Citation
Metallation, conformational analysis, hydrogen exchange and rearrangement in Amides

Material Information

Title:
Metallation, conformational analysis, hydrogen exchange and rearrangement in Amides
Creator:
Murugan, Ramiah, 1956-
Publication Date:
Language:
English
Physical Description:
xii, 164 leaves : ill. ; 28 cm.

Subjects

Subjects / Keywords:
Amides ( jstor )
Amines ( jstor )
Carbon ( jstor )
Hydrogen ( jstor )
Mass spectroscopy ( jstor )
Nitrogen ( jstor )
Oxygen ( jstor )
Protons ( jstor )
Signals ( jstor )
Solvents ( jstor )
Amides ( lcsh )
Chemistry thesis Ph.D
Conformational analysis ( lcsh )
Dissertations, Academic -- Chemistry -- UF
Rearrangements (Chemistry) ( lcsh )
Genre:
bibliography ( marcgt )
non-fiction ( marcgt )

Notes

Thesis:
Thesis (Ph.D.)--University of Florida, 1987.
Bibliography:
Bibliography: leaves 155-163.
General Note:
Typescript.
General Note:
Vita.
Statement of Responsibility:
Ramiah Murugan.

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:
030338420 ( ALEPH )
16767004 ( OCLC )
AEQ4817 ( NOTIS )
AA00004844_00001 ( sobekcm )

Downloads

This item has the following downloads:


Full Text


METALLATION, CONFORMATIONAL ANALYSIS, HYDROGEN EXCHANGE AND
REARRANGEMENT IN AMIDES
BY
RAMIAH MURUGAN
A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN
PARTIAL FULFILLMENT OF THE REQUIREMENTS
FOR THE DEGREE OF DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA


To my wife
Sutharchana Devi


ACKNOWLEDGMENTS
I would like to sincerely thank my research director,
Professor A. R. Katritzky, for his advice, guidance,
patience and support through out the last five years. I
would also like to thank Professor W. M. Jones for his
advice, support and blessings during the crucial moments of
lifemy marriage.
I would like to thank Professor W. S. Brey, Professor
J. A. Zoltewicz and Dr. R. W. King for their helpful
discussions during the course of this work.
I would also like to thank very much all the members of
our research group past and present of the last five years
for their friendship, support and wonderful discussions.
Special thanks are due to Mr. Jamshed N. Lam, Mr. Steve Cato
and Dr. Gordon Rewcastle for their suggestions after reading
through the manuscript.
I would also like to thank all the faculty and staff of
the Chemistry Department for their understanding and
friendship.
Last, but not least, I would like to thank my family,
especially my daughter, for putting up with me during the
process of writing and typing *-his dissertation.
in


TABLE OF CONTENTS
page
ACKNOWLEDGMENTS iii
LIST OF TABLES vii
LIST OF FIGURES viii
ABSTRACT xi
CHAPTERS
1. GENERAL INTRODUCTION 1
1.1. Structure of the Amide Group 2
1.1.1. Geometry 2
1.1.2. Rotational Barrier 4
1.2. Preparation of Amides 5
1.2.1. Acyclic and Cyclic Amides 6
1.2.2. Vinylogous Amides 7
1.3. Reactivity of Amides 8
1.4. Scope of the Work 10
2. METALLATION OF AMIDES 11
2.1. Introduction 11
2.1.1. Dipole Stabilized Carbanions 13
2.1.2. Carboxamido Group Stabilized Carbanions. 13
2.1.3. Synergistic Effects in Stabilization.... 15
2.1.4. Aim of the Work 16
2.2. Results and Discussion 16
2.2.1. Preparation of Amides 17
2.2.2. Lithiation of 1,3-Diacylimidazolidines.. 18
2.2.3. Lithiation of 1,3-
Diacylhexahydropyr imidines 19
2.2.4. Metallation of 1,3,5-Triacylhexahydro-
sym-triazines 20
2.3. Conclusions 21
2.4. Experimental 23
2.4.1. Reagents 23
2.4.2. Preparation of Acyl Derivatives of
Imidazolidine, Hexahydropyrimidine and
Hexahydro-sym-tr iazine 23
2.4.3. Lithiation of the Acyl Derivatives of
Imidasolidines, Hexahydropyrimidines and
Hexahydro-sym-tr iazines 26
2.4.4. Lithiation of 1,3-Dibenzoylimidazolidine 27
2.4.5. Lithiation of 1,3-
Dibensoylhexahydr opyr imidine 28


2.4.6. Lithiation of 1,3-
Dipivaloylhexahydro pyrimidine 28
2.4.7. Lithiation of 1, 3 5-.Tr ibenzoylhexahydro-
sym-triazine 29
2.4.8. Lithiation of 1,3,5-
Tripivaloylhexahydro-sym-triazine 30
3. CONFORMATIONAL ANALYSIS OF AMIDES 31
3.1. Introduction 31
3.1.1. Conformational Analysis Using DNMR 32
3.1.2. DNMR Studies of Monoamides 33
3.1.3. DNMR Studies of Polyamides 34
3.1.4. Aims of the Work 35
3.2. Results and Discussion 35
3.2.1. Conformers of Diamides and Triamides... 36
3.2.2. Model Compounds for Conformational
Analysis of Acyl Derivatives of Cyclic
Secondary Amines-Imidazolidine,
Hexahydropyrimidine and Hexahydro-sym-
tr iazine 37
3.2.3. 1,3-Diacylimidazolidines Conformational
Equilibria from iH NMR Spectra 43
3.2.4. 1,3-Diacylhexahydropyrimidines ^
Conformational Equilibria from h NMR
Spectra 46
3.2.5. 1,3,5-Triacylhexahydro-sym-tria^ines
Conformational Equilibria from XH NMR
Spectra 53
3.2.6. 1,3-Diacylimidazolidines Conformational
Study from JC NMR Spectra 58
3.2.7. 1,3-Diacylhexahyd ropy rimidines
Conformational Study from ^C NMR
Spectra 65
3.2.8. 1,3,5-Triacylhexahydro-symytriazines
Conformational Study from c NMR
Spectra 72
3.2.9. Kinetic Parameters 72
3.2.10.Mechanism of Conformers Interconversion 81
3.3. Conclusions 88
3.4. Experimental 89
3.4.1. Instruments and Methods 89
3.4.2. Preparation of Amides 90
4. HYDROGEN EXCHANGE IN AMIDES 91
4.1. Introduction 91
4.1.1. Hydrogen Deuterium Exchange in
4-Pyridones 92
v


