WKLV VWXG\ LV WKH FDUEHQH aFfIXURWURS\OLGHQH f VKRZQ LQ )LJXUH 7KLV FDUEHQH VKRXOG EH H[SHFWHG WR VKRZ DW OHDVW VRPH DURPDWLF FKDUDFWHU VLQFH LW GRHV VDWLVI\ WKH +XFNHO Q )LJXUH f UXOH Q f KDYLQJ SLHOHFWURQV 7KH VWUXFWXUH LV QRW DFWXDOO\ D VLPSOH DQQHODWHG F\FORKHSWDWULHQ\OLGHQH LQ RQH VHQVH EHFDXVH LW ODFNV D GRXEOH ERQG DQDORJRXV WR WKH RQH EHWZHHQ SRVLWLRQV DQG LQ F\FORn KHSWDWULHQ\OLGHQH 7KH TXHVWLRQ RI ZKHWKHU DURPDWLF FKDUDFWHU FDQ EH H[SHFWHG LQ FDUEHQH f FDQQRW EH DQVZHUHG D SULRUL ,Q IDFW WKH ZKROH FRQFHSW RI DURPDWLFLW\ LQ WURSRQRLG NHWRQHV KDV EHHQ DWWDFNHG E\ %HUWHOOL f EXW WKH FRQFHSW VHHPV VR XVHIXO LQ H[SODLQLQJ WKH EHKDYLRU RI WURSRQRLG GHULYHG FDUEHQHV WKDW LWV FRQWLQXHG XVH VHHPV MXVWLILHG IRU WKH WLPH EHLQJ 7KH IROORZLQJ DQDO\VLV WKRXJK LW LV PLWLJDWHG E\ %HUWHOOLnV DUJXPHQW KDV EHHQ XVHG WR DUULYH DW HVWLPDWHV RI UHODWLYH DURPD WLFLWLHV LQ WKH IROORZLQJ VHULHV RI NHWRQHV $V GHORFDOL]DWLRQ RI HOHFWURQV LQFUHDVHV LQ WKH ULQJ V\VWHPV WKH ERQG RUGHU RI WKH H[RF\FOLF & JURXSV ZLOO GHFUHDVH 7KLV ZLOO

PAGE 15

f f )LJXUH f SDUDOOHO WKH LQFUHDVLQJ FRQWULEXWLRQ RI WKH GLSRODU IRUP RI WKH r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n WLRQ IUHTXHQF\ 7KH NHWRQH FfIXURWURSRQH f KDYLQJ D & DEVRUSWLRQ DW FP r LV WKHUHIRUH OHVV DURPDWLF WKDQ EHQ]WURSRQH f KDYLQJ LWV & DEVRUSWLRQ DW FP A ,Q WXUQ EHQ]WURSRQH f LV OHVV DURPDWLF WKDQ WURSRQH VLQFH WKH FDUERQ\O IUHTXHQF\ RI

PAGE 16

WURSRQH f LV FP %\ WKLV FULWHULRQ IXURWURSRQH f KDV PRUH GHORFDOL]DWLRQ WKDQ D FURVVFRQMXJDWHG F\FORKHSWDGLHQRQH EHFDXVH DOO LWV EDQGV DSSHDU DW ORZHU IUHTXHQFLHV WKDQ WKH FDUERQ\O EDQG RI WKH GLHQRQH f VKRZQ LQ )LJXUH FD FP f )LJXUH f 7KH LQIHUHQFH WKDW IXURWURS\OLGHQH f VKRXOG KDYH OHVV DURPDWLF FKDUDFWHU WKDQ F\FORKHSWDWULHQ\OLGHQH f VXJJHVWV WKDW IXURWURS\OLGHQH OLNH RWKHU VOLJKWO\ GHVWDELOL]HG DURPDWLF FDUEHQHV f f DQG f PLJKW EH H[SHFWHG WR XQGHUJR FDUEHQHFDUEHQH UHDUUDQJHn PHQW 7KH H[DPLQDWLRQ RI D K\SRWKHWLFDO UHDFWLRQ SDWKZD\ RI D K\SRn WKHWLFDO UHDFWLRQ SDWKZD\ )LJXUH f VXJJHVWV D SRVVLEOH FRPSOLFDWLRQ $OWKRXJK WKH FDUEHQH f VKRXOG EH GHVWDELOL]HG UHODWLYH WR WKH f )LJXUH f F\FORSURSHQH f WKH SURGXFW f IURP RSHQLQJ WKH F\FORSURSHQH VKRXOG JLYH VRPH FDXWLRQ 7KH UHDUUDQJHG FDUEHQH f KDV D FDUEHQH FHQWHU DWWDFKHG WR DQ LVREHU rDQ VNHOHWRQ $OWKRXJK LVREHQ]RIXUDQ LV D SL V\VWHP LW DSSDUH GRHV QRW VKRZ WKH VWDELOL]DWLRQ

PAGE 17

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

PAGE 18

5(68/76 7KH FDUEHQH FfIXURWURS\OLGHQH f ZDV SUHSDUHG LQ DOO FDVHV HLWKHU E\ S\URO\VLV RU SKRWRO\VLV RI WKH VRGLXP VDOW RI WKH WRV\OK\GUD]RQH RI FfIXURWURSRQH f 7KH V\QWKHWLF VFKHPH IRU k f f )LJXUH f 1 SURGXFLQJ WKH UHTXLUHG NHWRQH ZDV RULJLQDOO\ GHYHORSHG E\ &RRN DQG )RUEHV 6RPH PRGLILFDWLRQV RI WKHLU SURFHGXUHV ZHUH XVHG LQ SUHn SDULQJ WKH NHWRQH IRU WKLV VWXG\ )RU H[DPSOH FRPPHUFLDOO\ DYDLOn DEOH IXUDQ GLFDUER[\OLF DFLG ZDV FRQYHUWHG WR LWV GLDF\O )LJXUH f FKORULGH f E\ WKH DFWLRQ RI WKLRQ\O FKORULGH LQ WKH SUHVHQFH RI D FDWDO\WLF DPRXQW RI 1 1GLPHWK\OIRUPDPLGH 7KH DFLG FKORULGH f ZDV QHYHU SXULILHG DQG FKDUDFWHUL]HG ,WV SUHVHQFH ZDV LQIHUUHG IURP

PAGE 19

LWV UHDFWLRQ ZLWK PHWKDQRO WR DIIRUG D TXDQWLWDWLYH \LHOG RI WKH NQRZQ GLPHWK\O HVWHU f SUHYLRXVO\ FKDUDFWHUL]HG DQG UHSRUWHG E\ &RRN DQG )RUEHV 8VLQJ WKH SURFHGXUHV RI &RRN DQG )RUEHV WKH UHGXFn WLRQ RI WKH GLPHWK\O HVWHU ZDV FDUULHG RXW XVLQJ OLWKLXP DOXPLQXP K\GULGH EXW WKH SHUFHQW \LHOGV UHSRUWHGO\ DWWDLQDEOH GLG QRW UHVXOW 'LUHFW UHGXFWLRQ RI WKH FUXGH GLDF\O FKORULGH f GLG DIIRUG WKH GLn DOFRKRO f LQ \LHOGV RI DERXW SHUFHQW 7KH GLDOFRKRO ZDV WUHDWHG R A[RF_ /,$,+ f§A R f&2&, f f n&+2+ rFKRK )LJXUH f ZLWK DFWLYDWHG PDQDJDQHVH GLR[LGH WR HIIHFW R[LGDWLRQ RI RQH RI WKH DOFRKRO JURXSV WR WKH DOGHK\GH VWDJH $JDLQ WKH \LHOGV UHSRUWHG LQ WKH OLWHUDWXUH GLG QRW UHVXOW 7KH UHDFWLRQ XVXDOO\ SURGXFHG RQO\ DERXW SHUFHQW RI WKH PD[LPXP DPRXQW RI K\GUR[\PHWK\OIXUDQ FDUER[DOGHK\GH f DFFRPSDQLHG E\ DERXW KDOI RI WKH XQUHDFWHG GLDOFRKRO GHWHUPLQHG E\ SURWRQ UHVRQDQFH VSHFWURVFRS\f 7KLV VLWXDWLRQ ZDV PDGH XVDEOH E\ WKH IDFW WKDW OHDG WHWUDDFHWDWH R[LGDWLRQ RI WKLV FUXGH PL[WXUH RI GLDOFRKRO DQG PRQRDOGHK\GH DIIRUGHG WKH f 0Q2] GLDOGHK\GH f LQ \LHOGV RI DERXW SHUFHQW EDVHG RQ GLDOFRKRO

PAGE 20

7KH IXUDQGLFDUER[DOGHK\GH f ZDV FRQGHQVHG ZLWK DFHWRQH XVLQJ WKH SURFHGXUH RI &RRN DQG )RUEHV WR JLYH H[DFWO\ WKH UHSRUWHG \LHOG RI SHUFHQW )LJXUH f &RQYHUVLRQ RI IXURWURSRQH LQWR LWV WRV\OK\GUD]RQH ZDV EHVW FDUULHG RXW E\ WUHDWPHQW RI WKH NHWRQH f ZLWK WRV\OK\GUD]LQH LQ WHWUDK\GURIXUDQ FRQWDLQLQJ D WUDFH RI DQK\GURXV SKRVSKRULF DFLG 7KH UHDFWLRQ ZRUNHG EHVW ZKHQ WKH UHDFWDQWV ZHUH PHUHO\ DOORZHG WR VWDQG WRJHWKHU DW URRP WHPSHUDWXUH IRU ILYH WR VHYHQ GD\V 7KLV SURFHGXUH JDYH WKH WRV\OK\GUD]RQH f LQ SHUFHQW FRQYHUVLRQ )LJXUH f I $ VROXWLRQ RI WKH WRV\OK\GUD]RQH LQ WHWUDK\GURIXUDQ ZDV WUHDWHG ZLWK VRGLXP K\GULGH WR SURGXFH WKH VRGLXP VDOW RI WKH WRV\OK\GUD]RQH f 7KH ZHLJKW RI WKH VRGLXP VDOW SURGXFHG VXJJHVWV IURP WKH VWRLFKLRPHWU\ RI WKH UHDFWLRQ WKDW RQH PROH RI WHWUDK\GURIXUDQ LV LQFOXGHG LQ WKH VDOW DV ERXQG VROYHQW $OO \LHOGV LQ UHDFWLRQV RI WKLV VRGLXP VDOW KDYH EHHQ DGMXVWHG WR UHIOHFW WKLV HIIHFW

PAGE 21

1F3 k VA:f§ $U 1 1 )LJXUH f f ,, 7KHUPDO GHFRPSRVLWLRQ RI WKH VRGLXP VDOW RI FfIXURWURSRQH WRV\OK\GUD]RQH f LQ WKH SUHVHQFH RI EHQ]HQH DW r & OHG WR IRUPDWLRQ RI WKH IRUPDO &+ LQVHUWLRQ SURGXFW f LQ SHUFHQW LVRODWHG \LHOG 7KH VWUXFWXUH RI f ZDV DVVLJQHG SULPDULO\ RQ WKH EDVLV RI LWV VSHFWUDO SURSHUWLHV $W WDX DQG WKHUH ZHUH WZR VLQJOHWV DVVLJQHG WR WKH IXUDQ K\GURJHQV DQG WR WKH EHQ]HQH K\GURn JHQV UHVSHFWLYHO\ 7KH WRWDO RI ERWK SHDNV ZDV VHYHQ K\GURJHQV 7KH YLQ\O K\GURJHQV +Df DSSHDUHG DW WDX DV D GRXEOHW VSOLW E\ +] WKURXJK FRXSOLQJ WR +Ef (DFK SHDN RI WKLV GRXEOHW VKRZHG D VOLJKW VSOLWWLQJ FD +] f DWWULEXWDEOH WR DOO\OLF FRXSOLQJ WR WKH WHUWLDU\ K\GURJHQ +Ff 7KH YLQ\O K\GURJHQV +Ef DSSHDUHG DV D GRXEOHW RI GRXEOHWV DW WDX ,Q WKLV SDWWHUQ WKH FRXSOLQJ +] f EHWZHHQ YLQ\OLF SURWRQV DQG WKH FRXSOLQJ +] f EHWZHHQ +Af DQG +Ff ZHUH ERWK HDVLO\ GLVFHUQLEOH 7KH WHUWLDU\ K\GURJHQ + f DSSHDUHG DW WDX ,W ZDV SULPDULO\ D WULSOHW SDWWHUQ VKRZLQJ VRPH VXSHULPSRVHG DOO\OLF VSOLWWLQJ 7KH LQIUDUHG VSHFWUXP LQGLFDWHG WKH PRQRVXEVWLWXWHG EHQ]HQH VWUXFWXUH E\ LWV DEVRUSWLRQV DW FP a r DQG FP r

PAGE 22

f )LJXUH f

PAGE 23

7KH SURWRQ PDJQHWLF UHVRQDQFH VSHFWUXP RI WKH FUXGH UHDFWLRQ PL[WXUH VKRZHG RQO\ WKH EHQ]HQH &+ LQVHUWLRQ SURGXFW f 1R HYLGHQFH RI D F\FORKHSWDWULHQH VWUXFWXUH ZDV SUHVHQW &DUHIXO H[DPLQDWLRQ RI WKH UHDFWLRQ PL[WXUH E\ DQDO\WLFDO WKLQOD\HU FKURPDn WRJUDSK\ IDLOHG WR VKRZ DQ\ ELSKHQ\O LQ WKH VDPSOH ,Q D FRPSHWLWLRQ UHDFWLRQ DOORZLQJ WKH FDUEHQH HTXDO DFFHVV WR EHQ]HQH DQG GAEHQ]HQH HVVHQWLDOO\ HTXDO DPRXQWV RI GHXWHUDWHG DQG QRQGHXWHUDWHG SURGXFWV ZHUH SURGXFHG DV GHWHUPLQHG E\ ERWK PDVV VSHFWURVFRS\ DQG E\ 0+] SURWRQ PDJQHWLF UHVRQDQFH $Q HIIRUW WR SUHSDUH WKH SURGXFW RI &+ LQVHUWLRQ LQWR F\FORn KH[DQH IDLOHG EHFDXVH RI ORZ \LHOGV 7KH FDUEHQH f XQGHUJRHV UHDFWLRQ ZLWK ROHILQV LQ GLR[DQH VROXWLRQ ZLWKRXW WDNLQJ GLR[DQH LQWR WKH UHDFWLRQ PL[WXUH 7KHVH REVHUYDWLRQV VXJJHVW WKDW WKH EHQ]HQH &+ LQVHUWLRQ UHDFWLRQ SUREDEO\ GRHV QRW UHVXOW IURP GLUHFW LQVHUWLRQ EXW WKURXJK DQ LQWHUPHGLDWH WKDW ZLOO EH GLVFXVVHG LQ D ODWHU VHFWLRQ RI WKLV UHSRUW $WWHPSWHG DGGLWLRQ RI WKH FDUEHQH f WR WKH GRXEOH ERQG LQ F\FORKH[HQH UHVXOWHG LQ D PL[WXUH WKDW FRXOG QRW EH VHSDUDWHG FOHDQO\ HQRXJK WR DOORZ FKDUDFWHUL]DWLRQ RI DQ\ RI WKH SURGXFWV 7KH SURWRQ PDJQHWLF UHVRQDQFH VSHFWUXP RI WKH FUXGH SURGXFW GLG VXJJHVW WKDW VRPH DGGLWLRQ WR WKH GRXEOH ERQG KDG RFFXUUHG 7KH SUHVHQFH RI RWKHU SURGXFWV LQ WKH UHDFWLRQ PL[WXUH VXJJHVWV WKDW FfIXURWURS\OLGHQH LV QRW LQFDSDEOH RI &+ LQVHUWLRQ EXW RQH LV OHIW WR VSHFXODWH DERXW ZKHWKHU WKH SURGXFWV DULVH E\ GLUHFW UHDFWLRQ RI WKH FDUEHQH RU E\ VHFRQGDU\ SURFHVVHV 'HFRPSRVLWLRQ RI WKH WRV\OK\GUD]RQH VDOW LQ D UHIOX[LQJ VROXWLRQ RI VW\UHQH LQ GLR[DQH E S r & f ZDV VXFFHVVIXO LQ SURGXFLQJ D

PAGE 24

SKHQ\OF\FORSURSDQH f WKDW FRXOG EH VHSDUDWHG DQG FKDUDFWHUL]HG
PAGE 25

352721 0$*1(7,& 5(621$1&( 63(&7580 2) 352'8&7 f )LJXUH f

PAGE 26

7 r f§ f§ f n, I 352721 0$*1(7,& 5(621$1&( 63(&7580 2) 352'8&7 f (1/$5*(' 9,(:6 2) $%; 3257,21 7 )LJXUH f