4.1.2.Aim of the Work 94
4.2. Results and Discussion 96
4.2.1. Hydrogen Deuterium Exchange in N-(4-
Pyridinoxymethyl )-4-pyridone 96
4.2.2. Hydrogen Deuterium Exchange in N-
(Phenoxymethyl)-4-pyridone and
N-(Arylthiomethyl)-4-pyridones 102
4.2.3. Hydrogen Deuterium Exchange in
2,6-Dimethyl-4-alkoxypyridine Model
Compounds 105
4.2.4. Hydrogen Deuterium Exchange in 4-
Alkoxypyridine Model compounds 106
4.3. Conclusions 115
4.4. Experimental 117
4.4.1. Methods and Reagents 117
4.4.2. Preparation of N-(4-pyridinoxymethyl)-
4-pyridone 118
4.4.3. Preparation of N-(Phenoxymethyl)-4-
pyridone and N-(Arylthiomethy1)-4-
pyr idone 119
4.4.4. Preparation of N-(4-Pyridylethyl)-
4-pyridone 121
4.4.5. Preparation of 2,6-Dimethyl-4-
alkoxypyri dines 121
4.4.6. Preparation of 4-Alkoxypyridine Model
Compounds 122
5. REARRANGEMENT IN AMIDES OXYGEN TO NITROGEN
MIGRATION OF ALKYL GROUPS 124
5.1. Introduction 124
5.2. Aim of the Work 126
5.3. Results and Discussion 128
5.3.1. Attempted Rearrangements by Chemical
Methods 136
5.3.2. Elucidation of Mechanism of
Rearrangement by Physical Methods 137
5.4. Conclusions 147
5.5. Experimental 148
5.5.1. Rearrangement of Alkyl Group from
Oxygen to Nitrogen in 4-Pyridones-
General Procedure 149
5.5.2. Preparation of the N-(3 5-Dideutero-4-
pyridinoxymethyl)-2,6-dideutero-4-
pyr idone 149
6. SUMMARY 150
BIBLIOGRAPHY 155
BIOGRAPHICAL SKETCH 164
v 1


LIST OF TABLES
Table page
2.1 Formation of a-Lithio Species of Amides and
their Reaction with Electrophiles 22
3.1 NMR Chemical Shifts (ppm), J Values (Hz) and
Relative Population (%) of 1,3-
Diacylimidazolidines (3.3) and (3.4) 44
3.2 NMR Chemical Shifts (ppm) and Relative
Population (%) of 1,3-Diacylhexahydropyrimidines
(3.5) and (3.6) 52
3.3 '"H NMR Chemical Shifts (ppm) and Relative
Population (%) of 1,3,5-Triacylhexahydro-sym-
triazines (3.7) and (3.8) 57
3.4 ^ C NMR Chemical Shifts (5 ppm) of 1,3-
Diacyl imidazol idines (3.3) and (3.4) 63
3.5 ^C NMR Chemical Shifts (6 ppm) of 1,3-
Diacylhexahydropyrimidines (3.5) and (3.6) 71
3.6 l^C NMR Chemical Shifts (6 ppm) of 1,3,5-
Triacylhexahydro-sym-triazines (3.7) and (3.8).... 76
3.7 Relative AG (kcal mole ^) for Different
Conformers of Amides (3.3 3.8) 77
3.8 Coalescence Temperatures and the Free Energies of
Activation of Amides (3.3 3.8) 79
5.1 Mass Spectral Data of the Molecular Ions for the
Rearranged Products from (4.3), (4.4) and a
Mixture of (4.3) and (4.4) 147
5.2 Calculated Mass Spectral Peak Intensities and the
Difference Between the Calculated and
Experimental Mass Spectral Peak Intensities 148
vi i


LIST OF FIGURES
Figure page
1.1 Major Resonance Forms for Amides Showing
Predicted Bond Lengths (A) and Bond Angles 3
1.2 Mean Values of Bond Lengths (A) and Angles in
Crystalline Amides 3
3.1 60 MHz ^H NMR Spectrum of 1,3-
Dibenzoylimidazolidine (in CDCl^) at 25C 39
3.2 300 MHz 1H NMR Spectrum of 1,3-
Dibenzoylimidazolidine (in CDCl^) at -30C 40
3 3 60 MHz ^H NMR Spectrum of 1,3-
Dip i va loyl imi dazo 1 i d i ne (in CDCl ^ ) at 25C 41
3 4 300 MHz ^H NMR Spectrum of 1,3-
Dipivaloylimidazolidine (in CDCl^) at -70C 42
3.5 60 MHz ^H NMR Spectrum of 1,3-
Dibenzoylhexahydropyrimidine (in CDCl^) at 25C. 48
3.6 300 MHz ^H NMR Spectrum of 1,3-
Dibenzoylhexahydropyrimidine (in CDCl-,) at
-30 C 7 49
3.7 60 MHz ^H NMR Spectrum of 1,3-
Dipivaloylhexahydropyrimidine (in CDCl-,) at
25 0C 7 50
3.8 300 MHz ^H NMR Spectrum of 1,3-
Dipivaloylhexahydropyrimidine (in CDCl-,) at
-1 0 3 0 C 7 51
3.9 60 MHz ^H NMR Spectrum of 1,3,5-
Tribenzoylhexahydro-sym-triazine (in CDCl-,) at
2 5 0 C 7 54
3.10 300 MHz ^H NMR Spectrum of 1,3,5
Tribenzoylhexahydro-sym-triazine (in CDCl-,) at
-30 0C 7 55
3.11 60 MHz ''H NMR Spectrum of 1,3,5-
Tripivaloylhexahydro-sym-triazine (in CDCl-,) at
2 5 0 C 7 56
v i i i


3.12 25 MHz 13C NMR Spectrum of 1,3-
Dibenzoylimidazolidine (in CDCl^) at 60C 59
3.13 75 MHz ^3C NMR Spectrum of 1,3-
Dibenzoylimidazolidine (in CDCl^) at -30C 60
3.14 25 MHz 13C NMR Spectrum of 1,3-
Dipivaloylimidazolidine (in CDCl-^) at 25C 61
3.15 75 MHz 13C NMR Spectrum of 1,3-
Dipivaloylimidazolidine (in CDCl^) at -70C 62
3.16 25 MHz ^3C NMR Spectrum of 1,3-
Dibenzoylhexahydropyrimidine (in CDCl^) at 60C. 66
3.17 75 MHz ^3C NMR Spectrum of 1,3-
Dibenzoylhexahydropyr imidine (in CDCl ,) at
-40 0C f 67
3.18 25 MHz 13C NMR Spectrum of 1,3-
Dipivaloylhexahydropyrimidine (in CDCl,) at
25 0C 68
3.19 75 MHz 13C NMR Spectrum of 1,3-
Dipivaloylhexahydropyrimidine (in CDCl,) at
-100C T 69
3.20 25 MHz 33C NMR Spectrum of 1,3,5-
Tribenzoylhexahydro-sym-triazine (in CDCl,) at
25 0C T 73
3.21 75 MHz '"3C NMR Spectrum of 1,3,5-
Tribenzoylhexahydro-sym-triazine (in CDCl,) at
-30 0 C T 74
3.22 25 MHz 13C NMR Spectrum of 1,3,5-
Tripivaloylhexahydro-sym-triazine (in CDCl,) at
250C . 1 75
4.1 60 MHz H NMR Spectrum of N-(4-
Pyridinoxymethyl)-4-pyridone (in DMSO-dg) 98
4.2 60 MHz 1H NMR Spectrum of N-(4-
Pyridinoxymethyl)-4-pyridone (in NaOD-DMSO-dfi)
After Exchange at 25C 99
4.3 60 MHz ^H NMR Spectrum of N-(4-
Pyridinoxymethyl)-4-pyridone (in NaOD-DMSO-d^)
After Exchange at 40C 100
IX


4.4 60 MHz 1H NMR Spectrum of 2-(4-
Pyridinoxy ) ethanol (in DMSO-dg) 109
4.5 60 MHz 1H NMR Spectrum of 2(4
Pyridinoxy) ethanol (in CD,ONa-CD,OD-DMSO-d.-) at
25C 7 7 110
4.6 60 MHz 1H NMR Spectrum of 2(4-
Pyridinoxy)ethanol (in CD.,ONa-CD,OD-DMSO-dfi )
After Exchange at 70C Ill
4.7 60 MHz 1H NMR Spectrum of 4-(2-
Aminophenoxy)pyridine (in CD^ONa-DMSO-dg) 112
4.8 60 MHZ 1H NMR Spectrum of 4(2-
Aminophenoxy)pyridine (in CD,ONa-DMSO-d,-) After
Exchange at 70C 113
4.9 Base catalyzed Hydrogen Deuterium Exchange in
Different N- and O-substituted 4-Pyridones 116
5.1 Mass Spectrum of (a) N-(4-Pyridinoxymethyl)-
4-pyridone (b) N-(4-Pyridinoxymethyl)-2,6-
dideutero-4-pyridone and (c) N-(3,5-Dideutero-4-
pyridinoxymethyl)-2,6-dideutero-4-pyridone 130
5.2 60 MHz ^H NMR Spectrum of N-(4-
Pyridinoxymethyl)-4-pyridone (in DMSO-dg) 132
5.3 60 MHz ^H NMR Spectrum of the Major Product of
Rearrangment Bis(N-4-pyridonyl)methane (in
DMSO-dg ) 133
5.4 60 MHz ^H NMR Spectrum of the Minor Product
Obtained N-(4-Pyridyl)-4-pyridone (in DMSO-dg) 134
5.5 Mass Spectrum of the Rearranged Product Obtained
from N-( 4-Pyr idinoxymethyl)-4-pyr idone 144
5.6 Mass Spectrum of the Rearranged Product Obtained
from N-(3,5-Dideutero-4-pyridinoxymethyl)-2,6-
dideute ro-4-pyr idone 145
5.7 Mass Spectrum of the Rearranged Product Obtained
from a Mixture of N-(4-Pyridinoxymethyl)-4-
pyridone and N-(3,5-Dideutero-4-
pyridinoxymehtyl)-2,6-dideutero-4-pyridone 146
x