PAGE 27

WDX DUHD DV WZR GRXEOHWV WKDW VKRZ RYHUODS EHWZHHQ WKH WZR FHQWUDO SHDNV 7KH JHPLQDO F\FORSURS\O K\GURJHQV $% SDLUf DSSHDU DV WKH H[SHFWHG SDLU RI RYHUODSSLQJ TXDUWHWV LQ WKH UHJLRQ WDX 7KH VSDFLQJ EHWZHHQ WKH PLGSRLQWV RI WKH WZR TXDUWHWV DEV YDOXH RI -J\f DOORZV HDV\ FDOFXODWLRQ RI WKH SUHGLFWHG VSDFLQJ EHWZHHQ OLQHV DQG LQ WKH ; SRUWLRQ RI WKH VSHFWUXP 7KH SUHGLFWHG VSDFLQJ EHWZHHQ OLQHV DQG +] f ZDV REVHUYHG DQG SHUPLWWHG DVVLJQPHQW RI OLQHV DQG DV WKH WZR RXWVLGH OLQHV LQ WKH ; SRUWLRQ RI WKH VSHFWUXP 7KH YDOXH RI -$% +] ZDV GLUHFWO\ PHDVXUDEOH IURP WKH VSHFWUXP 7KH LQIUDUHG VSHFWUXP RI f VKRZV DEVRUSWLRQV QHDU FPA DQG FP FRQVLVWHQW ZLWK WKH PRQRVXEVWLWXWHG EHQ]HQH VWUXFWXUH $EVRUSWLRQV DW FP r DQG FP r RIIHU FRQILUPDn WRU\ HYLGHQFH RI WKH F\FORSURSDQH ULQJ LQGLFDWHG E\ WKH DEVRUSWLRQ DW FP 3\URO\WLF GHFRPSRVLWLRQ RI WKH WRV\OK\GUD]RQH VDOW f LQ WKH SUHVHQFH RI EXWHQH JDYH WKH H[SHFWHG HWK\OF\FORSURSDQH f LQ DERXW SHUFHQW LVRODWHG \LHOG 7KH F\FORSURSDQH ZDV DFFRPSDQLHG E\ WKUHH PLQRU E\SURGXFWV WKDW ZHUH QHYHU LGHQWLILHG 7KH SURWRQ PDJQHWLF UHVRQDQFH VSHFWUXP RI f VKRZHG D WZRK\GURJHQ VLQJOHW DW WDX IRU WKH IXUDQ K\GURJHQV 7KH YLQ\OLF SURWRQV +Df DQG +DLf WKDW VKRZHG D SDLU RI GRXEOHWV LQ WKH SKHQ\OF\FORSURSDQH f DSSHDUHG LQ WKLV HWK\OF\FORSURSDQH DV DQ RYHUODSSHG SDLU RI GRXEOHWV VSOLW E\ +] DW WDX 7KH RWKHU SDLU RI YLQ\OLF K\GURJHQV +Af DQG +ALf DSSHDUHG DV D SDLU RI VHSDUDWHG GRXEOHWV DW WDX VKRZLQJ WKH VDPH :IRUP FRXSOLQJ REVHUYHG LQ WKH SKHQ\OF\FORSURSDQH f ,W LV LQWHUHVWLQJ WR REVHUYH WKH VPDOOHU V\PPHWU\ GLVWXUEDQFH

PAGE 28

352721 0$*1(7,& 5(621$1&( 63(&7580 2) 352'8&7 f f + &+Sf§&+A )LJXUH f

PAGE 29

SURGXFHG E\ WKH HWK\O JURXS LQ f FRPSDUHG ZLWK WKH ODUJHU HIIHFW RI WKH SKHQ\O JURXS LQ f :KHUHDV WKH IXUDQ K\GURJHQV ZHUH UHn VROYDEOH LQ f WKH\ ZHUH QRW UHVROYDEOH LQ f )XUWKHU HYLGHQFH RI ORZHU GLVWXUEDQFH RI V\PPHWU\ LV SURYLGHG E\ WKH IDFW WKDW WKH SDLU RI GRXEOHWV UHSUHVHQWLQJ WKH YLQ\OLF K\GURJHQV + f DQG + f DUH RYHU ODSSHG LQ f EXW ZHOO VHSDUDWHG LQ f 7KH UHPDLQGHU RI WKH VSHFWUXP RI WKH HWK\OF\FORSURSDQH f ZDV D FRPSOH[ HLJKWK\GURJHQ VLJQDO LQ WKH UHJLRQ RI WDX WKDW LQFOXGHG WKH F\FORSURS\O K\GURJHQV DQG WKH K\GURJHQV RQ WKH HWK\O JURXS 7KHUPDO GHFRPSRVLWLRQ RI WKH WRV\OK\GUD]RQH VDOW f LQ WKH SUHVHQFH RI LVREXWHQH JDYH D UHPDUNDEO\ FOHDQ UHDFWLRQ SURGXFLQJ WKH GLPHWK\OF\FORSURSDQH f LQ SHUFHQW \LHOG 7KH VWUXFWXUH ZDV DVVLJQHG SULPDULO\ RQ WKH EDVLV RI WKH SURWRQ PDJQHWLF UHVRQDQFH VSHFWUXP 7KLV PROHFXOH SURYLGHV DQ H[FHOOHQW H[DPSOH RI WKH SURn IRXQG HIIHFWV RI PROHFXODU V\PPHWU\ RQ QXFOHDU PDJQHWLF UHVRQDQFH $ SODQH RI V\PPHWU\ FDQ EH GUDZQ WKURXJK WKH GLPHWK\OF\FORSURSDQH f 7KLV SODQH LQFOXGHV WKH SODQH RI WKH F\FORSURS\O ULQJ DQG ELVHFWV WKH SODQH RI WKH IXVHG IXURWURS\O ULQJ V\VWHP 7KLV V\PPHWU\ UHVXOWV LQ PDJQHWLF HTXLYDOHQFH RI WKH IXUDQ K\GURJHQV DQG ERWK VHWV RI YLQ\O K\GURJHQV LQ WKH VHYHQPHPEHUHG ULQJ 7KLV UHVXOWV LQ D VLPSOLILHG VSHFWUXP IRU WKH FRPSRXQG $ WZRK\GURJHQ VLQJOHW IRU WKH IXUDQ K\GURJHQV DSSHDUHG DW WDX ,QVWHDG RI WKH PRUH FRPSOH[ YLQ\O DEVRUSWLRQV REVHUYHG LQ WKH VW\UHQH DGGXFW f DQG LQ WKH EXWHQH DGGXFW f D VLPSOH $% SDWWHUQ DSSHDUHG $ GRXEOHW FHQWHUHG DW WDX VKRZHG D WZRK\GURJHQ VLJQDO IRU WKH + f SDLU $QRWKHU GRXEOHW FHQWHUHG DW WDX ZDV SUHVHQWHG E\ WKH +Af SDLU RI K\GURJHQV 7KH FRXSOLQJ EHWZHHQ +Df DQG +Af ZDV +] DERXW WKH VDPH YDOXH

PAGE 30

352721 0$*1(7,& 5(621$1&( 63(&7580 2) 352'8&7 f f + + ? $ &f& 9 )LJXUH f

PAGE 31

REVHUYHG LQ RWKHU FRPSRXQGV LQ WKLV VHULHV 7KH WZR PHWK\O JURXSV SURGXFHG WKH H[SHFWHG VL[K\GURJHQ VLQJOHW DW WDX DFFRPSDQLHG E\ D QHDUE\ VLQJOHW IRU WKH WZR HTXLYDOHQW F\FORSURS\O K\GURJHQV DW WDX 7KH SURIRXQG HIIHFWV RI FKDQJHV LQ V\PPHWU\ LQ VSLURF\FOR SURSDQHV VXFK DV f f DQG f SURYLGH DQ H[FHOOHQW EDVLV IRU DVVLJQPHQW RI VWHUHRFKHPLFDO FRQILJXUDWLRQV LQ FLV DQG WUDQV GLVXEVWLWXWHG VSLURF\FORSURSDQHV E\ QXFOHDU PDJQHWLF UHVRQDQFH 7UDQV GLVXEVWLWXWHG VSLURF\FORSURSDQHV VHH )LJXUH f FDQ EH H[SHFWHG WR KDYH HTXLYDOHQW VHWV RI IXUDQ K\GURJHQV DQG YLQ\OLF K\GURJHQV IDFLQJ HDFK RWKHU DFURVV WKH ULQJ 7KLV LV EHFDXVH URWDWLRQ V\PPHWU\ D[LV DERXW WKH WZRIROG D[LV RI V\PPHWU\ VKRZQ LQ WKH GUDZLQJ PDNHV WKHVH VHWV RI K\GURJHQV HTXLYDOHQW 2Q WKH RWKHU KDQG FLV GLVXEVWLWXWHG VSLURF\FORSURSDQHV FDQ EH H[SHFWHG WR VKRZ WKH VDPH NLQG RI FRPSOH[ SDWWHUQ REVHUYHG IRU WKH YLQ\O K\GURJHQV DV ZDV VHHQ LQ WKH PRQRVXEVWLWXWHG VSLURF\FORSURSDQHV f DQG f UHVXOWLQJ IURP WKH QRQHTXLYDOHQF\ RI IDFLQJ SDLUV RI K\GURJHQV RQ WKH RSSRVLWH VLGHV RI WKH VHYHQPHPEHUHG ULQJ $ PRGHO IRU FLVGLVXEVWLWXWHG VSLURF\FORSURSDQHV RI WKLV W\SH KDV EHHQ SUHSDUHG E\ .UDMFD IURP WKH UHDFWLRQ RI EHQ]RWURS\OLGHQH ZLWK F\FORKH[HQH 7KLV FRPSRXQG f VKRZV D QXFOHDU PDJQHWLF UHVRQDQFH SDWWHUQ LQ WKH YLQ\O UHJLRQ

PAGE 32

WKDW LV HVVHQWLDOO\ LGHQWLFDO WR WKH SDWWHUQ VKRZQ E\ WKH SKHQ\OF\FOR SURSDQH f $ VLPLODU YLQ\OLF DEVRUSWLRQ SDWWHUQ KDV EHHQ XVHG WR )LJXUH f DVVLJQ VWHUHRFKHPLFDO FRQILJXUDWLRQV LQ D VHULHV RI VSLURF\FORSUR SDQHV GHULYHG IURP WKH UHDFWLRQV RI GLPHWK\OF\FORKH[DGLHQ\OLGHQH ZLWK YDULRXV ROHILQV 7KLV LV VKRZQ LQ )LJXUH %RWK FLV DQG WUDQVGLVXEVWLWXWHG VSLURF\FORSURSDQHV RI WKLV W\SH ZHUH SUHSDUHG )LJXUH f %RWK LVRPHUV VKRZHG WKH H[SHFWHG HIIHFW RI V\PPHWU\ GLIIHUHQFHV XSRQ WKH QXFOHDU PDJQHWLF UHVRQDQFH VSHFWUD LQ WKH YLQ\OLF UHJLRQ :LWK WKH DERYHGHVFULEHG EDVLV IRU PDNLQJ VWHUHRFKHPLFDO DVVLJQPHQWV LQ GLVXEVWLWXWHG VSLURF\FORSURSDQHV LW LV SRVVLEOH WR VWXG\ WKH VWHUHRVSHFLILFLW\ RI WKH UHDFWLRQ RI IXURWURS\OLGHQH f ZLWK ROHILQV 7KH VWHUHRVSHFLILFLW\ WHVW LV ZLGHO\ XVHG DV D FKHPLFDO WHVW IRU GLVWLQJXLVKLQJ EHWZHHQ VLQJOHW DQG WULSOHW VWDWHV LQ FDUEHQHV 6WHUHRVSHFLILF DGGLWLRQ L H DGGLWLRQ WR ROHILQV WR SURGXFH F\FORSUR

PAGE 33

SDQHV LQ ZKLFK ROHILQ VWHUHRFKHPLVWU\ LV SUHVHUYHG LV FKDUDFWHULVWLF RI VLQJOHW FDUEHQHV 1RQVWHUHRVSHFLILF DGGLWLRQ LQ ZKLFK ROHILQ VWHUHRFKHPLVWU\ LV QRW SUHVHUYHG LV FKDUDFWHULVWLF RI WULSOHW FDUEHQHV $ VWHUHRFKHPLFDO VWXG\ ZDV XQGHUWDNHQ XVLQJ FLV DQG WUDQV EXWHQHV DV DFFHSWRU ROHILQV IRU WKH FDUEHQH f 7KHUPDO GHFRPSRn VLWLRQ RI WKH WRV\OK\GUD]RQH VDOW LQ WKH SUHVHQFH RI FLVEXWHQH DW r & DQG LQ WKH SUHVHQFH RI WUDQVEXWHQH DW WKH VDPH WHPn SHUDWXUH SURGXFHG WZR FUXGH UHDFWLRQ PL[WXUHV WKDW ZHUH YLUWXDOO\ LGHQWLFDO LQ WKHLU SURWRQ PDJQHWLF UHVRQDQFH VSHFWUD *DV FKURPDWRn JUDSKLF H[DPLQDWLRQ RI WKH FUXGH UHDFWLRQ PL[WXUHV XVLQJ D IRRW FDSLOODU\ FROXPQ FRDWHG ZLWK 8FRQ /% VKRZHG DW OHDVW FRPn SRQHQWV LQ WKH UHDFWLRQ PL[WXUHV 0RVW RI WKH FKURPDWRJUDSKLF SHDNV ZHUH LQ WKH VDPH TXDQWLWDWLYH UHODWLRQ WR HDFK RWKHU LQ ERWK PL[WXUHV 6HSDUDWLRQ RI WKH PDLQ SHDN RQ D SUHSDUDWLYH JDV FKURPDWRJUDSKLF LQVWUXPHQW WKRXJK LW JDYH D OHVVSHUIHFW VHSDUDWLRQ WKDQ WKH FDSLOODU\ LQVWUXPHQW GLG DOORZ VRPH QDUURZLQJ LQ WKH FKRLFH RI WKH VLJQLILFDQW SHDNV LQ WKH FKURPDWRJUDPV SUHSDUHG RQ WKH FDSLOODU\ LQVWUXPHQW VLQFH WKLV IUDFWLRQ ZDV VKRZQ E\ QXFOHDU PDJQHWLF UHVRQDQFH WR FRQn WDLQ WKH PDMRU FRPSRQHQWV SUHVHQW LQ WKH FUXGH SURGXFW 7KH VLJQLILn FDQW DUHD WXUQHG RXW WR EH D JURXS RI WZR VPDOOHU SHDNV DQG RQH PDMRU SHDN WKDW ZHUH QRW HYHQ ZHOO VHSDUDWHG RQ WKH FDSLOODU\ LQVWUXPHQW 4XDQWLWDWLYH GLIIHUHQFHV ZHUH VHHQ LQ WKH UHODWLRQ RI WKH WZR VPDOOHU SHDNV ZKHQ FRPSDULQJ VDPSOHV SUHSDUHG E\ WKHUPDO UHDFWLRQ ZLWK WKH FLV DQG WUDQV ROHILQV EXW WKH VLJQLILFDQFH RI WKLV GLIIHUHQFH EHWZHHQ WKHVH WZR VPDOOHU SHDNV PD\ EH WULYLDO EHFDXVH RI WKH IROORZLQJ REVHUn YDWLRQV 7KH SURWRQ PDJQHWLF UHVRQDQFH VSHFWUD YLGH LQIUDf RI