Abstract of Dissertation Presented to the. Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy
METALLATION, CONFORMATIONAL ANALYSIS, REARRANGEMENT AND
HYDROGEN EXCHANGE IN AMIDES
BY
RAMIAH MURUGAN
MAY, 1987
Chairman: Alan R. Katritzky
Major Department: Chemistry
Amides are known to stabilize a carbanion a to the
nitrogen. The synergistic effect of amide groups on
carbanion stability was previously unknown. Thus,
metallation of 1,3-diacylimidazolidines, 1,3-
diacylhexahydropyrimidines and 1,3,5-triacylhexahydro-sym-
triazines has been investigated. The results show no
substantial additional stabilization by the second amide
function. This might be due to steric crowding caused by
the alkyl or aryl group of the acyl units.
Little was known about restricted rotation around C-N
bonds of bis- and trisamides. A ^H and ^C variable
temperature NMR study of acyl derivatives of cyclic
secondary amines, imidazolidines, hexahydropyrimidines and
hexahydro-sym-triazines, has been performed. Conformer
populations were determined at different temperatures and
their barriers to rotation around the amide C-N bond
xi


calculated from their coalescence temperatures. A possible
mechanism of conformational interconversion was predicted
from the observed spectral change with temperature.
Base catalyzed hydrogen exchange on various N- and 0-
substituted 4-pyridones, including vinylogous amides, was
investigated. Exchange of the 2,6-protons of N-aryloxy- and
N-arylthiomethyl-4-pyridones was five times faster than that
of N-methyl-4-pyridone, indicating the participation of the
heteroatom in the exchange reaction. This participation is
very clear in N-(4-pyridinoxymethyl)-4-pyridone which
exchanges the pyridone 2,6-protons in addition to the
pyridine 3,5-protons at temperatures between 40-50C.
Studies of model compounds such as 2(4
pyridinoxymethyl)ethanol, confirm this explanation.
The mechanism for the thermal rearrangement of alkyl
groups from oxygen to nitrogen in 4-pyridones had been
proposed but not proved. A mechanistic study of the thermal
rearrangement using the labelled compound N-(3,5-dideutero-
4-pyridinoxymethyl)-2,6-dideutero-4-pyridone and its
unlabelled analogue was investigated. Based on the product
ratios obtained by mass spectrometry the rearrangement was
found to be intermolecular.
XI 1


CHAPTER 1
GENERAL INTRODUCTION
For nearly two centuries the study of amides has proved
to be a rapidly expanding and intriguing area for
investigation. Not only is the amide moiety an important
constituent of many biologically significant compounds but
an understanding of its formation, properties and reactions
is essential for the dynamic growth of peptide chemistry.
This holds great promise for major discoveries essential to
human well being. Besides their biological importance,
amides are of fundamental chemical interest because of their
distinct physical and chemical properties related to the
conjugation between the nitrogen lone pair electrons and the
carbonyl it bond. It is appropriate to survey briefly the
chemistry of amides prior to the discussion of this work.
The following discussion on amides can not hope to be
comprehensive but is intended to give some idea of the
trends observed in this work.
1


2
1.1. Structure of the Amide Group
The physical structure of the amide group has been the
subject of much recent work. Reviews on the molecular and
electronic structure [70MI1] and nuclear magnetic resonance
(NMR) properties [70CR517] summarize much of the new
developments including the shape and stereochemistry of the
amide group and spectroscopic properties.
(1.1)
1.1.1. Geometry
The molecular structure of the amide group in both the
condensed and gaseous phases is fairly well established.
However, several complicating features need to be taken into
consideration when interpreting physical measurements on
these compounds. One of these features is the partial
double bond character of the C(0)-N bond resulting from
delocalization of the nitrogen lone pair electrons into the
n-system of the carbonyl bond. There are two extreme
valence bond forms, zero conjugation (1.2a) and complete
conjugation (1.2b) as shown in Figure 1.1.


3
(1.2b)
Fig. 1.1 Major Resonance Forms for Amides Showing Predicted
Bond Lengths () and Bond Angles [79MI1].
X-ray diffraction studies of crystalline amides [70MI1]
show a fairly constant geometry for the amide group. All the
heavy atoms of the amide functionality are essentially in a
plane. The mean values of the bond lengths and the bond
angles are given in (1.3) (Figure 1.2).
Fig. 1.2
1.44
o
0.95
0
Mean Values of Bond Lengths (A) and Angles in
Crystalline Amides [79MI1].
The gas phase microwave and electron diffraction
studies [70M11], [74BCSJ631] compared to X-ray diffraction


4
studies of crystalline amides show that the bond angles
remain essentiality the same but the C-0 bond length is
reduced to 1.19-1.20 with concomitant lengthening of the
C-N bond to 1.36-1.37 . This implies that there is a
greater contribution from structure (1.2a) in the gas phase
than in the solid phase.
1.1.2. Rotational Barrier
One of the most fundamental concepts in all
investigations of structure is conformational analysis. In
amides the consequence of partial double-bond character is
the existence of conformational isomers (1.4) and (1.5),
arising from the lack of free rotation about the C(0)-N
bond. The existence of these isomers has been established
by dipole moment measurement [64JAM337], infrared and Raman
spectroscopic studies [70MI1] and by nuclear magnetic
resonance (NMR).
cis (E) trans (Z)
(1.4)
(1.5)


5
Amides have been intensively studied by NMR [70CR517].
Though most of these studies have dealt with rotational
isomerization about the C(0)-N bond, considerable attention
has also been given to chemical shifts, J couplings, proton
exchange and association of the amides.
The effect of solvent and concentration on the free
energy of activation (barrier) has been studied [65JCP3320,
7OMI1]. The barrier increased with increase in solvent
polarity. Similarly, the barrier is also increased with
concentration. In both cases the ground state was expected
to be stabilized by polar solvents and by dipole-dipole
association at higher concentrations.
The effect on the barrier of substituents on both the
nitrogen and the carbonyl group has been investigated and a
number of references are available [70CR517, 74JAM2260,
67JAM4300].
1.2. Preparation of Amides
The amide linkage can be assembled in several ways, and
this is reflected in the variety of methods available for
the synthesis of amides [70MI1], their cyclic analogues the
lactams [70MI1], and the vinylogous amides the 4-pyridones
[74MI1].