PAGE 34

ERWK UHDFWLRQ PL[WXUHV ZHUH LGHQWLFDO %RWK FUXGH UHDFWLRQ PL[WXUHV DSSHDUHG WR EH SUHGRPLQDQWO\ WKH WUDQVVSLURF\FORSURSDQH YLGH LQIUDf 7KHUH ZDV QR LQGLFDWLRQ RI WKH SUHVHQFH RI WKH FLVVSLURF\FORSUR SDQH LQ HLWKHU VDPSOH WR WKH OLPLW RI GHWHFWLRQ E\ WKH SURWRQ PDJQHWLF UHVRQDQFH VSHFWUD 7KHUPDO UHDFWLRQ RI WKH WRV\OK\GUD]RQH VDOW ZLWK WUDQVEXWHQH LV PRVW OLNHO\ WR SURGXFH WKH PRUH VWDEOH WUDQV VSLURF\FORSURSDQH LI SURGXFW LVRPHUL]DWLRQ LV WDNLQJ SODFH $ SKRWRn FKHPLFDO GHFRPSRVLWLRQ RI WKH VDOW LQ WKH SUHVHQFH RI FLVEXWHQH LV PRVW OLNHO\ WR SURGXFH WKH FLVVSLURF\FORSURSDQH EHFDXVH RI H[SHFWHG ORZHU SUREDELOLW\ RI WKHUPDO FLVWUDQV LVRPHUL]DWLRQ DW WKH PLOGHU WHPSHUDWXUHV FD r & XVHG $ FRPSDULVRQ RI WKH FDSLOODU\ FKURPDWRJUDPV RI WKHVH WZR UHDFWLRQV VKRZHG WKH VDPH TXDQWLWDWLYH UHODWLRQ DPRQJ WKH WKUHH SHDNV LQ WKLV VLJQLILFDQW DUHD $SSDUHQWO\ WKH PDMRU SHDN LV WKH WUDQVVSLURF\FORSURSDQH YLGH LQIUDf 7KH WZR PLQRU SHDNV ZHUH QHYHU LGHQWLILDEOH IRU WKH UHDVRQV RI VPDOO VDPSOH VL]H DQG GLIILFXOW\ RI SXULILFDWLRQ 7KH SURWRQ PDJQHWLF UHVRQDQFH VSHFWUD VXJJHVW WKDW WKHVH DUH SUREDEO\ PDLQO\ &+ LQVHUWLRQ SURGXFWV 7KH DWWDLQPHQW RI WKH VDPH SURGXFW PL[WXUH IURP FDUEHQH UHDFWLRQV ZLWK D SDLU RI LVRPHULF FLVDQG WUDQVROHILQV LV WKH FULWHULRQ IRU FRPn SOHWH ORVV RI VWHUHRVSHFLILFLW\ LQ WKH UHDFWLRQ 7KH IDLOXUH WR LVRODWH DQ\ RI WKH FLV VSLURF\FORSU RSDQH IURP WKH UHDFWLRQV ZLWK WKH EXWHQHV DQG WR GHPRQVWUDWH WKH VWDELOLW\ RI WKH FLV LVRPHU WR UHDFWLRQ FRQGLWLRQV GRHV OHDYH WKH H[SHULPHQW RSHQ WR WKH FULWLFLVP WKDW WKH FLVLVRPHU LV SRVVLEO\ EHLQJ IRUPHG WKHQ LV GHFRPn SRVLQJ WR HLWKHU WKH WUDQVLVRPHU RU WR VRPH RWKHU SURGXFW 7KLV SRVVLELOLW\ LV LPSRVVLEOH WR H[FOXGH ULJRURXVO\ LQ WKH SUHVHQW FDVH EXW VRPH LQIHUHQFHV IRU WKH VWDELOLW\ RI WKH FLVLVRPHU FDQ EH GUDZQ

PAGE 35

IURP D VWXG\ RI NQRZQ PRGHO FRPSRXQGV &\FORSURSDQHV RI WKH W\SH f DUH VXEMHFW WR D FOHDYDJH RI WKH F\FORSURS\O ULQJ IROORZHG E\ )LJXUH f LVRPHUL]DWLRQ WR DQ LQGDQH GHULYDWLYH 7KH VXEVWLWXWHG F\FORSURSDQH Df XQGHUJRHV LVRPHUL]DWLRQ DW r& EXW WKH XQVXEVWLWXWHG F\FORn SURSDQH Ef LV VWDEOH DW r & 6LPLODUO\ RQH VKRXOG H[SHFW DQ HQKDQFHG UDWH RI LVRPHUL]DWLRQ LQ WKH YLQ\OVXEVWLWXWHG VSLURF\FOR SURSDQH f )LJXUH f EHFDXVH RI VWDELOL]DWLRQ RI UDGLFDO LQWHUn PHGLDWH f 7KH LVRPHUL]DWLRQ LV VORZ DW r & VLQFH WKH F\FORn SURSDQH FDQ EH LVRODWHG DV WKH PDLQ SURGXFW IURP UHDFWLRQ PL[WXUHV H[SRVHG WR WKDW WHPSHUDWXUH IRU KU YLGH LQIUDf 7KLV VXJJHVWV WKDW FLVGLDON\OVSLURF\FORSURSDQHV ZRXOG UHTXLUH VXEVWDQWLDOO\ KLJKHU WHPSHUDWXUHV EHIRUH LVRPHUL]DWLRQ WR WKH WUDQV LVRPHU ZRXOG RFFXU DW D VLJQLILFDQW UDWH )LJXUH f

PAGE 36

,VRODWLRQ DQG FKDUDFWHUL]DWLRQ RI WKH WUDQV VSLURF\FORSURSDQH SURGXFHG IURP WKH UHDFWLRQ RI FDUEHQH f ZLWK WKH FLV DQG WUDQV EXWHQHV SURYHG WR EH DV GLIILFXOW DV WKH IRUHJRLQJ GLVFXVVLRQ ZRXOG VXJJHVW 5HDFWLRQ RI WUDQVEXWHQH E\ GHFRPSRVLWLRQ RI WKH VRGLXP VDOW DW r& SURGXFHG D FUXGH UHDFWLRQ PL[WXUH WKH SURWRQ PDJn QHWLF UHVRQDQFH VSHFWUXP RI ZKLFK VXJJHVWHG WKDW WKH PDLQ FRPSRQHQW f )LJXUH f ZDV WKH WUDQV GLPHWK\OF\FORSURSDQH f FRQWDPLQDWHG ZLWK &+ LQVHUWLRQ SURGXFWV 3UHSDUDWLYH OD\HU FKURPDWRJUDSK\ RQ VLOLFD JHO SODWHV GLG QRW LPSURYH WKH DSSHDUDQFH RI WKH VSHFWUXP YHU\ PXFK XQWLO WKH PDLQ EDQG ZDV FROOHFWHG DQG UHFKURPDWRJUDSKHG RQ VLOLFD JHO SODWHV XVLQJ YHU\ ORZ VDPSOH ORDGLQJ 7KLV DOORZHG VHSDUDWLRQ LQWR WKUHH EDQGV WKH PDMRU RQH RI ZKLFK JDYH D VSHFWUXP VXJJHVWLQJ D IDLUO\ SXUH VDPSOH RI WKH WUDQVDGGXFW f %HFDXVH RI VPDOO VDPSOH VL]H QHLWKHU RI WKH WZR PLQRU FRPSRQHQWV ZDV LGHQWLILHG 7KH \LHOG RI WKH WUDQV DGGXFW f DSSHDUV WR EH LQ WKH QHLJKERUKRRG RI SHUFHQW EXW H[WHQVLYH KDQGOLQJ RI VPDOO VDPSOHV PDNHV WKLV QXPEHU XQUHOLDEOH 7KH DVVLJQPHQW RI WKH VWUXFWXUH f UHVWV SULn PDULO\ RQ WKH SURWRQ PDJQHWLF UHVRQDQFH VSHFWUXP 7KHUH LV WKH XVXDO VKDUS VLQJOHW DW WDX IRU WKH IXUDQ K\GURJHQV )URP WKH GLVFXVVLRQ RQ SDJHV DQG RQH ZRXOG H[SHFW WKH $% SDWWHUQ WKDW LV REVHUYHG LQ WKH YLQ\OLF UHJLRQ SURGXFHG E\ WKH K\GURJHQV RQ

PAGE 37

fe < \f§nUf§ )LJXUH f

PAGE 38

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

PAGE 39

GHXWHUDWHG VW\UHQH UHDFWLRQ LW ZDV NQRZQ WKDW WKLV UHDFWLRQ VKRZQ LQ )LJXUH f FDQ EH XVHG WR SURGXFH UDWKHU SXUH VDPSOHV RI WKH SKHQ\O F\FORSURSDQH 7KH UHTXLUHG GHXWHUDWHG VW\UHQH ZDV SUHSDUHG E\ WKH VWHUHRn VSHFLILF DGGLWLRQ RI GLF\FORKH[\OERUDQH WR SKHQ\ODFHW\OHQH IROORZHG E\ K\GURO\VLV ZLWK GHXWHULRDFHWLF DFLG WR IUHH WKH VW\UHQH )RUPDO DGGLWLRQ RI WKH FDUEHQH WR WKLV ROHILQ ZDV FDUULHG RXW E\ S\URO\VLV RI WKH WRV\OK\GUD]RQH VDOW LQ D GLOXWH VROXWLRQ RI WKH ROHILQ LQ ERLOLQJ GLR[DQH E S r & f 7KH UHVXOWLQJ SKHQ\OF\FORSURSDQH ZDV VHSDUDWHG E\ SUHSDUDWLYH OD\HU FKURPDWRJUDSK\ 8VH RI GAEHQ]HQH DV D VROYHQW DOORZHG REVHUYDWLRQ RI WKH JHPLQDO F\FORSURS\O K\GURJHQV E\ 0+] SURWRQ PDJQHWLF UHVRQDQFH VSHFWURVFRS\ DV WZR GRXEOHWV DSSHDULQJ DW WDX 2QH RI WKH GRXEOHWV ZDV VSOLW E\ +] WKH RWKHU E\ +] %\ GRXEOH LUUDGLDWLRQ WR GHFRXSOH WKH QHLJKERULQJ F\FORSURS\O K\GURJHQ +Af IURP WKH JHPLQDO SDLU WKH IRXU VLJQDOV ZHUH FDXVHG WR FROODSVH WR WZR VLJQDOV KDYLQJ D VHSDUDWLRQ RI DERXW +] ,QWHJUDWLRQ RI WKH IRXU VLJQDOV EHIRUH GHFRXSOLQJf DQG WKH WZR VLJQDOV DIWHU GHFRXSOLQJf VKRZHG WKH SUHVHQFH RI DQ HTXDO PL[WXUH RI WKH WZR SRVVLEOH LVRPHUV 7KRXJK WKH IRUPDWLRQ RI DQ HTXDO PL[WXUH RI WKH WZR SRVVLEOH GHXWHULR SKHQ\OF\FORSURSDQHV LQ WKLV VWXG\ VXJJHVWV QRQVWHUHRVSHFLILF DGGLWLRQ RI WKH FDUEHQH WR WKH ROHILQ WKH UHVXOW LV QRW FRQFOXVLYH XQOHVV WKH SRVVLELOLW\ RI ROHILQ LVRPHUL]DWLRQ EHIRUH UHDFWLRQ DQG WKH SRVVLn ELOLW\ RI SURGXFW LVRPHUL]DWLRQ DIWHU UHDFWLRQ DUH H[FOXGHG 7KH ROHILQ ZDV GHWHUPLQHG WR EH VWHUHRFKHPLFDOO\ VWDEOH XQGHU WKH UHDFWLRQ FRQGLWLRQV E\ D FRQWURO H[SHULPHQW 7KH VWDELOLW\ RI WKH SURGXFW LV QRW VR HDVLO\ SURYHG 6HSDUDWLRQ RI WKH WZR VWHUHRLVRPHULF SURGXFWV LV QRW

PAGE 40

352721 0$*1(7,& 5(621$1&( 63(&7580 2) 352'8&7 Df 6+2:,1* 6,03/,),&$7,21 2) $%; )LJXUH f

PAGE 41

SRVVLEOH VR D GLUHFW WHVW IRU LVRPHUL]DWLRQ XQGHU UHDFWLRQ FRQGLWLRQV LV QRW SRVVLEOH 7KH EHVW UHPDLQLQJ RSWLRQ LV WR FRQGXFW WKH UHDFWLRQ DW D WHPSHUDWXUH DW ZKLFK SURGXFW LVRPHUL]DWLRQ LV KLJKO\ XQOLNHO\ 2QH FDQ DOVR GUDZ LQIHUHQFHV DERXW WKH WKHUPDO VWDELOLW\ DQG WKH SKRWRFKHPLFDO VWDELOLW\ RI WKH SKHQ\OF\FORSURSDQH DGGXFW E\ H[DPLQDn WLRQ RI PRGHO FRPSRXQGV YLGH LQIUDf 7KH UHDFWLRQ ZLWK WUDQVGHXWHULRVW\UHQH ZDV UHSHDWHG E\ GHFRPn SRVLQJ WKH VRGLXP VDOW RI WKH WRV\OK\GUD]RQH SKRWRO\WLFDOO\ DW DERXW r & 7KLV SURFHGXUH DOVR SURGXFHG DQ HTXDO DPRXQW RI WKH WZR SRVVLEOH VWHUHRLVRPHUV 7KRXJK LW PLJKW KDYH EHHQ GHVLUDEOH WR KDYH FDUULHG RXW WKH SKRWRO\VLV DW HYHQ ORZHU WHPSHUDWXUHV WKH SURSHUWLHV RI WKLV FDUEHQH DUH VXFK WKDW LW GRHV QRW DGG UHDGLO\ WR ROHILQV DW ORZ WHPSHUDWXUHV 7KLV SRLQW ZLOO EH GLVFXVVHG IXUWKHU LQ FRQQHFWLRQ ZLWK UHDFWLRQV RI WKLV FDUEHQH ZLWK EXWDGLHQH 7KH VW\UHQH GLG QRW LVRPHUL]H XQGHU SKRWRO\VLV 7KH SKRWRO\WLF DQG WKHUPDO VWDELOLW\ RI WKH SKHQ\OF\FORSURSDQH Df FDQ EH LQIHUUHG IURP WKH IROORZLQJ GDWD 7KH YLQ\OF\FORSUR SDQH f VHH )LJXUH f UHTXLUHV WHPSHUDWXUHV JUHDWHU WKDQ r& IRU DQ DSSUHFLDEOH UDWH RI ULQJRSHQLQJ IROORZHG E\ FORVXUH WR WKH F\FORSHQWHQH f 7KH VDPH YLQ\OF\FORSURSDQH ZDV GHWHUPLQHG YLGH LQIUDf WR EH SKRWRO\WLFDOO\ VWDEOH XQGHU UHDFWLRQ FRQGLWLRQV 7KH VRPHZKDW VLPLODU SKHQ\OVSLUR fQRQD WULHQH f VKRZQ LQ )LJXUH UHTXLUHV WHPSHUDWXUHV JUHDWHU WKDQ r& IRU LVRPHUL]DWLRQ WR WKH SKHQ\OELF\FOR fQRQD WULHQH f EXW LWV LVRPHUL]DWLRQ LV DLGHG E\ WKH IRUPDWLRQ RI D QHZ VWDEOH FRPn SRXQG RI D W\SH WKDW FDQQRW EH IRUPHG IURP f 7KH YLQ\OF\FOR R SURSDQH f UHDUUDQJHV WR f DW & 2Q WKH RWKHU KDQG WKH

PAGE 42

EXWDGLHQH DGGXFW f LV VWDEOH HQRXJK WR EH LVRODWHG E\ SUHSDUDWLYH JDV FKURPDWRJUDSK\AA r FK f FK )LJXUH f 3\URO\VLV RI WKH WRV\OK\GUD]RQH VDOW f LQ WKH SUHVHQFH RI EXWDGLHQH DW r& SURGXFHV DOPRVW H[FOXVLYHO\ WKH DGGLWLRQ SURGXFW f SHUFHQW \LHOGf VKRZQ LQ )LJXUH ,W KDV EHHQ K\SRWKn HVL]HG WKDW WULSOHW FDUEHQHV PLJKW UHDFW ZLWK GLHQHV LQ WKH DGGLWLRQ PRGH )HZ FDUEHQHV LI DQ\ DFWXDOO\ GR DGG LQ WKLV PDQQHU

PAGE 43

E\ GLUHFW UHDFWLRQ 0RVW DGGXFWV DULVLQJ IURP D IRUPDO DGGLWLRQ DUH SURGXFWV IURP WKH WKHUPDO LVRPHUL]DWLRQ RI LQLWLDOO\ IRUPHG DGGLWLRQ SURGXFWV VXFK DV f 7KDW SURYHG WR EH WUXH LQ WKLV FDVH DOVR 7KHUPDO GHFRPSRVLWLRQ RI WKH WRV\OK\GUD]RQH VDOW LQ EXWDGLHQH DW r& IRU VKRUW UHDFWLRQ WLPHV KU RU OHVVf SURGXFHG WKH DGGXFW f +HDWLQJ RI WKH YLQ\OF\FORSURSDQH f f 7R7 ff )LJXUH f DW r & IRU KU FDXVHG FRPSOHWH FRQYHUVLRQ WR WKH LVRPHULF F\FORSHQWHQH f 6WUXFWXUDO DVVLJQPHQW RI WKH DGGLWLRQ SURGXFW f ZDV EDVHG RQ WKH IROORZLQJ VSHFWUDO GDWD ,Q WKH SURWRQ PDJQHWLF UHVRQDQFH VSHFWUXP WKHUH LV WKH H[SHFWHG WZRK\GURJHQ VLQJOHW DW WDX IRU WKH IXUDQ K\GURJHQV 6LQFH WKLV PROHFXOH KDV WKH VDPH NLQG RI V\PPHWU\ DV WKH GLPHWK\OF\FORSURSDQH f VKRZQ LQ )LJXUH RQH FDQ SUHGLFW WKH VDPH NLQG RI $% SDWWHUQ IRU WKH YLQ\O K\GURJHQV +Df DQG +Af LQ WKH VHYHQPHPEHUHG ULQJ 7KLV H[SHFWHG IRXUOLQH $% SDWWHUQ LV REVHUYHG LQ f 2QH RI WKH GRXEOHWV LQ WKH $% SDWWHUQ LV FHQWHUHG DW WDX DQG LV VSOLW E\ +] 7KH RWKHU GRXEOHW LV FHQWHUHG DW WDX UHSUHVHQWLQJ WKH +Af K\GURJHQVf EXW WKH OHIW KDOI RI WKH GRXEOHW KDV D SDUWLDOO\ VXSHULPSRVHG SHDN IURP WKH YLQ\OLF K\GURJHQV LQ WKH F\FORSHQWHQH ULQJ +Ff 7KH LQWHJUDO IRU WKH ORZHU

PAGE 44

rp }} P B B W W} B B Z 7 }‘! W \ P 352721 0$*1(7,& 5(621$1&( 63(&7580 2) 352'8&7 f )LJXUH f

PAGE 45

ILHOG GRXEOHW LV WZR K\GURJHQV 7KH LQWHJUDO IRU WKH XSSHUILHOG GRXEOHW FRQWDLQLQJ WKH VLJQDO IRU WKH F\FORSHQWHQH ROHILQLF K\GURJHQV LQGLFDWHV D WRWDO RI IRXU K\GURJHQV 7KH UHPDLQGHU RI WKH VSHFWUXP LV D VKDUS VLQJOHW DW WDX ZLWK D FRUUHFW LQWHJUDO IRU WKH IRXU DOO\OLF K\GURJHQV +Af 7KH ODFN RI GLVFHUQLEOH VSOLWWLQJ RI WKH DOO\OLF K\GURJHQV LV FRQVLVWHQW ZLWK WKH UHSRUWHG +] DOO\OLF VSOLWWLQJ LQ F\FORSHQWHQH LWVHOI 7KH KLJK V\PPHWU\ RI WKH DGGXFW f JLYHV ULVH WR VRPH GRXEW DV WR ZKHWKHU WKH & & ERQG LQ WKH F\FORSHQWHQH ULQJ VKRXOG HYHQ EH LQIUDUHG DFWLYH DW DOO 1HYHUWKHOHVV WKHUH LV D ZHDN DEVRUSWLRQ DW FP r WKDW GRHV ILW WKH NQRZQ SDWWHUQ IRU & & VWUHWFK LQ ILYHPHPEHUHG ULQJV F\FOREXWHQH FP F\FORSHQWHQH FP F\FORKH[HQH FP f 6WUXFWXUDO DVVLJQPHQW RI WKH DGGLWLRQ SURGXFW ZLWK EXWDGLHQH ZDV EDVHG RQ WKH IROORZLQJ LQIRUPDWLRQ 7KH IXUDQ K\GURJHQV DSSHDUHG DV D WZRK\GURJHQ VLQJOHW DW WDX 7KH YLQ\O UHJLRQ VKRZHG FOHDUO\ WKH UHVXOWV RI WKH V\PPHWU\GLVWXUELQJ H[RF\FOLF YLQ\O JURXS 7KH SDWWHUQ IRU WKH + f DQG + f K\GURJHQV ZDV D SDUWLDOO\ RYHU ODSSLQJ SDLU RI GRXEOHWV VKRZLQJ WKH VDPH +] FRXSOLQJ EHWZHHQ WKH $% SDLU LQ WKH VHYHQPHPEHUHG ULQJ WKDW KDV EHHQ REVHUYHG LQ f DQG f 7KLV IRXUOLQH VLJQDO IRU WKH + f DQG+Df K\GURJHQV ZDV DERXW WDX $QRWKHU IRXUOLQH VLJQDO IRU WKH +Af DQG +ALf K\GURJHQV DSSHDUHG DW DERXW WDX 2QFH DJDLQ VLQFH WKHVH WZR K\GURJHQV DUH QRQHTXLYDOHQW WKH :IRUP FRXSOLQJ RI FD +] ZDV REVHUYHG LQ DGGLWLRQ WR WKH FRXSOLQJ ZLWK WKH +Df DQG +DLf K\GURJHQV 7KH YLQ\OLF K\GURJHQV EHORQJLQJ WR WKH H[RF\FOLF YLQ\O JURXS DSSHDUHG EHWZHHQ WKH WZR VHWV RI VLJQDOV IRU WKH $% SDLU LQ WKH VHYHQPHPEHUHG ULQJ 7KH + Af VLJQDO DSSHDUHG IURP DERXW WR

PAGE 46

} L f§f§ 7aL c ‘‘ L f§ Sf§Lf§ LU 352721 0$*1(7,& 5(621$1&( 63(&7580 2) 352'8&7 f f )LJXUH f

PAGE 47

‘ r ‘f§n ‘ff§ ULf§ U 9 f§7 K 352721 0$*1(7,& 5(621$1&( 63(&7580 2) 352'8&7 f 6+2:,1* (1/$5*(0(17 2) $%; 3257,21 )LJXUH f

PAGE 48

WDX ZLWK SULPDULO\ D IRXUOLQH SDWWHUQ 7KH +f DQG +f K\GURJHQV ZHUH DW WDX SUHVHQWLQJ D FRPSOH[ SDWWHUQ WKDW KDG VR PXFK ILQH VWUXFWXUH WKDW GLUHFW PHDVXUHPHQW RI WKH FRXSOLQJ FRQVWDQWV ZDV QRW SRVVLEOH 8VH RI D 0+] VSHFWURPHWHU PDGH LW SRVVLEOH WR UHVROYH HDFK VHW RI YLQ\OLF K\GURJHQV ERWK WKH $% SDLU DQG WKH H[RF\FOLF YLQ\O K\GURJHQV VXIILFLHQWO\ WR DOORZ DQ DFFXn UDWH LQWHJUDWLRQ IRU HDFK VLJQDO $OO RI WKH LQWHJUDOV ZHUH VDWLVIDFn WRU\ 7KH UHPDLQGHU RI WKH VSHFWUXP SUHVHQWHG WKH H[SHFWHG $%; SDWWHUQ IRU WKH F\FORSURS\O K\GURJHQV 'LUHFW PHDVXUHPHQW RI ZDV +] 7KH $% SRUWLRQ RI WKH VSHFWUXP IRU WKH YLFLQDO F\FORn SURS\O K\GURJHQVf ZDV DW WDX 7KH ; SRUWLRQ ZDV DW DERXW WDX 7KH $% VLJQDO DOORZHG HDV\ UHFRJQLWLRQ RI WKH H[SHFWHG SDLU RI RYHUODSSLQJ TXDUWHWV 7KH ; VLJQDO JDYH DQ LQWHJUDO WKDW ZDV VOLJKWO\ ORZHU WKDQ WKH FRUUHFW YDOXH EHFDXVH VRPH RI WKH OLQHV ZHUH EXULHG LQ LQVWUXPHQW QRLVH )RXU RI WKH OLQHV ZHUH YLVLEOH EXW RQO\ WZR RI WKHP ZHUH YHU\ VWURQJ 7KH VSHFWUXP DOVR VKRZHG D VKDUS VLQJOHW DW DERXW WDX IURP D FRQWDPLQDWLQJ LQKLELWRU GLWHUW EXW\OPHWK\O SKHQROf SLFNHG XS GXULQJ H[SRVXUH RI WKH VDPSOH WR D FRPPHUFLDO JUDGH RI WHWUDK\GURIXUDQ (OHPHQWDO DQDO\VLV ZDV PDGH LPSRVVLEOH EHFDXVH RI WKH SUHVHQFH RI WKH LQKLELWRU VLQFH LW ZDV GLIILFXOW WR VHSDUDWH IURP WKH VDPSOH 7KH SUREOHP ZDV VXUn PRXQWDEOH E\ WKH UHDG\ FRQYHUVLRQ RI WKH DGGXFW WR WKH DGGXFW f ZKLFK ZDV HDV\ WR VHSDUDWH IURP WKH LQKLELWRU DQG WR SURYLGH LQ SXUH IRUP IRU HOHPHQWDO DQDO\VLV 7KH H[RF\FOLF YLQ\O 2 & JURXS LQ f ZDV VKRZQ E\ LQIUDUHG 'HFRPSRVLWLRQ RI WKH WRV\OK\GUD]RQH VDOW E\ SKRWRO\VLV DW ORZ WHPSHUDWXUHV LQ WKH SUHVHQFH RI EXWDGLHQH FDXVHG D UHPDUNDEOH

PAGE 49

FKDQJH LQ WKH FKDUDFWHU RI UHDFWLRQ ZLWK WKLV ROHILQ $W WHPSHUDWXUHV RI r WR r & LW SURGXFHV WKH SURGXFW f VKRZQ LQ )LJXUH LQ DERXW SHUFHQW \LHOG DV WKH RQO\ K\GURFDUERQ SURGXFW LGHQWLILDEOH 7KH VWUXFWXUH RI f ZDV LGHQWLILHG E\ WKH VWULNLQJ VLPLODULWLHV LQ LWV VSHFWUD ZLWK WKH VSHFWUD RI D QXPEHU RI VLPLODU FRPSRXQGV UHFHQWO\ SUHSDUHG DQG HOXFLGDWHG LQ GHWDLO E\ &REXUQ ,Q WKH SURWRQ PDJn QHWLF UHVRQDQFH VSHFWUXP WKH IXUDQ K\GURJHQV SURGXFHG D WZRK\GURJHQ VLQJOHW DW WDX 7KH YLQ\OLF K\GURJHQV +tf SURGXFHG DQ $% SDWWHUQ FHQWHUHG QHDU WDX VSOLW E\ +] 7KH RWKHU YLQ\OLF K\GURJHQV +Af SURGXFH D SRRUO\ UHVROYHG SHDN DW WDX 7KH DOO\OLF K\GURJHQV DSSHDU DV D EURDGHQHG SHDN DW WDX 7KH F\FORSURS\O K\GURJHQ +Hf DSSHDUV DV D GRXEOHW DW DERXW WDX FRXSOHG E\ DERXW +] WR WKH RWKHU F\FORSURS\O K\GURJHQ +Af ZKLFK DSSHDUV XSILHOG DV D PXOWLSOHW DW WDX 3KRWRO\VLV RI WKH WRV\OK\GUD]RQH VDOW DW LQWHUPHGLDWH WHPSHUDn WXUHV FD r &f SURGXFHG D PL[WXUH RI f DQG WKH DGGLWLRQ SURGXFW f IURP UHDFWLRQ ZLWK EXWDGLHQH 7KH UDWLR ZDV DERXW 1RQH RI WKH DGGXFW f ZDV SURGXFHG ,Q FRQWURO H[SHULPHQWV WKH DGGXFW f ZDV VKRZQ WR EH VWDEOH WR SKRWRO\VLV WKHUHIRUH LW LV QRW WKH VRXUFH RI WKH SURGXFW f 7KH SURGXFW f ZDV VKRZQ WR EH WKHUPDOO\ VWDEOH IRU DW OHDVW PLQXWHV DW r & VLQFH LW FRXOG EH SXULILHG E\ SUHSDUDWLYH JDV FKURPDWRJUDSK\ 7R VHH LI QRUPDO FDUEHQH EHKDYLRU FRXOG EH HOLFLWHG DW ORZ WHPSHUDWXUHV DQ HIIRUW ZDV PDGH WR DGG WKH FDUEHQH WR WUDQV EXWHQH E\ SKRWRO\VLV RI WKH WRV\OK\GUD]RQH VDOW DW r & 1RUPDO FDUEHQH DGGLWLRQ WR WKH ROHILQ GLG QRW RFFXU DV VKRZQ E\ WKH SURWRQ

PAGE 50

352721 0$*1(7,& 5(621$1&( 63(&7580 2) 352'8&7 f r f I &+a&+f§&+ &+ f )LJXUH f

PAGE 51

PDJQHWLF UHVRQDQFH VSHFWUXP RI WKH FUXGH SURGXFW 7KH IULDEOH DSSHDUDQFH RI WKH SURGXFW VXJJHVWHG WKDW LW ZDV DW OHDVW SDUWO\ SRO\PHULF ,Q H[SHULPHQWV GHVLJQHG WR DOORZ HTXDO DPRXQWV RI ROHILQ DFFHSWRUV WR FRPSHWH IRU WKH FDUEHQH f WKH IROORZLQJ UHODWLYH UDWH GDWD ZHUH REWDLQHG 2/(),1 5(/$7,9( 5$7( EXWHQH LVREXWHQH EXWDGLHQH 7DEOH f 2QH H[SHULPHQW ZDV GRQH WR DWWHPSW WR REVHUYH D VLJQDO LQ WKH SURWRQ PDJQHWLF UHVRQDQFH VSHFWUXP LQGLFDWLQJ WKH RSHUDWLRQ RI WKH FKHPLFDOO\ LQGXFHG G\QDPLF QXFOHDU SRODUL]DWLRQ &,'13f SKHQRP HQRQ 6XFK DQ REVHUYDWLRQ ZRXOG EH LQGLFDWLYH RI WKH SUHVHQFH RI D WULSOHW FDUEHQH 7KHUPDO GHFRPSRVLWLRQ RI WKH WRV\OK\GUD]RQH VDOW LQ VROXWLRQ LQ DQ QPU VDPSOH WXEH FRQWDLQLQJ D PL[WXUH RI DSSUR[LPDWHO\ SHUFHQW F\FORKH[HQH LQ GAGLPHWK\O VXOIR[LGH IDLOHG WR VKRZ WKH &,'13 SKHQRPHQRQ 7KLV FRXOG EH DWWULEXWDEOH WR WKH ORZ VROXELOLW\ RI WKH WRV\OK\GUD]RQH VDOW LQ WKLV PHGLXP LQGLFDWHG E\ WKH IDLOXUH WR REVHUYH WKH SUHVHQFH RI WKH VDOW LQ WKH VSHFWUXP RI WKH VROXWLRQ

PAGE 52

',6&866,21 7KHUPRO\VLV RU SKRWRO\VLV RI WRV\OK\GUD]RQH VDOWV RI WURSRQH DQG VXEVWLWXWHG WURSRQHV LQ VROXWLRQ KDYH EHHQ IRXQG WR JLYH DW OHDVW ILYH GLIIHUHQW NLQGV RI UHDFWLYH VSHFLHV )LJXUH f 8QVXEVWLWXWHG WURSRQH f VKRZV FKHPLVWU\ RI RQO\ WKH VLQJOHW FDUEHQH ,f 0RQRDQQHODWHG WURSRQHV f DQG f VKRZ VRPH FKHPLVWU\ H[SHFWHG RI WKH VLQJOHW FDUEHQH ,f EXW LQ JHQHUDO WKHLU FKHPLFDO EHKDYLRU LV GRPLQDWHG E\ WKH ELF\FORKHSWDWULHQH ,,,f DQG WKH UHDUUDQJHG VLQJOHW DQG WULSOHW DU\O FDUEHQHV ,9f DQG 9f A 7KH GLDQQHODWHG WURSRQH f VKRZV RQO\ WKH FKHPLVWU\ RI WKH ELF\FORKHSWDWULHQH ,,,f DQG WKH DU\O FDUEHQH SUHVXPDEO\ VLQJOHW ,9f DQG WULSOHW 9f 7KH GLDQQHODWHG DQG WULDQQHODWHG WURSRQHV f DQG f VKRZ W\SLFDO GLDU\O FDUEHQH FKHPLVWU\ 7KH\ KDYH EHHQ VKRZQ WR KDYH WULSOHW JURXQG VWDWHV EXW WKHLU FKHPLVWU\ LV GRPLQDWHG E\ WKH VLQJOHW A 7KH UHDVRQV IRU WKHVH GLIIHUHQFHV FDQ EH TXDOLWDWLYHO\ UDWLRQDOL]HG LQ WHUPV RI WKH H[SHFWHG UHODWLYH HQHUJLHV RI WKH GLIIHUHQW LQWHUPHGLDWHV &DUEHQH VWDELOLWLHV DUH WKRXJKW WR UXQ SDUDOOHO WR FDWLRQ VWDELOLn WLHV 0RQRDQQHODWLRQ NQRZQ WR GHVWDELOL]H WKH WURS\O FDWLRQ VKRXOG QRW EH H[SHFWHG WR KDYH VLJQLILFDQW HIIHFW RQ WKH VWDELOLW\ RI WKH LQWHUn PHGLDWH F\FORSURSHQH ,,,f 0RQRDQQHODWLRQ VKRXOG WKHQ GHFUHDVH WKH VWDELOLW\ RI WKH FDUEHQH UHODWLYH WR WKH F\FORSURSHQH LQWHUPHGLDWH PDNLQJ WKH UHDUUDQJHPHQW HDVLHU 7KH GLDQQHODWHG VSHFLHV f DQG WKH WULDQQHODWHG VSHFLHV f E\ LQFRUSRUDWLQJ LQWR WKH IXVHG EHQ]HQH V\VWHPV WKH GRXEOH ERQG WKDW PXVW VXIIHU DWWDFN LQ RUGHU IRU