6
1.2.1. Acyclic and Cyclic Amides
The most common synthetic pathway for amides themselves
is that of bond formation between a carbonyl-carbon atom and
an amino-nitrogen atom, and this is achieved by treatment of
either ammonia or a primary or a secondary amine with an
acylating agent. This yields a primary, secondary, or
tertiary amide, respectively. The other common pathway for
amide formation is the introduction of a carbonyl group into
an unsaturated amino compound, for example, partial
hydration of either a nitrile or an imidoyl derivative,
producing the primary or secondary amide, respectively. The
imidoyl derivative itself can in principle be obtained by
alkylation of the nitrile. Methods of N-alkyl or N-aryl
bond formation (other than direct replacement of the amido-
H) principally require rearrangements such as in the Schmidt
or Beckmann reactions. Synthesis of amides by formation of
the bond between an alkyl or aryl group and the carbonyl
carbon atom is the most difficult method to achieve and
requires more specific reagents such as ketenes,
isocyanates, and isocyanides. Neither direct oxidation nor
reduction of suitable precursors has wide applicability in
amide synthesis.
The synthesis of lactams (cyclic amides) generally
follows the same procedures as for acyclic amides except


7
where special factors such as ring size and ease of reaction
are concerned. Further modification of the parent lactam can
be achieved by alkylation of the nitrogen atom, and
sometimes of the carbon a to the carbonyl group using
conditions similar to those for acyclic amide alkylation.
The new method available for a-metallation of amides (a to
nitrogen) followed by electrophilic addition giving cx-
electrophile substituted amides [84CR471]. This was one of
the methods used for preparing a-metalloamine synthetic
equivalents (for further details see Chapter 2).
1.2.2. Vinylogous Amides
4-Pyridones can be prepared in two basic ways, by ring
closure reactions and by the transformation of other ring
compounds. For example, in the latter case 4-pyrones can be
transformed into 4-pyridones just by treating the
corresponding 4-pyrones with the required amines. However,
the ring closure reactions yielding 4-pyridones have many
more possiblities, using (i) a triketone or a ketoaldehyde
and ammonia [65JAM3186], (ii) 6-diketones and aromatic
Schiff bases [69BCSJl357 ] (iii) 6-diketones and
benzonitrile [69BCSJ2389], (iv) di-l-propynyl ketone and
primary amines (60A1409J, and (v) primary and secondary
enamines, prepared from ethyl acetoacetate or 6-diketones,
with diketene [69M132].


8
1.3. Reactivity of Amides
Since all three atoms in the O-C-N chain are
potentially reactive, amides become versatile organic
compounds. This is primarily due to the delocalization of
the n electrons along the O-C-N chain. Hence the ground-
state structure of amide is a hybrid of the two resonance
forms (1.6a) and (1.6b). Although versatility often means
complexity, simplification here can be achieved by
recognizing that the majority of reactions of amides fall
into two classes. The first involves nucleophilic attack by
the oxygen atom, or occasionally by the nitrogen atom, on
either positively charged or neutral electrophilic reagents.
Here the resonance form (1.6b) is usually the more
appropriate reactive species. The second, and less common
process involves nucleophilic addition to the amide carbonyl
group of (1.6a). Most other reactions of amides such as
dehydration, elimination, deamination, etc., are sequential
to these two processes.
(1.6a)
(1.6b)


9
Because of n electron delocalization along the O-C-N
chain, the electrophilic properties of the carbonyl carbon
atom are attenuated. Hence amides are much less reactive
electrophiles than carboxylic esters. Enhancement of
polarization of the C=0 bond, either by protonation or
complexation of the oxygen atom, is usually necessary before
such a reaction can occur. Since amides are relatively weak
bases, with protonation and complexation occuring on oxygen,
they should also be feeble nucleophiles with oxygen being
the most nucleophilic site. This explains why neutral
amides react only with the more powerful electrophilic
reagents forming, initially, the O-substituted derivative.
Although N-substituted compounds are commonly isolated from
reaction mixtures, they usually originate from
rearrangements of the O-substituted derivatives and
therefore represent the thermodynamically stable product
[7OMI1] (for further details see chapter 5). Direct N-
substitution occurs only in special circumstances, either
when powerful electrophilic species such as diazoalkanes are
used or when the reaction is carried out in the presence of
a strong base, which creates the amide conjugate base as the
reactive species. For example, N-alkylation is conveniently
achieved by treating a lactam successively with sodium
hydride and alkyl halide in benzene.
Amides usually get hydrolyzed with N-acyl bond fission
to regenerate the parent carbo:vlic acid and an amine.


10
Since the initial step requires nucleophilic addition to the
carbonyl group and with amines particularly amine anions,
being poor leaving groups, it is not surprising that this
reaction is often sluggish. Water itself, for example, is
virtually inert and many amides can be recrystallized from
this solvent. Hydrolysis is much easier either under
alkaline conditions, where the more powerful HO- nucleophile
is available, or under acidic conditions, where the
protonation of the substrate assists both nucleophilic
attack by H2O and expulsion of the amine. Hydrolysis of
lactams is similar, but is generally easier because of ring
strain. However, the vinylogous amide, 4-pyridone, is quite
stable under the acidic or basic conditions normally used
for the hydrolysis of amides [74MI1].
1.4. Scope of the Work
The main objectives of this work were (i) to
investigate the synergistic effect of amide functionality on
the a-metallation of amides, (ii) to study the
conformational behavior (equilibria and kinetics) of bis
and tris-amides using NMR spectroscopy, (iii) to elucidate
the mechanism of the rearrangement of an imidate to an amide
in a vinylogous amide, and (iv) to study the base catalyzed
hydrogen deuterium exchange behavior of different 0- and N-
substituted vinylogous amides.