PAGE 53

k f $ % + f $ + % IXVHG EHQ]HQH ULQJ f $ IX V HG 'HQ]HQH ULQJ % + f $ % IXV HG EHQ]HQH ULQJ + f $ IXV HG EHQ]HQH ULQJ % + f $ % IXVHG EHQ]HQH ULQJ )LJXUH f : 4

PAGE 54

UHDUUDQJHPHQW WR RFFXU UHGXFH WKH SUREDELOLW\ RI UHDUUDQJHPHQW E\ LQFUHDVLQJ WKH UHODWLYH HQHUJ\ RI WKH LQWHUPHGLDWH F\FORSURSHQH EHFDXVH RI ORVV RI EHQ]HQRLG DURPDWLFLW\ 7KH GLDQQHODWHG VSHFLHV f GRHV QRW UHTXLUH DV PXFK ORVV RI DURPDWLFLW\ WR IRUP WKH F\FORn SURSHQH ,,,f VR LW XQGHUJRHV UHDUUDQJHPHQW HDVLO\ 0DQ\ FDUEHQHV WKDW DUH IRUPHG LQ WKHLU VLQJOHW VWDWHV UHDFW LQ WKHLU VLQJOHW VWDWHV EHFDXVH WKH VLQJOHW LV VR UHDFWLYH WKDW UHDFWLRQ RFFXUV EHIRUH FROOL VLRQDO GHDFWLYDWLRQ WR WULSOHW LI WKDW LV WKH JURXQG VWDWH FDQ RFFXU (TXLOLEUDWLRQ EHWZHHQ D UHDFWLYH VLQJOHW DQG D UHODWLYHO\ XQUHDFWLYH WULSOHW FDQ DOVR FDXVH WKH VDPH HIIHFW 7KH SUHVHQW FDUEHQH f ILWV WKLV RYHUDOO VFKHPH EXW DV D UHVXOW RI LWV XQXVXDO VWUXFWXUH LW VHHPV WR KDYH D XQLTXH SODFH LQ WKH VFKHPH ,Q WKH ILUVW SODFH XQOLNH DQ\ RI WKH RWKHU FDUEHQHV VWXGLHG XQGHU FHUWDLQ FRQGLWLRQV DERYH DERXW r & f LWV FKHPLVWU\ LV DSSDUn HQWO\ GRPLQDWHG E\ WKH WULSOHW 7KH FRPSOHWH ORVV RI VWHUHRVSHFLILFLW\ LQ UHDFWLRQV RI FfIXUR WURS\OLGHQH LV FRQVLVWHQW ZLWK WULSOHW EHKDYLRU 7KH QRQVWHUHRVSHFLILF DGGLWLRQ RI D FDUEHQH LQ VROXWLRQ LV QRZ ZHOO HVWDEOLVKHG DV D FULWHULRQ IRU LQWHUSUHWLQJ WKH UHDFWLRQ LQ WHUPV RI D WZRVWHS UHDFWLRQ L H YLD WULSOHW 7KH SUHVHQW VWHUHRVSHFLILFLW\ VWXGLHV PXVW EH WDNHQ ZLWK WKH FDYHDW RI *DVSDU DQG +DPPRQG LQ PLQG WKDW 1RQVWHUHRVSHFLILF DGGLWLRQ FDQQRW EH WDNHQ DV D SURRI WKDW DQ DWWDFNLQJ VSHFLHV LV D WULSOHW XQOHVV LW KDV DOVR EHHQ VKRZQ WKDW XQGHU VRPH RWKHU FRQGLWLRQV D VSHFLHV RI WKH VDPH FRPSRVLWLRQ FDQ JLYH VWHUHRVSHFLILF DGGLWLRQ &ORVV LQ D PRUH UHFHQW YLHZ DVVHUWV WKDW QRQ VWHUHRVSHFLILF UHDFn WLRQV FDQ DOZD\V EH LQWHUSUHWHG DV SURFHHGLQJ YLD WKH WZRVWHS PHFK DQLVP L H YLD WULSOHW

PAGE 55

7KH UHODWLYH UHDFWLYLWLHV RI FfIXURWURS\OLGHQH LQ UHDFWLRQV ZLWK ROHILQV DOVR ILW WKH WULSOHW SDWWHUQ ,W LV ZHOO DFFHSWHG WKDW FRQn MXJDWHG GLHQHV VXFK DV EXWDGLHQH VKRZ D KLJK UHODWLYH UDWH RI UHDFWLRQ ZLWK WULSOHWV EHFDXVH RI DOO\OLF VWDELOL]DWLRQ RI WKH GLUDGLFDO LQWHUPHGLDWH )LJXUH f LQ WKH WZRVWHS UHDFWLRQ 7KH FRPPRQ XVH RI EXWDGLHQH DV D WULSOHW VFDYHQJHU WR LPSURYH VWHUHRVSHFLILFLW\ RI 95 )LJXUH f FDUEHQH UHDFWLRQV E\ VHOHFWLYHO\ GUDLQLQJ RII WULSOHW LOOXVWUDWHV WKLV SULQFLSOH 7KH UHODWLYH UDWHV IRXQG LQ WKLV SUHVHQW VWXG\ DOVR ILW WKH UHODWLYH UDWH SDWWHUQ IRU WKH UDWH RI UDGLFDO DGGLWLRQ YV DEVWUDFWLRQ ZLWK WKH VDPH ROHILQV ,QWHUSUHWLQJ WKH UHDFWLRQ RI FfIXURWURS\OLGHQH ZLWK EHQ]HQH LQ WHUPV RI WULSOHW FKHPLVWU\ LV DLGHG E\ FRQVLGHUDWLRQ RI VRPH UHODWHG UHSRUWV LQ WKH OLWHUDWXUH %LVFDUERPHWKR[\fFDUEHQH KDV EHHQ JHQHUn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f DQG

PAGE 56

WKH &+ LQVHUWLRQ SURGXFW f LQ D UDWLR RI WR 7KH SKRWRn VHQVLWL]HG UHDFWLRQ JDYH WKH VDPH WZR FRPSRXQGV LQ D UDWLR RI WR )LJXUH f 7KH LQFUHDVHG DPRXQW RI WKH SKHQ\OPDORQDWH f ZKHQ WKH FDUEHQH LV SUHSDUHG LQ WKH WULSOHW VWDWH LV FRQVLVWHQW ZLWK WKH LQWHUn PHGLDF\ RI WKH GLUDGLFDO ZKLFK FDQ HLWKHU FORVH WR WKH QRUFDUDGLHQH UHODWHG WR WKH F\FORKHSWDWULHQH RU XQGHUJR K\GURJHQ VKLIW WR IRUP WKH SKHQ\OPDORQDWH ,QFUHDVHG WULSOHW FKDUDFWHU LQ WKH DWWDFNLQJ FDUEHQH LQFUHDVHV WKH DPRXQW RI WKH &+ LQVHUWLRQ SURGXFW ,I WKH VORZ VWHS RI WKH UHDFWLRQ LV DWWDFN RI WULSOHW FDUEHQH XSRQ D EHQ]HQH GRXEOH ERQG WKH DEVHQFH RI D GHXWHULXP LVRWRSH HIIHFW LV WR EH H[SHFWHG 7KLV ZDV GHPRQVWUDWHG LQ WKH SUHVHQW VWXG\ ZLWK FfIXURWURS\OLGHQH 6WLOO WKHUH DUH KD]DUGV LQ LQWHUSUHWLQJ WKH LQVHUWLRQ RI IXUR WURS\OLGHQH LQWR WKH &+ ERQGV RI EHQ]HQH DV QHFHVVDULO\ D WULSOHW EHKDYLRU $ GLUDGLFDO LQWHUPHGLDWH VXFK DV WKDW VKRZQ LQ )LJXUH FRXOG DULVH IURP DQRWKHU SDWK &RQVLGHU IRU H[DPSOH WKH VL[ PHPEHUHG FDUERF\FOLF FDUEHQH GLPHWK\OF\FORKH[DGLHQ\OLGHQH ,W DSSDUHQWO\ UHDFWV ZLWK ROHILQV LQ WKH VLQJOHW VWDWH LQ VROXWLRQ ,W UHDFWV ZLWK EHQ]HQH WR SURGXFH D VSLURQRUFDUDGLHQH f VKRZQ LQ )LJXUH 7KLV VSLURQRUFDUDGLHQH LVRPHUL]HV DW r& WR SURGXFH WKH LQWHUPHGLDWH f WKDW LV YHU\ PXFK OLNH WKH GLUDGLFDO LQWHUPHGLDWH

PAGE 57

WKDW FRXOG DULVH IURP WULSOHW DWWDFN XSRQ WKH EHQ]HQH GRXEOH ERQG +HUH LV DSSDUHQWO\ D VLQJOHW SDWKZD\ WR WKH GLUDGLFDO LQWHUPHGLDWH )LJXUH f 1RQH RI WKH DQDORJRXV QRUFDUDGLHQH ZDV GHWHFWHG LQ WKH IXURWURS\OLGHQH FDVH HYHQ ZKHQ WKH UHDFWLRQ ZDV FDUULHG RXW E\ SKRWRO\VLV DW URRP WHPSHUDWXUH EXW WKH SRVVLELOLW\ RI WKDW LQWHUPHGLDWH LV YHU\ UHDO EHn FDXVH RI WKH FRPSOH[LW\ RI WKH PL[WXUH WKDW ZDV SURGXFHG LQ WKH UHDFn WLRQ 7KH DEVHQFH RI D GHXWHULXP LVRWRSH HIIHFW ZRXOG DOVR EH H[SHFWHG IURP WKH VLQJOHW SDWKZD\ $OWKRXJK QR RQH SLHFH RI HYLGHQFH LQ WKLV UHSRUW FDQ EH VDLG WR ULJRURXVO\ SURYH WKDW FfIXURWURS\OLGHQH LV EHKDYLQJ DV D WULSOHW DW WHPSHUDWXUHV DERYH r& FHUWDLQO\ WKH PDVV RI HYLGHQFH WDNHQ DV D ZKROH ORRNV IDLUO\ FRQYLQFLQJ 2QH WKLQJ LV FHUWDLQWKH F\FOR SURSHQH LQWHUPHGLDWH W\SH ,,, )LJXUH f GRPLQDWHV DW ORZHU WHPSHUDn WXUHV 7KLV LV VKRZQ E\ WKH WUDSSLQJ RI WKH F\FORSURSHQH LQWHUPHGLDWH f VHH )LJXUH f E\ WKH 'LHOV$OGHU UHDFWLRQ ZLWK EXWDGLHQH WR IRUP WKH DGGXFW f VKRZQ LQ )LJXUH 7KH F\FORSURSHQH VHHPV OLNHO\ WR KDYH IRUPHG IURP WKH VLQJOHW VWDWH RI WKH FDUEHQH VLQFH WKH FDU EHQH LV DOPRVW FHUWDLQO\ LQLWLDOO\ IRUPHG LQ WKH VLQJOHW VWDWH DQG VLQFH LQWUDPROHFXODU UHDFWLRQV VHHP WR EH IDYRUHG IRU FDUEHQHV LQ WKH

PAGE 58

L Q L VLQJOHW VWDWH f )RU H[DPSOH GLUHFW LUUDGLDWLRQ RI DOLSKDWLF DOSKDGLD]RNHWRQHV SURGXFHV D SUHGRPLQDQFH RI WKH SKRWRFKHPLFDO :ROII UHDUUDQJHPHQW EXW SKRWRVHQVLWL]HG LUUDGLDWLRQ ZKLFK VKRXOG LQFUHDVH WULSOHW IRUPDWLRQ SURGXFHV DQ LQFUHDVHG DPRXQW RI F\FOR SURSDQHV VXJJHVWLQJ QRUPDO LQWHUPROHFXODU FDUEHQH UHDFWLRQV )RUPDWLRQ RI WKH F\FORSURSHQH LQWHUPHGLDWH f LV D SDUWLFXn ODUO\ VXUSULVLQJ UHVXOW VLQFH WKH FfIXURWURS\OLGHQH f KDV QRW VKRZQ DQ\ HYLGHQFH RI UHDUUDQJHPHQW WR WKH LVREHQ]RIXUDQ VNHOHWRQ DV PLJKW KDYH EHHQ H[SHFWHG )LJXUH f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f f DQG f LQ )LJXUH 3HUKDSV WKH ULQJRSHQLQJ RI WKH F\FORSURSHQH LQWHUPHGLDWH f WR WKH LVREHQ]RIXUDQ\O FDUEHQH LV SUHFOXGHG EHFDXVH QRW HQRXJK DURPDWLFLW\ LV JDLQHG LQ WKDW GLUHFWLRQ :K\ GRHV WULSOHW FKHPLVWU\ SUHGRPLQDWH LQ WKH UHDFWLRQV RI IXURWURS\OLGHQH DW PRGHUDWH WR KLJKHU WHPSHUDWXUHV" 7KH DSSDUHQW HDVH RI FURVVLQJ IURP VLQJOHW WR WULSOHW VXJJHVWV WKDW WKHVH WZR HOHFn WURQLF VWDWHV DUH DW YHU\ VLPLODU HQHUJ\ OHYHOV LQ WKLV FDUEHQH 7KH HIIHFW RI WHPSHUDWXUH LQ FKDQJLQJ WKH FKDUDFWHU RI WKH UHDFWLRQV RI WKLV FDUEHQH KDV D IHZ LQWHUHVWLQJ SDUDOOHOV LQ WKH OLWHUDWXUH

PAGE 59

&ORVV KDV UHSRUWHG D FDVH LQ ZKLFK WKHUH PD\ EH D WHPSHUDWXUH HIIHFW XSRQ D VLQJOHWWULSOHW HTXLOLEULXP 'LSKHQ\O FDUEHQH NQRZQ WR KDYH D WULSOHW JURXQG VWDWH ZDV SURGXFHG E\ LUUDGLDWLRQ RI GL SKHQ\OGLD]RPHWKDQH LQ WKH SUHVHQFH RI ROHILQV ,Q UHDFWLRQV ZLWK FLV DQG WUDQVEXWHQHV F\FORSURSDQHV DFFRXQW IRU QR PRUH WKDQ SHUn FHQW RI WKH K\GURFDUERQ SURGXFWV +\GURJHQ DEVWUDFWLRQ ZDV WKH PDLQ UHDFWLRQ SDWKZD\ $W r& WKH FLVDQG WUDQV GLPHWK\O GLSKHQ\OF\FORSURSDQHV ZHUH IRUPHG LQ D UDWLR RI IURP WKH FLV EXWHQH 7KH FRUUHVSRQGLQJ UDWLR IURP WKH WUDQV ROHILQ ZDV /RZHU WHPSHUDWXUHV FDXVHG LQFUHDVHG VWHUHRVSHFLILFLW\ $W r& WKH SURGXFW UDWLR IURP WKH FLV EXWHQH ZDV $W D JLYHQ WHPn SHUDWXUH WKH SURGXFW UDWLR ZDV IRXQG WR EH LQGHSHQGHQW RI WKH EXWHQH FRQFHQWUDWLRQ RYHU D UDQJH RI IROG GLOXWLRQ ZLWK F\FORKH[DQH 7KH SUHVHQFH RI R[\JHQ IDLOHG WR FKDQJH WKH LVRPHU UDWLR RI SURGXFWV &ORVV SRVWXODWHG WKH IROORZLQJ VFKHPH )LJXUH f DV D SRVVLEOH H[n SODQDWLRQ RI KLV REVHUYDWLRQV +H VXJJHVWHG WKDW LQWHUV\VWHP FURVVLQJ LV PXFK IDVWHU WKDQ DQ\ RWKHU UHDFWLRQ LQ WKH V\VWHP DQG WKDW WKH UHYHUVH FURVVLQJ LV DOVR YHU\ IDVW VR WKDW ERWK VLQJOHW DQG WULSOHW DUH HIIHFWLYHO\ LQ HTXLOLEULXP 7KH UHODWLYH UDWHV RI WKH VLQJOHW NDJf DQG WKH WULSOHW N f DGGLWLRQ VWHSV DQG WKH SRVLWLRQ RI WKH VLQJOHWWULSOHW HTXLOLEULXP ERWK GHWHUPLQH WKH IUDFWLRQ RI VWHUHRVSHFLILF VLQJOHWVWDWH DGGLWLRQ 6LQFH GLSKHQ\OPHWK\OHQH LV NQRZQ WR KDYH D WULSOHW JURXQG VWDWH WKH UDWH RI FURVVLQJ WR WKH WULSOHW NAf PXVW EH JUHDWHU WKDQ WKH UDWH RI WULSOHW FURVVLQJ WR WKH VLQJOHW N WKHUHIRUH LQ YLHZ RI WKH REVHUYHG SURGXFW UDWLRV WKH UDWH RI VLQJOHW DGGLWLRQ N f PXVW EH PXFK JUHDWHU WKDQ WKH UDWH RI WULSOHW DGGLWLRQ NtWf ,I WKH GLIIHUHQFH LQ WKH IUHH HQHUJLHV RI DFWLYDWLRQ IRU WKH WZR DGGLWLRQ UHDFWLRQV LV

PAGE 60

ODUJHU WKDQ WKH IUHH HQHUJ\ GLIIHUHQFH EHWZHHQ WKH WZR HOHFWURQLF VWDWHV WKH WHPSHUDWXUH GLIIHUHQFH FRXOG EH H[SODLQHG RQ WKLV EDVLV DORQH ,W LV QRW SRVVLEOH WR GHWHUPLQH ZKHWKHU D WHPSHUDWXUH HIIHFW XSRQ WKH SRVLWLRQ RI VLQJOHWWULSOHW HTXLOLEULXP LV EHLQJ REVHUYHG EXW WKLV LV D SRVVLELOLW\ )LJXUH f 7KHUPDO HIIHFWV XSRQ WKH SRSXODWLRQ RI HOHFWURQLF VWDWHV DUH NQRZQ LQ FHUWDLQ SKRWRFKHPLFDOO\ SURGXFHG QRQFDUEHQH VSHFLHV $Q H[DPSOH LV D VWXG\ RI S\UHQHG4 LQ D SRO\PHWK\OPHWKDFU\ODWH PDWUL[ 7KH WULSOHW \LHOG SOXV WKH IOXRUHVFHQFH \LHOG ZDV QHDU XQLW\ DW r& $V WKH WHPSHUDWXUH ZDV UDLVHG WZR HIIHFWV ZHUH REVHUYHG )LUVW WKH WULSOHW \LHOG LQFUHDVHG ZLWK LQFUHDVLQJ WHPSHUDWXUH VXJJHVWLQJ D WHPSHU DWXUHGHSHQGHQW SURF HV V WKDW SURGXFHV LQFUHDVLQJ LQWHUV\VWHP

PAGE 61

FURVVLQJ IURP YLEUDWLRQDOO\ H[FLWHG VLQJOHW WR VHFRQG WULSOHW VWDWH Af 7KH VHFRQG HIIHFW REVHUYHG ZDV D IDOOLQJ RII RI WKH VXP RI WULSOHW \LHOG DQG IOXRUHVFHQFH \LHOG IURP WKH H[SHFWHG YDOXH RI XQLW\ DV WHPSHUDWXUH LQFUHDVHG 7KLV VXJJHVWHG D WKHUPDOO\ GHSHQGHQW UDGLDWLRQOHVV WUDQVLWLRQ IURP WKH ILUVW VLQJOHW VWDWH WR WKH JURXQG VWDWH 7KH HQHUJ\ RI DFWLYDWLRQ IRU WKH WHPSHUDWXUHGHSHQGHQW FRPn SRQHQW RI WKH LQWHUV\VWHPFURVVLQJ SURFHVV ZDV GHWHUPLQHG WR EH DERXW NFDO SHU PROH 7KH HQHUJ\ RI DFWLYDWLRQ IRU WKH UDGLDWLRQn OHVV WUDQVLWLRQ IURP VLQJOHW WR JURXQG VWDWH ZDV DERXW NFDO SHU PROH $ VRPHZKDW VLPLODU VWXG\ RI EHQ]SHU\OHQH KDV VKRZQ WKDW VLQFH WKH VHFRQG H[FLWHG VLQJOHW RI WKLV PROHFXOH OLHV RQO\ DERXW FP r NFDO SHU PROHf DERYH WKH ILUVW H[FLWHG VLQJOHW WKHUH LV VLJQLILFDQW WKHUPDO SRSXODWLRQ RI WKH VHFRQG H[FLWHG VLQJOHW VWDWH DW r& :KHWKHU IXURWURS\OLGHQH LV VKRZLQJ D VLPLODU WKHUPDO HIIHFW XSRQ SRSXODWLRQ RI HOHFWURQLF VWDWHV LV QRW SRVVLEOH WR GHWHUPLQH VR ORQJ DV WKH HOHFWURQLF VWDWHV WKHPVHOYHV FDQQRW EH REVHUYHG H[FHSW WKURXJK WKHLU FKHPLVWU\ 7KLV LV EHFDXVH WKH UHODWLYH UDWHV RI UHn DFWLRQ RI WKH HOHFWURQLF VSHFLHV ZLWK WKHLU WUDSSLQJ DJHQWV DUH XQNQRZQ ,W LV SRVVLEOH WR GUDZ VHYHUDO VSHFXODWLYH VFKHPHV WKDW FRXOG ILW WKH SUHVHQWO\ NQRZQ IDFWV DERXW FfIXURWURS\OLGHQH 6RPH RI WKHVH DUH VKRZQ LQ DEEUHYLDWHG IRUP LQ )LJXUH ,W VHHPV UHDVRQn DEOH WR DVVXPH WKDW WKH F\FORSURSHQH LV ORZHU LQ HQHUJ\ WKDQ WKH LQLWLDOO\ IRUPHG VLQJOHW FDUEHQH 7KH UHODWLYH HQHUJLHV RI WKH WULSOHW DQG VLQJOHW VWDWHV VKRZQ LQ )LJXUH FDQ RQO\ EH WKH VXEMHFW RI

PAGE 62

)LJXUH f

PAGE 63

VSHFXODWLRQ IURP WKH SUHVHQW GDWD ,W LV LQWHUHVWLQJ WR FRQVLGHU WKH TXHVWLRQ DV WR ZKHWKHU HTXLOLEULD H[LVW EHWZHHQ WKH VSHFLHV LQ )LJXUH EXW WKHUH LV QR H[SHULPHQWDO EDVLV IRU D GHWHUPLQDWLRQ RI WKLV TXHVWLRQ $ K\SRWKHWLFDO H[SHULPHQW FDQ EH GHYLVHG WR DQVZHU WKLV TXHVWLRQ ,I RQH FDQ VKRZ WKDW WKHUH LV ; SHUFHQW IRUPDWLRQ RI F\FOR SURSHQH XQGHU D JLYHQ VHW RI FRQGLWLRQV DQG WKDW WKHUH LV PRUH WKDQ ;f SHUFHQW RI FDUEHQH DGGLWLRQ REVHUYHG XQGHU WKH VDPH FRQGLn WLRQV LQ WKH DEVHQFH RI D F\FORSURSHQH WUDS RQH FRXOG UHDVRQDEO\ FRQFOXGH WKDW DQ HTXLOLEULXP EHWZHHQ F\FORSURSHQH DQG VLQJOHW FDUEHQH GRHV H[LVW 6XFK DQ H[SHULPHQW VHHPV WR FDOO IRU H[WUDRUGLQDULO\ KLJK \LHOGV LQ WKHVH FDUEHQH UHDFWLRQV WKDW DUH XQOLNHO\ WR EH DWWDLQn DEOH ,Q DOO RI WKHVH VFKHPHV LW VHHPV UHDVRQDEOH WKDW VLQJOHW FKHPLVWU\ LV QRW REVHUYHG YLD LQWHUPROHFXODU ROHILQ WUDSSLQJ VLQFH WKH LQWUDPROHFXODU UHDFWLRQ WR IRUP WKH F\FORSURSHQH ZRXOG EH H[n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fIXURWUR S\OLGHQH ZRXOG VKHG DGGLWLRQDO OLJKW RQ WKHVH PDWWHUV EXW WKH VHSDUDn WLRQ DQG SXULILFDWLRQ RI VXFK ODUJH PROHFXOHV IRUPHG LQ VXFK ORZ \LHOGV SUHVHQWV IRUPLGDEOH H[SHULPHQWDO GLIILFXOWLHV

PAGE 64

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n SRQHQWV ZHUH YLVXDOL]HG E\ WKHLU TXHQFKLQJ RI IOXRUHVFHQFH XQGHU XOWUDYLROHW OLJKW $QDO\WLFDO JDV FKURPDWRJUDSK\ ZDV DFFRPSOLVKHG ZLWK D 9DULDQ $HURJUDSK 6HULHV DPH LRQL]DWLRQ LQVWUXPHQW XVLQJ D IW FDSLOODU\ FROXPQ FRDWHG ZLWK 8FRQ /% $QDO\WLFDO UHVXOWV ZHUH REWDLQHG E\ SODQLPHWULF PHDVXUHPHQW DQG E\ SHDN KHLJKW WLPHV SHDNZLGWKDWKDOIKHLJKW PHDVXUHPHQW

PAGE 65

$OO FKHPLFDOV DUH UHDJHQW JUDGH XVHG DV VXSSOLHG XQOHVV RWKHUn ZLVH VWDWHG 7KH IXUDQ GLFDUER[\OLF DFLG ZDV XVHG DV VXSSOLHG E\ $OGULFK &KHPLFDO &RPSDQ\ 0LOZDXNHH :LVFRQVLQ 6ROYHQWV ZHUH GULHG E\ SDVVDJH WKURXJK D FROXPQ RI HLWKHU IUHVKO\ UHDFWLYDWHG /LQGH 0ROHFXODU 6LHYH $f RU :RHOP EDVLF DOXPLQD DFWLYLW\ JUDGH IROORZHG E\ VWRUDJH RYHU FDOFLXP K\GULGH XQGHU D QLWURJHQ DWPRVSKHUH 'LK\GUR[\PHWK\OfIXUDQ 7KLV FRPSRXQG KDV EHHQ UHSRUWHG DV WKH SURGXFW RI WKH UHGXFWLRQ RI GLPHWK\O IXUDQGLFDUER[\ODWH 7KH UHSRUWHG \LHOG RI SHUFHQW GLG QRW UHVXOW IURP XVH RI WKH SXEn OLVKHG SURFHGXUH 7KH IROORZLQJ SURFHGXUH JDYH SHUFHQW FRQYHUn VLRQ EDVHG RQ WKH GLDFLG $ PL[WXUH RI J PROHVf IXUDQGLFDUER[\OLF DFLG J PROHVf WKLRQ\O FKORULGH PO EHQ]HQH DQG PO 1 1GLPHWK\OIRUPDPLGH ZDV KHDWHG DW UHIOX[ IRU KU 7KH UHDFWLRQ LV HVVHQWLDOO\ FRPSOHWH ZKHQ DOO RI WKH VROLG KDV GLVVROYHG 7KH EHQ]HQH DQG H[FHVV WKLRQ\O FKORULGH ZHUH UHPRYHG LQ YDFXXP E\ URWDU\ HYDSRUDWRU 7KH FUXGH GLDF\O FKORULGH IRUPHG LQ HVVHQWLDOO\ TXDQWLWDWLYH \LHOG ZDV UHGXFHG GLUHFWO\ ZLWKRXW SXULILn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f

PAGE 66

H[WUDFW ZDVKHG ZLWK EULQH GULHG ZLWK DQK\GURXV 0J62A DQG ILOWHUHG 5HPRYDO RI WKH VROYHQW RQ D URWDU\ HYDSRUDWRU XVLQJ DVSLUDWRU YDFXXP JDYH J RI FUXGH GLK\GUR[\PHWK\OIXUDQ 7KH SURGXFW ZDV LGHQWLILHG E\ WKH FRUUHVSRQGHQFH RI LWV VSHFWUDO SURSHUWLHV ZLWK WKH YDOXHV UHSRUWHG LQ WKH OLWHUDWXUH )XUDQGLFDUER[DOGHK\GH 7KLV FRPSRXQG ZDV SUHSDUHG IURP GLK\GUR[\PHWK\OfIXUDQ LQ WZR VWHSV E\ WKH SURFHGXUH RI &RRN DQG )RUEHV 7KH ILUVW VWHS SDUWLDO R[LGDWLRQ RI WKH GLDOFRKRO ZLWK DFWLYDWHG PDQJDQHVH GLR[LGH JDYH \LHOGV RI DERXW SHUFHQW LQVWHDG RI WKH UHSRUWHG SHUFHQW 7KH EHVW \LHOGV RI GL DOGHK\GH ZHUH REn WDLQHG E\ OHDG WHWUDDFHWDWH R[LGDWLRQ RI WKH FUXGH K\GUR[\PHWK\O IXUDQFDUER[DOGHK\GH FRQWDLQLQJ DERXW SHUFHQW RI XQUHDFWHG JO\FRO UDWKHU WKDQ E\ VHSDUDWLRQ DQG SXULILFDWLRQ RI WKH PRQRn DOGHK\GH 7KLV SURFHGXUH DOORZHG WKH OHDG WHWUDDFHWDWH WR R[LGL]H QRW RQO\ WKH PRQRDOGHK\GH LQ WKH PL[WXUH EXW DOVR WKH JO\FRO WKDW KDG QRW EHHQ R[LGL]HG E\ WKH PDQJDQHVH GLR[LGH 7KLV UHTXLUHG XVH RI DERXW SHUFHQW PRUH OHDG WHWUDDFHWDWH WKDQ ZRXOG KDYH EHHQ UHTXLUHG IRU R[LGDWLRQ RI DQ HTXDO ZHLJKW RI K\GUR[\PHWK\OIXUDQ FDUER[DOGHK\GH WR WKH GLDOGHK\GH 7KLV SURFHGXUH JDYH DERXW SHUn FHQW FRQYHUVLRQ RI WKH JO\FRO WR IXUDQGLFDUER[DOGHK\GH 7KH SURGXFH ZDV LGHQWLILHG E\ WKH FRUUHVSRQGHQFH RI LWV VSHFWUDO SURSHUWLHV DQG PHOWLQJ SRLQW ZLWK WKH YDOXHV UHSRUWHG LQ WKH OLWHUDWXUH E\ &RRN DQG )RUEHV A Ff)XURWURSRQH 7KLV FRPSRXQG ZDV SUHSDUHG E\ FRQGHQVDn WLRQ RI IXUDQGLFDUER[DOGHK\GH ZLWK DFHWRQH XVLQJ WKH SURFHGXUH RI &RRN DQG )RUEHV 7KH \LHOG DQG WKH SK\VLFDO DQG VSHFWUDO SURSHUWLHV RI WKH SURGXFW ZHUH H[DFWO\ DV UHSRUWHG