CHAPTER 2
METALLATION OF AMIDES
2.1. Introduction
The main aim of the metallation studies on amides was
for the transformation of amines into a-substituted amines.
Therefore, before discussing the objective of this work a
brief discussion is given on the different methods available
for amine transformation. The classical methods for the
preparation and transformation of amines employ (i)
nucleophilic substitution by nitrogen, (ii) nucleophilic
addition to a carbon nitrogen double bond and (iii) radical
substitution at carbon adjacent to nitrogen (scheme 2.1).
+
N Y N E
N
/ I I
N
I
Scheme 2.1
Recent methods however, involve introducing an
activating group on the nitrogen atom and then removing the
proton from the carbon adjacent to the nitrogen using metal
11


12
alkyls, to generate a-metallo amine synthetic equivalents.
Then addition of an electrophile followed by the removal of
activating group gives the a-electrophile substituted amine
(scheme 2.2).
H
NH
Scheme 2.2
-Z
+
t
(2.1)
A number of species have been used as activating
groups. In a recent review [84CP.471] the different groups
used for this transformation have been discussed, it also
compares the advantages and disadvantages of the different
groups which arise either from the initial introduction of
the group or removal after the transformation. In all the
groups discussed the main idea behind the activation was
their ability to stabilize an carbanion by dipole
stabilization.


13
2.1.1. Dipole Stabilized Carbanions
A carbanion is considered to be dipole stabilized when
it is adjacent to a heteroatom which is the positive end of
a dipole (Scheme 2.2). The group Z can provide
stabilization in the transition state leading to (2.1) by
complexation with the metal of the base, by dipole
stabilization, and/or by resonance delocalization [84CR471].
Mechanism of metalation has been reviewed [84CR471]. In
addition to dipole stabilization in the lithiation of amides
by IR observation in a stopped-flow spectrometer and syn
substitution indicate, complexation plays a major role in
the reaction (see (2.2) of Scheme 2.3).
2.1.2. Carboxamido Group Stabilized Carbanions
The observation that dipole stabilized carbanions (2.2)
can be formed from amides and undergo electrophilic
substitution as shown in scheme 2.3 led to investigations of
a number of systems in which the activating function Z
contains a carbonyl group [78CR275, 79AG(E)239, 81JOC4108].
The carbonyl group should be efficiently added to and
cleaved from the amine, as well as being resistant to
nucleophilic addition by the alkyl lithium base which is
required to form the carbanionic intermediate (2.2).


14
O
R
H
sec-BuLi
*
CH2R
o
CHR
ch2r
Scheme 2.3
1
O" Li
I I
r/c^S^hr
I
CH2R
(2.2)
Various substituents adjacent to the carbonyl have been
investigated in different amides and the 1,1-diethylpropyl
group was found to be the best of all those considered
[81JOC4316].
Alhough a great number of acyl groups have been used in
the transformation of amines into a-substituted amines,
there has been no investigation of whether there is
synergistic effect, with two or more amide functionalities,
on the stabilization of a carbanion.


15
2.1.3. Synergistic Effects in Stabilization
Dipole stabilized anions of type RR'C NR"-X=Y are known
for a wide variety of groups X=Y [77TL1839,78CR275 ] .
However, little is known about the synergistic effect of
such stabilization in derivatives of type RC (NR'-X=Y)2.
Recently, it has been demonstrated [83T4133] that lithiation
of methylenebispyrazles, to give metallated derivatives of
type (2.3), is indeed somewhat easier than the formation of
the corresponding monocyclic analogues (2.4).
CHLi
CH2Li
T )
CH2Li
(2.3)
(2.4a)
(2.4b)
The classic example of the synergistic effect has been
the work on cyclohexane-1,3-dithiane which has been greatly
exploited in organic synthesis [74JAM1807, 77JAM8262,
6 5AG(E)107 5, 6 5AG(E)1077, 75JOC231J.


16
2.1.4. Aim of the Work
The aim was to study the a-metallation behavior of a
series of compounds containing the structural feature
CH2(NRCOR')2.
2.2. Results and Discussion
Cyclic 1,3-diamines and 1,3,5-triamines were chosen as
the starting compounds and the acyl derivatives of these
compounds were prepared for the study. The acyl unit was
either a benzoyl or a pivaloyl group.
The compounds prepared for the study were 1,3-
dibenzoylimidazolidine (2.5), 1,3-dipivaloylimidazolidine
(2.6), 1,3-dibenzoylhexahydropyrimidine (2.7), 1,3-
dipivaloylhexahydropyrimidine (2.8), 1,3,5-
tribenzoylhexahydro-sym-triazine (2.9) and 1,3,5-
tripivaloylhexahydro-sym-triazine (2.10) .
NCOR
CO
R
(2.5) R = C6H5
(2.6) R = C(CH3)3
^^NCOR
CO
R
(2.7) R = C,H.
D J
(2.8) R = C(CH3)3
CO
R
(2.9)R = C6H5
(2.10)R = C(CH3)3


17
2-.2.1. Preparation of Amides
Compounds (2.5) and (2.6) were prepared from 1,2-
ethylene diamine, formalin and benzoyl chloride or pivaloyl
chloride, respectively (scheme 2.4) Compounds (2.7) and
(2.8) were prepared from 1,3-propanediamine, formalin and
benzoyl chloride or pivaloyl chloride, respectively (scheme
2.4). However, compounds (2.9) and (2.10) were prepared
from sym-trioxane and benzonitrile or pivalonitrile,
respectively (scheme 2.5).
H0N(CH0) NH0 + HCHO
Z n Z
1.NaOH
2.RCOC1
(2.5)
R = C6H5
n=2
(2.6)
R = C(CH3)3
CM
II
c
Scheme 2.4
(2.7)
R = C,H,
6 5
n=3
(2.8)
R = C(CH3)3
n=3
RCN
h3o*
CO
R
(2.9) R = C&H5
(2.10) R = C(CH3)3
Scheme 2.5


18
2.2.2. Lithiation of 1,3-Diacylimidazolidines
Lithiation of (2.5) with lithium diisopropylamide (LDA)
in tetrahydrofuran (THF) at -78C gave a dark brown solution
of a carbanion. Under most conditions, the very reactive
carbanion reacted with more of (2.5) acting as an
electrophile, to give the self condensation product (2.11).
Formation of (2.11) was also confirmed by the appearance of
a ketone carbonyl signal in the NMR. Addition of LDA to
a mixture of (2.5) and an electrophile in THF still gave
(2.11). Use of benzaldehyde or para-tolualdehyde as the
electrophile gave the corresponding benzyl alcohol, along
with starting material, as observed from ^H and 13C NMR
spectra, and dimers of compound (2.5) as observed from mass
spectrometry.
The use of amide (2.6) was an attempt to avoid self
condensation by the introduction of steric crowding around
the carbonyl group. However, this method failed as (2.6)
did not react with LDA, even at 0C. Evidently the tert-
butyl group increased the steric crowding not only around
the carbonyl but also around the C-2 carbon, thus hindering
the approach of the base LDA to the C-2 hydrogen. Similar
explanations have also been given for 1,4-dibenzoyl-2,3-
dimethylquinoxalines not reacting with LDA [84JCS(Pi ) 1949 ] .


19
Use of less nucleophilic tert-butyl1ithium for
deprotonation instead of LDA gave the expected product after
treatment with an electrophile. By this procedure the C-2
methylated compound (2.12) was obtained from compound (2.5)
using methyl iodide as the electrophile. However, the
expected product was not isolated with compound (2.6) and
methyl iodide.
(2.11) E = COC6H5
(2.12) E = CH3
ncoc6h5
CO
2.2.3. Lithiation of 1,3-Diacylhexahydropyrimidines
Lithiation of (2.7) with LDA also afforded a dark
colored solution indicating the formation of the carbanion,
but again on work-up only the self condensation product
(2.13) was obtained. The same product (2.13) was also
obtained on adding LDA to a solution of (2.7) and an
electrophile in THF. When benzaldehyde or para-tolualdehyde
was used as the electrophile, the corresponding benzyl
alcohol was formed, as evidenced by and NMR. Use of
tert-butyl1ithium as the base with compound (2.7) gave the
expected carbanion which was trapped with D-,0 to give
(2.14) .


20
A more stable carbanion was obtained from (2.8) in THF
at -78C with LDA, and this was trapped with D^O to give
(2.15), and with methyl iodide to give (2.16). The ^H NMR
spectrum of (2.15) showed four signals with chemical shifts
identical to the starting material (2.8), however, the
intensity of the signal for the C-2 proton was one fourth of
the signal for the C-4 and C-6 protons.
(2.13)
R = C,H-
0 j
E =
COC,H,
0 j
^^NCOR
(2.14)
R = C6H5
E =
D
^tr^E
(2.15)
R = C(CH3)3
E =
D
CO
(2.16)
R = C(CH3)3
E =
ch3
R
2.2.4. Metallation of 1,3,5-Triacylhexahydro-sym-triazines
Low solubility of (2.9) in THF and DME below 0C
prevented the usual procedure with LDA as base. However,
LDA addition at 25C gave the carbanion which was trapped
with D2O to give (2.17). Metallation under polar conditions
was attempted, but treatment of (2.9) with dimsyl sodium
followed by an electrophile gave only starting material
back .


21
Lithiation of (2.10) in THF at -78C with LDA gave the
carbanion, which was trapped with D2O to give (2.18).
(2.17) R = C6H5 E = D
(2.18) R = C(CH3)3 E = D
2.3. Conclusions
Lithiation studies with 1,3-diacylimidazolidines, 1,3-
diacylhexahydropyrimidines and 1,3,5-triacylhexahydro-sym-
triazines (Table 2.1) indicate that no substantial
additional increase in carbanion stability occurs as a
result of the introduction of the second dipolar stabilizing
group. This might be due to the fact that the conformer
favoring the double stabilization was not the predominant
conformer (discussed in chapter 3). Within the amides
studied the carbanions derived from the benzoyl derivatives
(2.5), (2.7) and (2.9) were found to be less stable, with
(2.5) being the least. However, carbanions derived from
pivaloyl derivatives (2.8) and (2.10) were found to be more
stable with (2.8) being the most. This might have been due
to the increase in steric crowding around the amide C=0
bonds, making them less susceptible for nucleophilic


22
Table 2.1
Formation of a-Lithio Species of Amides and
their Reaction with Electrophiles
Amide
Procedure3
Electrophile
Product
Yield (%)
(2.5)
A
-
( 2.11) b
90
(2.5)
B
CH3I
(2.12)
20
(2.7)
A
-
( 2.13 ) b
80
(2.7)
B
D2
(2.14)
20
(2.8)
A
d2o
(2.15)
50
(2.8)
A
CH3I
(2.16)
80
(2.9)
A
d2o
(2.17)
65
(2.10)
A
d20
(2.18)
85
a For a description of General Procedure A and B see
Expe rimental.
b The same product was also obtained in presence of
electrophiles.