PAGE 67

Ff)XURWURSRQH WRV\OK\GUD]RQH $ VROXWLRQ RI J PROHVf SWROXHQHVXOIRQ\OK\GUD]LQH DQG D WUDFH RI SKRVSKRULF DFLG LQ PO RI GU\ WHWUDK\GURIXUDQ ZDV DOORZHG WR VWDQG LQ D VWRSSHUHG IODVN IRU WKUHH WR VHYHQ GD\V DW URRP WHPSHUDWXUH 7KH VROXWLRQ ZDV GLOXWHG ZLWK RQH YROXPH RI FKORURIRUP DQG DOORZHG WR VWDQG LQ D UHIULJHUDWRU FDELQHW FD r&f IRU WR KU 7KH UHVXOWLQJ VOXUU\ RI FU\VWDOV ZDV SRXUHG RQWR D %XFKQHU ILOWHU 7KH FROOHFWHG \HOORZ FU\VWDOV ZHUH ZDVKHG ZLWK IUHVK FKORURIRUP RQ WKH ILOWHU 7KH FRPELQHG ZDVK VROYHQW DQG PRWKHU OLTXRU ZHUH HOXWHG IURP D FROXPQ RI VLOLFD JHO [ FP f XVLQJ PHWK\OHQH FKORULGH 7KH ILUVW \HOORZf IUDFWLRQ ZDV FROOHFWHG DQG HYDSRUDWHG WR GU\QHVV 7KH UHVLGXH ZDV ZDVKHG ZLWK FKORURIRUP DQG ILOWHUHG 7KH UHVXOWLQJ VHFRQG FURS RI \HOORZ FU\VWDOV ZKHQ FRPELQHG ZLWK WKH ILUVW FURS RQ WKH ILOWHU JDYH D WRWDO RI J SHUFHQW FRQYHUVLRQf RI WKH NHWRQH WRV\OK\GUD]RQH P S r& Z GHFRPSRVLWLRQ $QDO &DOHG IRU & MT16 & + 1 )RXQG & + 1 7KH VSHFWUDO GDWD ZHUH LU .%U FP f QPU G'062f WR FRPSOH[ SDWWHUQ WRWDO +f VLQJOHW +f FfIXURWURSRQH WRV\OK\GUD]RQH VRGLXP VDOW $ VROXWLRQ RI J IXURWURSRQH WRV\OK\GUD]RQH LQ PO GU\ WHWUDK\GURIXUDQ ZDV VWLUUHG XQGHU GU\ QLWURJHQ ZKLOH J VRGLXP K\GULGH ZDVKHG ZLWK SHQWDQHf ZDV DGGHG $IWHU WR KU DW URRP WHPSHUDWXUH PO SHQWDQH ZDV DGGHG WR WKH UHDFWLRQ PL[WXUH 7KH UHVXOWLQJ VOXUU\ RI \HOORZ VROLG ZDV ILOWHUHG LQ D GU\ QLWURJHQ DWPRVSKHUH GU\ ER[f WR UHFRYHU J RI WKH VRGLXP VDOW

PAGE 68

'HFRPSRVLWLRQ RI WRV\OK\GUD]RQH VDOW LQ SUHVHQFH RI EHQ]HQH Ff)XURWURSRQHWRV\OK\GUD]RQH VRGLXP VDOW J PPROHf ZDV VWLUUHG ZLWK PO EHQ]HQH LQ D VHDOHG )LVFKHU3RUWHU $HURVRO &RPSDWLELOLW\ 7HVW 7XEH FRQWDLQLQJ DQ DWPRVSKHUH RI GU\ QLWURJHQf DQG KHDWHG LQ DQ RLO EDWK NHSW DW r& $IWHU KU WKH WXEH ZDV FRROHG DQG RSHQHG 7KH GDUN EURZQ VOXUU\ ZDV WDNHQ IURP WKH WXEH DQG ILOWHUHG WKURXJK D VLQWHUHG JODVV IXQQHO 7KH VROLG ILOWHU FDNH ZHLJKHG J 7KH ILOWUDWH XSRQ HYDSRUDWLRQ RI WKH EHQ]HQH OHIW D UHVLGXH RI J 7KLV FUXGH UHVLGXH ZDV FKURPDWRJUDSKHG RQ SUHSDUDWLYH VLOLFD JHO SODWHV GHYHORSHG ZLWK KH[DQH FRQWDLQLQJ SHUFHQW EHQ]HQH 7KH OHDGLQJ EDQG RI WKH FKURPDWRJUDP ZDV FROn OHFWHG VWULSSHG IURP WKH DGVRUEHQW ZLWK HWKDQRO DQG UHFRYHUHG E\ HYDSRUDWLQJ WKH ILOWHUHG VROXWLRQ 7KLV UHVXOWHG LQ FROOHFWLRQ RI J RI WKH EHQ]HQH LQVHUWLRQ SURGXFW f P S r & $QDO &DOHG IRU & +]2 & + )RXQG & + 7KH VSHFWUDO GDWD ZHUH LU .%U FP f QPU &'&f DQG WZR VLQJOHWV WRWDO +f FRPSOH[ +f FRPSOH[ +f FRPSOH[ +f PDVV VSHFWUXP H9f PROHFXODU LRQf 'HFRPSRVLWLRQ RI WRV\OK\GUD]RQH VDOW LQ HTXLPRODU EHQ]HQHGA EHQ]HQH $ UHSHDW RI WKH DERYH SUHSDUDWLRQ LQ WKH SUHVHQFH RI DQ HTXLPRODU PL[WXUH RI EHQ]HQH DQG KH[DGHXWHUDWHG EHQ]HQH SURGXFHG D PL[WXUH RI WKH EHQ]HQH LQVHUWLRQ SURGXFW DQG WKH GHXWHUDWHG EHQ]HQH LQVHUWLRQ SURGXFW DV GHWHUPLQHG E\ QPU 0+] f DQG E\ PDVV VSHFWURVFRS\

PAGE 69

'HFRPSRVLWLRQ RI WRV\OK\GUD]RQH VDOW LQ SUHVHQFH RI VW\UHQH $ VROXWLRQ RI J PPROHVf VW\UHQH LQ PO GU\ GLR[DQH ZDV KHDWHG WR r & LQ D IODVN HTXLSSHG ZLWK WKHUPRPHWHU VWLUULQJ EDU DQG DQ LQOHW IRU GU\ QLWURJHQ 'U\ VROLG WRV\OK\GUD]RQH VDOW J PPROHVf ZDV DGGHG WR WKH VROXWLRQ DOO DW RQFH $IWHU KU WKH UHDFWLRQ PL[WXUH ZDV TXLFNO\ FRROHG LQ DQ LFH EDWK DV VWLUULQJ ZDV FRQWLQXHG 7KH FUXGH EURZQ VOXUU\ LQ WKH IODVN ZDV UHPRYHG DQG ILOWHUHG WKHQ WUHDWHG RQ D URWDU\ HYDSRUDWRU WR UHPRYH WKH GLR[DQH DQG DV PXFK VW\UHQH DV SRVVLEOH 7KH UHVXOWLQJ UHVLGXH ZDV GLVn VROYHG LQ FKORURIRUP DQG VWUHDNHG RQ D SUHSDUDWLYH VLOLFD JHO SODWH 'HYHORSPHQW RI WKH SODWH LQ D PL[WXUH RI KH[DQH DQG FKORURIRUP JDYH J RI VRPHZKDW LPSXUH VSLUR DGGXFW LQ WKH PDMRU EDQG 7KLV PDWHULDO ZDV SXULILHG E\ UHSHWLWLRQ RI WKH VLOLFD JHO FKURPDWRJUDSK\ XVLQJ KH[DQH DV WKH VROYHQW IRU GHYHORSPHQW RI WKH SODWH 7KLV JDYH J RI WKH RLO\ OLTXLG SKHQ\OVSLURF\FORSURSDQH f FRQYHUVLRQ SHUFHQW $QDO &DOHG IRU &A+A2 & + )RXQG & + 7KH VSHFWUDO GDWD ZHUH LU ILOP FP7Af QPU &&f VLQJOHW +f DQG WZR VLQJOHWV WRWDO +f FRPSOH[ +f FRPSOH[ +f PDVV VSHFWUXP H9f PROHFXODU LRQf 7KHUPDO GHFRPSRVLWLRQ RI WRV\OK\GUD]RQH VDOW LQ SUHVHQFH RI WUDQVGHXWHULRVW\UHQH 7KH DERYH SUHSDUDWLRQ ZDV UHSHDWHG XVLQJ WUDQVGHXWHULRVW\UHQH LQ SODFH RI VW\UHQH ([DPLQDWLRQ RI WKH QPU

PAGE 70

VSHFWUXP VKRZHG WKDW WKH SURGXFW FRQVLVWHG RI HTXDO SDUWV RI WKH FLV DQG WUDQV F\FORSURSDQHV 7KH VSHFWUXP VKRZHG D VLPSOLILHG $%; SDWWHUQ DV GHVFULEHG LQ WKH WH[W RI WKLV UHSRUW 3KRWRO\WLF GHFRPSRVLWLRQ RI WRV\OK\GUD]RQH VDOW LQ SUHVHQFH RI WUDQVGHXWHULRVW\UHQH $ VROXWLRQ SUHSDUHG DV LQ WKH H[SHULPHQW DERYH ZDV LUUDGLDWHG LQ D VHDOHG WXEH PDJQHWLFDOO\ VWLUUHGf ZLWK WZR 6HDUV5RHEXFN VXQODPSV DW D GLVWDQFH RI DSSUR[LPDWHO\ LQFKHV 'XULQJ WKH UHDFWLRQ DQG WKH ZRUNXS WKH SURGXFW ZDV QRW H[SRVHG WR WHPSHUDWXUHV H[FHHGLQJ r & 7KH UHVXOWLQJ SKHQ\OF\FORSURSDQH FRQVLVWHG RI HTXDO SDUWV RI WKH FLV DQG WUDQV SURGXFWV DV VKRZQ E\ QPU 7HVW RI WKH WKHUPDO DQG SKRWRO\WLF VWDELOLW\ RI WUDQVGHXWHULR VW\UHQH $ VPDOO VDPSOH RI WUDQVGHXWHULRVW\UHQH LQ DQ QPU VDPSOH WXEH ZDV KHDWHG LQ D VWHDP FRQH IRU KU 7KH QPU VSHFWUXP ZDV XQFKDQJHG E\ WKH KHDWLQJ 7KH VDPSOH ZDV DOVR XQFKDQJHG DIWHU LW ZDV LUUDGLDWHG E\ WZR 6HDUV 5RHEXFN VXQODPSV IRU KU 'HFRPSRVLWLRQ RI WRV\OK\GUD]RQH VDOW LQ SUHVHQFH RI EXWHQH 7KH VDOW = J PPROHVf ZDV KHDWHG ZLWK J EXWHQH OLTXLGf WKDW KDG EHHQ GLVWLOOHG LQWR D )LVKHU 3RUWHU $HURVRO &RPSDWLELOLW\ 7HVW 7XEH 7KH WXEH ZDV NHSW LQ DQ RLO EDWK DW & IRU KU 7KH H[FHVV EXWHQH ZDV WKHQ UHOHDVHG 7KH FUXGH UHVLGXH ZDV VOXUULHG ZLWK EHQ]HQH DQG ILOWHUHG WKURXJK D VLQWHUHG JODVV ILOWHU 7KH VROLG ILOWHU FDNH ZHLJKHG J 7KH FUXGH ILOWUDWH OHIW D UHVLGXH RI J DIWHU HYDSRUDWLRQ RI WKH EHQ]HQH 7KLV UHVLGXH DERXW SHUFHQW SXUHf DIIRUGHG WKH HWK\O VSLURF\FORSURSDQH f DIWHU SXULILFDWLRQ E\ SUHSDUDWLYH YDSRU SKDVH FKURPDWRJUDSK\ RQ DQ IW [ LQ FROXPQ SDFNHG ZLWK PHVK $QDNURP $%6 FRDWHG ZLWK SHUFHQW ZZ 6(

PAGE 71

$QDO +LJK UHVROXWLRQ PDVV VSHFWURVFRS\ H9f &DOHG IRU &+2 )RXQG 7KH VSHFWUDO GDWD ZHUH LU OLTXLG ILOP FP QPU &&OAf V VLQJOHW +f RYHUn ODSSLQJ GRXEOHWV WRWDO +f FRPSOH[ +f FRPn SOH[ +f PDVV VSHFWUXP H9f PROHFXODU LRQf &A+A2f &M M+MT2f &K+f & +2f &+f 'HFRPSRVLWLRQ RI WRV\OK\GUD]RQH VDOW LQ SUHVHQFH RI LVREXWHQH 7KH VDOW J PPROHVf ZDV KHDWHG ZLWK FD J OLTXLG LVRn EXWHQH LQ D VHDOHG )LVKHU3RUWHU $HURVRO &RPSDWLELOLW\ 7HVW 7XEH LQ DQ RLO EDWK DW r& IRU KU 7KH H[FHVV LVREXWHQH ZDV WKHQ UHOHDVHG WR FRRO WKH FRQWHQWV RI WKH WXEH 7KH FUXGH UHVLGXH WKDW UHPDLQHG ZDV VOXUULHG LQ EHQ]HQH DQG ILOWHUHG 7KH VROLG ILOWHU FDNH ZHLJKHG J 7KH ILOWUDWH DIWHU HYDSRUDWLRQ RI WKH EHQ]HQH ZHLJKHG J 3XULILFDWLRQ RI WKLV UHVLGXH E\ WDNLQJ WKH OHDGLQJ EDQG RQ D WKLQOD\HU SODWH VLOLFD JHOf GHYHORSHG LQ KH[DQH JDYH J RI WKH SXULILHG GLPHWK\O VSLURF\FORSURSDQH f 7KH KLJK SXULW\ RI WKH FUXGH SURGXFW DV VKRZQ E\ LWV QPU VSHFWUXP VXJJHVWV WKDW D ODUJH ORVV RI PDWHULDO RFFXUUHG GXULQJ KDQGOLQJ WKDW ZDV QRW DWWULEXWDEOH PHUHO\ WR SXULILFDWLRQ $QDO +LJK UHVROXWLRQ PDVV VSHFWURVFRS\ H9f &DOHG IRU & +r )RXQG 7KH VSHFWUDO GDWD ZHUH LU OLTXLG ILOP FP rf QPU &&f VLQJOHW +f GRXEOHW +f

PAGE 72

GRXEOHW +f VLQJOHW +f VLQJOHW + PDVV VSHFWUXP H9f PROHFXODU LRQf &A+A2f} F L+ LLrf &Q+2f & M M+J2f & +J2f 7KHUPDO GHFRPSRVLWLRQ RI WRV\OK\GUD]RQH VDOW LQ SUHVHQFH RI FLV DQG WUDQVEXWHQHV 7KH VDPH S\URO\VLV WHFKQLTXH GHVFULEHG DERYH ZDV XVHG WR GHFRPSRVH VDPSOHV RI WKH WRV\OK\GUD]RQH VDOW LQ WKH SUHVHQFH RI FLV DQG WUDQVEXWHQHV 7KH UHVXOWLQJ FUXGH UHn DFWLRQ PL[WXUHV KDG HVVHQWLDOO\ LGHQWLFDO QPU VSHFWUD DQG JDV FKURn PDWRJUDPV FDSLOODU\ FROXPQ 8FRQ /%f 3\URO\VLV RI D J VDPSOH PPROHVf RI WKH VDOW ZLWK PO OLTXLG WUDQVEXWHQH DW r& SURGXFHG D FUXGH SURGXFW ZHLJKLQJ J &DUHIXO SUHSDUDWLYH OD\HU FKURPDWRJUDSK\ VLOLFD JHO DGVRUEHQW KH[DQH VROYHQWf RI WKLV PDWHULDO DW ORZ SODWH ORDGLQJV JDYH J RI WUDQV GLPHWK\OVSLURF\FORSURSDQH f SHUFHQW FRQYHUVLRQ $QDO +LJK UHVROXWLRQ PDVV VSHFWURVFRS\ H9f &DOHG IRU & + rn )RXQG 7KH VSHFWUDO GDWD ZHUH LU OLTXLG ILOP FP Af QPU &&f VLQJOHW +f GRXEOHW +f GRXEOHW +f WKUHH VKDUS SHDNV WRWDO +f FRPSOH[ +f PDVV VSHFWUXP H9f PROHFXODU LRQf &A+MA2f &Q+2f &Q+f & ` +J2f & Kf 3KRWRO\VLV RI WRV\OK\GUD]RQH VDOW LQ SUHVHQFH RI FLVEXWHQH 7KH SKRWRO\WLF GHFRPSRVLWLRQ RI J WRV\OK\GUD]RQH VDOW ZLWK J FLVEXWHQH ZDV FDUULHG RXW E\ LUUDGLDWLQJ WKH VWLUUHG VOXUU\ LQ D VHDOHG WXEH IRU KU XVLQJ WZR 6HDUV5RHEXFN VXQODPSV DW D GLVWDQFH

PAGE 73

RI DERXW LQFKHV 7KLV SURFHGXUH SURGXFHG D FUXGH SURGXFW PL[WXUH WKDW JDYH DQ QPU VSHFWUXP DQG JDV FKURPDWRJUDP WKDW ZHUH HVVHQWLDOO\ LGHQWLFDO WR WKRVH SURGXFHG E\ WKH WKHUPDO GHFRPSRVLWLRQ RI WKH VDOW LQ WKH SUHVHQFH RI FLV DQG WUDQVEXWHQHV GHVFULEHG DERYH 3KRWRO\VLV RI WRV\OK\GUD]RQH VDOW LQ SUHVHQFH RI WUDQVEXWHQH DW ORZ WHPSHUDWXUH 3KRWRO\WLF GHFRPSRVLWLRQ RI J WRV\OK\GUDn ]RQH VDOW E\ LUUDGLDWLRQ IRU KU ZLWK D +DQRYLD ZDWW PHUFXU\ ODPS DW D WHPSHUDWXUH RI r& SURGXFHG D FUXGH UHDFWLRQ PL[WXUH WKDW FRQWDLQHG QR F\FORSURSDQH f DV GHWHUPLQHG E\ QPU 'HWHUPLQDWLRQ RI UHODWLYH UDWHV RI UHDFWLRQ ZLWK YDULRXV ROHILQV 5HODWLYH UDWHV RI UHDFWLRQ ZLWK YDULRXV ROHILQV ZHUH GHWHUPLQHG XVLQJ WKH S\URO\VLV PHWKRG LQ D VHDOHG WXEH DV SUHYLRXVO\ GHVFULEHG 7KH WHPSHUDWXUH RI WKH RLO EDWK ZDV NHSW DW r& IRU DOO UXQV ,Q HDFK UXQ D FRPSDULVRQ RI SURGXFW IRUPDWLRQ IURP HDFK RI WZR ROHILQV ZDV GRQH (DFK ROHILQ ZDV SUHVHQW LQ HTXLPRODU DPRXQWV PHDVXUHG E\ FRQGHQVLQJ HTXDO YROXPHV RI WKH JDVHRXV ROHILQV LQWR WKH UHDFWLRQ WXEH E\ XVH RI D PHUFXU\ILOOHG JDV EXUHW 7KH SURGXFW UDWLRV ZHUH GHWHUPLQHG E\ FDSLOODU\ FROXPQ JDV FKURPDWRJUDSK\ DV GHVFULEHG XQGHU WKH *HQHUDO KHDGLQJ RI WKLV VHFWLRQ 7KH UHVXOWV DUH SUHVHQWHG LQ 7DEOH SDJH 3\URO\VLV ZLWK EXWDGLHQH DW r& )XURWURSRQH WRV\OK\n GUD]RQH VDOW J PPROHVf ZDV KHDWHG ZLWK FD PO OLTXLG EXWDGLHQH LQ D VHDOHG )LVKHU3RUWHU $HURVRO &RPSDWLELOLW\ 7HVW 7XEH LQ DQ RLO EDWK NHSW DW r& IRU KU ([FHVV EXWDGLHQH ZDV YHQWHG WR WKH DWPRVSKHUH DIWHU WKH WXEH ZDV UHPRYHG IURP WKH EDWK DQG RSHQHG 7KH UHVLGXH WKDW UHPDLQHG LQ WKH WXEH ZDV VOXUULHG LQ

PAGE 74

EHQ]HQH DQG ILOWHUHG WKURXJK VLQWHUHG JODVV 7KH FOHDU DPEHU EHQn ]HQH VROXWLRQ ZDV VWUHDNHG RQ D SUHSDUDWLYH OD\HU SODWH VLOLFD JHOf WKDW ZDV GHYHORSHG ZLWK KH[DQH 7KH OHDGLQJ EDQG RI PDWHULDO JDYH J RI WKH DGGXFW RI EXWDGLHQH f SHUFHQW \LHOG $ VPDOO EDQG RI PDWHULDO IROORZLQJ WKH DGGXFW ZDV WRR VPDOO IRU LGHQWL ILFDWLRQ $QDO &DOHG IRU &+ & + )RXQG & + 7KH VSHFWUDO GDWD ZHUH LU OLTXLG ILOP FP Af QPU &&OAf VLQJOHW + WZR GRXEOHWV ZLWK RYHUODSSLQJ VLJQDO WRWDO +f VLQJOHW +f PDVV VSHFWUXP H9f PROHFXODU LRQf 3\URO\VLV ZLWK EXWDGLHQH DW r & 7KH WRV\OK\GUD]RQH VDOW J PPROHVf ZDV S\URO\]HG ZLWK EXWDGLHQH E\ WKH DERYHGHVFULEHG PHWKRG XVLQJ DQ RLO EDWK WHPSHUDWXUH RI r & DQG UHDFWLRQ WLPH RI KU 6LPLODU ZRUNXS DQG FKURPDWRJUDSK\ VKRZHG RQO\ D YHU\ ZHDN OHDGLQJ EDQG FRUUHVSRQGLQJ WR WKH DGGXFW f J f IROORZHG E\ D VHFRQG EDQG WKDW DIIRUGHG J RI WKH DGGXFW WKH YLQ\O F\FORSURSDQH f $ \LHOG ILJXUH LV QRW JLYHQ LQ WKLV UHDFWLRQ EHFDXVH WKH VKRUW UHDFWLRQ WLPH DQG ORZ WHPSHUDWXUH SUREDEO\ GLG QRW GHFRPSRVH DOO RI WKH VRGLXP VDOW $QDO $QDO\VLV ZDV GRQH E\ WKHUPDO LVRPHUL]DWLRQ RI WKH DGGXFW WR WKH NQRZQ DGGXFW E\ KHDWLQJ LW DW r & IRU KU 7KH VSHFWUDO GDWD ZHUH LU OLTXLG ILOP FP Af QPU &&f VLQJOHW V+f FRPSOH[ +f $%; SDWWHUQ +f $Q LPSXULW\ JDYH D VLQJOHW DW

PAGE 75

3KRWRO\VLV RI WRV\OK\GUD]RQH VDOW ZLWK EXWDGLHQH DW ORZ WHPSHUDWXUH 7KH WRV\OK\GUD]RQH VDOW J PPROHVf ZDV SKRWRO\]HG LQ D VWLUUHG UHDFWRU DW r WR r & XVLQJ WKH +DQRYLD ZDWW ODPS IRU KU :RUNXS LQFOXGLQJ WKLQOD\HU FKURPDWRJn UDSK\ DV GHVFULEHG EHIRUH DIIRUGHG J RI WKH 'LHOV$OGHU DGGXFW f SHUFHQW FRQYHUVLRQ $QDO +LJK UHVROXWLRQ PDVV VSHFWURVFRS\ H9f &DOHG IRU &+ )RXQG 7KH VSHFWUDO GDWD ZHUH LU OLTXLG ILOP FP Af QPU &&f VLQJOHW +f GRXEOHW +f EURDG f EURDG +f GRXEOHW +f PXOWLSOHW +f PDVV VSHFWUXP H9f PROHFXODU LRQf & +T2f &+f & +J2f & M A+S2f 3KRWRO\WLF VWDELOLW\ RI YLQ\OF\FORSURSDQH f $ VDPSOH RI WKH YLQ\OF\FORSURSDQH f ZDV LUUDGLDWHG ZLWK WZR 6HDUV5RHEXFN VXQn ODPSV IRU KU ,W ZDV XQFKDQJHG DIWHU LUUDGLDWLRQ 3KRWRO\VLV RI WRV\OK\GUD]RQH VDOW ZLWK EXWDGLHQH DW r & $ VPDOOVFDOH SKRWRO\VLV FD PJ VDOWf ZDV UXQ LQ WKH SUHVHQFH RI EXWDGLHQH DW r & 7KH SURGXFW UDWLR ZDV GHWHUPLQHG E\ D JDV FKURPDWRJUDSKLF DQDO\VLV VHH *HQHUDO KHDGLQJf RI WKH FUXGH SURGXFW IROORZHG E\ DQRWKHU VLPLODU DQDO\VLV DIWHU UHPRYDO RI DOO DGGXFW E\ WKLQOD\HU FKURPDWRJUDSK\ 7KH UHVXOW VKRZHG WKDW WKH 'LHOV$OGHU DGGXFW f DQG WKH YLQ\OF\FORSURSDQH f ZHUH SUHVHQW LQ D UDWLR ZLWK QRQH RI WKH DGGXFW f SUHVHQW

PAGE 76

&,'13 ([SHULPHQW $ VDWXUDWHG VROXWLRQ RI WKH WRV\OK\GUD]RQH VDOW LQ DQ QPU WXEH FRQWDLQLQJ D VROXWLRQ RI FD SHUFHQW F\FORKH[HQH LQ GA'062 ZDV KHDWHG LQ WKH YDULDEOH WHPSHUDWXUH SUREH RI WKH 9DULDQ $$ DW r & IRU PLQ 1R FKDQJH LQ WKH VSHFWUXP ZDV GHWHFWHG EHIRUH GXULQJ DQG DIWHU KHDWLQJ

PAGE 77

/,67 2) 5()(5(1&(6 & / (QQLV 3K 'LVVHUWDWLRQ 8QLYHUVLW\ RI )ORULGD 0DUFK : 0 -RQHV DQG & /DZUHQFH (QQLV $P &KHP 6RF B f 5 *OHLWHU DQG 5 +RIIPDQQ $P &KHP 6RF f : 0 -RQHV 0 ( 6WRZH ( ( :HOOV -U DQG ( : /HVWHU $P &KHP 6RF f 3 + *HEHUW 3K 'LVVHUWDWLRQ 8QLYHUVLW\ RI )ORULGD 0DUFK / : &KULVWHQVHQ ( ( :DDOL DQG : 0 -RQHV $P &KHP 6RF f 6H\IHUWK < 3 0XL DQG 5 'DPUDXHU $P &KHP 6RF f ( %DOGZLQ DQG 5 $ 6PLWK $P &KHP 6RF f : 0 -RQHV %XUUHOO 1 +DPRQ 5REHUW & -RLQHV DQG & / (QQLV 7HWUDKHGURQ /HWW f 0RULWDQL HW DO 7HWUDKHGURQ /HWW f 0RULWDQL HW DO $P &KHP 6RF f 6 0XUDKDVKL 0RULWDQL DQG 0 1LVKLQR $P &KHP 6RF f ( .UDMFD 7VXWRPX 0LWVXKDVQL DQG: 0 -RQHV $P &KHP 6RF f ( .UDMFD 3K 'LVVHUWDWLRQ 8QLYHUVLW\ RI )ORULGD $XJXVW 7KRPDV &REXUQ 3K' 'LVVHUWDWLRQ 8QLYHUVLW\ RI )ORULGD $XJXVW

PAGE 78

3 6 6NHOO $FFRXQWV RI &KHPLFDO 5HVHDUFK f 0DLWODQG -RQHV -U DQG :DWDUX $QGR $P &KHP 6RF f a : 0 -RQHV DQG 3 0\N\WND XQSXEOLVKHG UHVXOWV $ 6WUHLWZLHVHU -U 0ROHFXODU 2UELWDO 7KHRU\ IRU 2UJDQLF &KHPLVWV -RKQ :LOH\ DQG 6RQV 1HZ
PAGE 79

/ %HOODP\ 7KH 5 6SHFWUD RI &RPSOH[ 0ROHFXOHV -RKQ :LOH\ DQG 6RQV 1HZ
PAGE 80

%,2*5$3+,&$/ 6.(7&+ 7KRPDV +RZDUG /HGIRUG ZDV ERUQ $XJXVW LQ 0DFRQ *HRUJLD WR 0U DQG 0UV +RZDUG :LOOLDP /HGIRUG +H ZDV JUDGXn DWHG IURP 6ZDLQVERUR +LJK 6FKRRO 6ZDLQVERUR *HRUJLD LQ DQG HQWHUHG WKH 8QLYHUVLW\ RI *HRUJLD DV D IRXU\HDU *HQHUDO 0RWRUV 6FKRODU WKDW 6HSWHPEHU :KLOH WKHUH KH ZDV HOHFWHG WR 3KL %HWD .DSSD DQG UHFHLYHG WKH 0HUFN $ZDUG DQG WKH $PHULFDQ ,QVWLWXWH RI &KHPLVWV $ZDUG +H REWDLQHG WKH GHJUHH RI %DFKHORU RI 6FLHQFH LQ &KHPLVWU\ LQ -XQH 7KH SHULRG ZDV VSHQW LQ LQGXVn WULDO UHVHDUFK LQ RUJDQLF FKHPLVWU\ ZLWK 7HQQHVVHH (DVWPDQ &RPSDQ\ .LQJVSRUW 7HQQHVVHH ,Q KH HQUROOHG LQ WKH *UDGXDWH 6FKRRO RI WKH 8QLYHUVLW\ RI )ORULGD ZLWK D :RRGURZ :LOVRQ 1DWLRQDO )HOORZVKLS +H ZDV DOVR D *UDGXDWH 6FKRRO )HOORZ GXULQJ KLV JUDGXDWH VWXG\ +H LV D PHPEHU RI WKH $PHULFDQ &KHPLFDO 6RFLHW\ DQG 3KL %HWD .DSSD 0U /HGIRUG LV PDUULHG WR WKH IRUPHU -RDQ 0F'DQLHO RI 2QHRQWD $ODEDPD +H ZLOO EH ZRUNLQJ IRU WKH (VVR 5HVHDUFK /DERUDWRULHV RI ([[RQ 86$ LQ %DWRQ 5RXJH /RXLVLDQD

PAGE 81

, FHUWLI\ WKDW KDYH UHDG WKLV VWXG\ DQG WKDW LQ P\ RSLQLRQ LW FRQn IRUPV WR DFFHSWDEOH VWDQGDUGV RI VFKRODUO\ SUHVHQWDWLRQ DQG LV IXOO\ DGHn TXDWH LQ VFRSH DQG TXDOLW\ DV D GLVVHUWDWLRQ IRU WKH GHJUHH RI 'RFWRU RI 3KLORVRSK\ :LOOLDP 0 3URIHVVRU RI FHUWLI\ WKDW KDYH UHDG WKLV VWXG\ DQG WKDW LQ P\ RSLQLRQ LW FRQn IRUPV WR DFFHSWDEOH VWDQGDUGV RI VFKRODUO\ SUHVHQWDWLRQ DQG LV IXOO\ DGHn TXDWH LQ VFRSH DQG TXDOLW\ DV D GLVVHUWDWLRQ IRU WKH GHJUHH RI 'RFWRU RI 3KLORVRSK\ D 0HUOH $ %DWWLVWH 3URIHVVRU RI &KHPLVWU\ FHUWLI\ WKDW KDYH UHDG WKLV VWXG\ DQG WKDW LQ P\ RSLQLRQ LW FRQn IRUPV WR DFFHSWDEOH VWDQGDUGV RI VFKRODUO\ SUHVHQWDWLRQ DQG LV IXOO\ DGHn TXDWH LQ VFRSH DQG TXDOLW\ DV D GLVVHUWDWLRQ IRU WKH GHJUHH RI 'RFWRU RI 3KLORVRSK\ *HRUJH % %XWOHU 3URIHVVRU RI &KHPLVWU\ FHUWLI\ WKDW KDYH UHDG WKLV VWXG\ DQG WKDW LQ P\ RSLQLRQ LW FRQn IRUPV WR DFFHSWDEOH VWDQGDUGV RI VFKRODUO\ SUHVHQWDWLRQ DQG LV IXOO\ DGHn TXDWH LQ VFRSH DQG TXDOLW\ DV D GLVVHUWDWLRQ IRU WKH GHJUHH RI 'RFWRU RI 3KLORVRSK\ $Z IHIF 5RJHA* %DWHV 3URIHVVRU RI &KHPLVWU\

PAGE 82

, FHUWLI\ WKDW KDYH UHDG WKLV VWXG\ DQG WKDW LQ P\ RSLQLRQ LW FRQn IRUPV WR DFFHSWDEOH VWDQGDUGV RI VFKRODUO\ SUHVHQWDWLRQ DQG LV IXOO\ DGHn TXDWH LQ VFRSH DQG TXDOLW\ DV D GLVVHUWDWLRQ IRU WKH GHJUHH RI 'RFWRU RI 3KLORVRSK\ 5LFKDUG + +DPPHU $VVRFLDWH 3URIHVVRU RI 3KDUPDFHXn WLFDO &KHPLVWU\ 7KLV GLVVHUWDWLRQ ZDV VXEPLWWHG WR WKH 'HSDUWPHQW RI &KHPLVWU\ LQ WKH &ROOHJH RI $UWV DQG 6FLHQFHV DQG WR WKH *UDGXDWH &RXQFLO DQG ZDV DFn FHSWHG DV SDUWLDO IXOILOOPHQW RI WKH UHTXLUHPHQWV IRU WKH GHJUHH RI 'RFn WRU RI 3KLORVRSK\ $XJXVW 'HDQ *UDGXDWH 6FKRRO

PAGE 83

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