23
addition reactions. In addition, ring size was also found
to be a factor. Five-membered ring was found to be more
influenced by the steric nature of the acyl unit than the
six-membered.
2.4. Experimental
Melting points were recorded on a Bristoline hot-stage
microscope and were uncorrected. Proton NMR spectra were
recorded on a Varian EM 360L spectrometer using internal
Me^Si as the reference. IR spectra were obtained on a
Perkin-Elmer 283 B spectrophotometer.
2.4.1. Reagents
Tetrahydrofuran (THF) was refluxed over and distilled
from sodium benzophenone ketyl. n-BuLi (1.6 M in hexane)
and t-BuLi (1.7 M in pentane) were standardised by titration
[80CC87]. Diisopropylamine was refluxed over and distilled
from CaH^.
2.4.2. Preparation of Acyl Derivatives of Imidazolidines,
Hexahydropyrimidines and Hexahydro-sym-triazines
Preparation of 1,3-dibenzoylimidazolidine (2.5):
Ethylenediamine (5 g, 0.08 M) and formaldehyde (6 g,
37% solution) at 100C were stirred for 0.5 h. The viscous


24
colorless liquid was then kept at 55-60C. Benzoyl chloride
(20 g, 0.14 M) was added dropwise over 30 min. while
maintaining a pH of 8-10 with 10% NaOH solution (75 mL).
The mixture was then stirred for 1 h at 25C. The 1,3-
dibenzoylimidazolidine separated out and was recrystallized
from acetone (10 g, 40%) as plates, m.p. 140C
( lit. [ 73JHC439 ] m.p. 140-141C); \> ( CHB r, ) 1628 cm-1; 6
max j
(CDC13) 3.88 (4 H, s), 5.19 (2 H, s), and 7.55 (10 H, s).
Preparation of 1,3-dipivaloylimidazolidine (2.6):
Ethylenediamine (5 g, 0.08 M), formaldehyde (6 g, 37%
solution) and water (50 mL) were stirred at 100C for 1 h.
To the viscous colorless liquid, aqueous sodium hydroxide
(32 g, 0.8 M in 120 mL of water) was added. The mixture was
cooled to between -10 and -20C and trimethylacetyl chloride
(19.2 g, 0.16 M) added dropwise. After further stirring for
1 h, 1,3-dipivaloylimidazolidine (9 g, 50%), separated. The
crude solid was washed with water and recrystallized from
chloroform, to give prisms, m.p. 141C (Found: C, 64.7; H,
10.1; N, 11.4. ^i3H24N2^2 rec3u;'-res C, 64.9; H, 10.1; N,
11.6%); v = (CHBr,) 1620 cm-1; (CDCl,) 1.28 (18 H, s),
ma x j j
3.79 (4 H, s), and 5.05 (2 H, s).
Preparation of 1,3-dibenzoylhexahydropyrimidine (2.7):
Propane-1,3-diamine (15 g, 0.20 M), water (150 mL) and
formaldehyde (3_ 25 mL 1 r ¡r l c ; e d 100eC for 2 h.
Sodium hydroxide (2.5 M, 75 mL) was added at 25C and then


25
benzoyl chloride (28 g, 0.20 M) dropwise. After stirring
for another 1 h, 1,3-dibenzoylhexahydropyrimidine (15 g,
25%) separated. Crystallization from ether-chloroform gave
plates, m.p. 94-95C (lit.[67AJC1643], m.p. 92-96C); v
luc X
(CHBr3)1625 cm-1; 6 (CDC13) 1.80 (2 H, m), 3.81 (4 H, t, J=6
Hz), 5.17 (2 H, s) and 7.40 (10 H, s).
Preparation of 1,3-dipivaloylhexahydropyrimidine (2.8):
Propane-1,3-diamine (3.7 g, 0.05 M), formaldehyde (37%
25 mL) and water (150 mL) were stirred at 100C for 2h.
Sodium hydroxide (2.5 M, 70 mL) was added at -40C, and then
pivaloyl chloride (12.1 g, 0.10 M) was added dropwise.
After stirring the mixture at 0C for 1 h, column
chromtography (alumina and ether) gave 1,3-
dipivaloylhexahydropyrimidine (4 g, 32%) which crystallized
as plates (from ether), m.p. 115C (Found: C, 65.9; H,
10.0; N, 11.3. C]_4H26N22 requires C, 66.1; H, 10.3; N,
11.0%); v (CHBr,) 1620 cm*1; 6 (CDCl,) 1.28 (18 H, s),
Iua X j j
1.70 (2 H, m), 3.76 (4 H, t, J=6 Hz) and 5.31 (2 H, s).
Preparation of 1,3,5-tribenzoylhexahydro-sym-triazine (2.9):
Compound (2.9) was prepared as reported earlier
[76S467], it formed prisms from ether-chloroform, m.p. 221C
(lit. [76S467], m.p. 220-223C); \> (CHBr,) 1640 cm"1; 6
- max 3
(CDC13) 5.30 (6 H, s), 7.40 (15 H. s).


26
Preparation of 1,3,5-tripivaloylhexahydro-sym-triazine
(2.10) :
Compound (2.10) was prepared following the literature
method [7 6 S 4 6 7 ] for (2.9) in 45% yield as needles from
ether-chloroform, m.p. 134-136C (Found: C, 63.8; H, 9.9; N,
12.2. ci8H33N33 requires C, 63.7; H, 9.7; N, 12.3 %);
v (CHBr,) 1630 cm-1; 6 (CDC1-.) 1.35 (27 H, s) and 5.40 (6
Illa X j j>
H, S) .
2.4.3. Lithiation of the Acyl Derivatives of Imidazolidines,
Hexahydropyrimidines and Hexahydro-sym-triazines
General procedure A:
LDA (1 mmol) was prepared by adding dropwise di
isopropylamine (0.14 mL, 1 mmol) to n-butyllithium in hexane
(1 mmol) at -20C under nitrogen. Stirring was continued
until it became cloudy (0.5 h) and then dry THF (5 mL) was
added. The mixture was then cooled to -78C and the amide
(1 mmol) in dry THF (10 mL) was added. Stirring was
continued for 1 h at -78C and for 10 h more at 20C. Water
(1 mL) was added, and solvents removed at 40-50C/20 mmHg.
The residue in methylene chloride (50 mL) was washed with
saturated aqueous NaCl (10 mL) and water (10 mL) and then
dried (sodium sulphate) and evaporated at 40-50C/20 mmHg.
Products were separated by column chromatography.


27
General procedure B:
Similar to procedure A except that t-butyl1ithium was
used instead of LDA.
2.4.4. Lithiation of 1,3-Dibenzoylimidazolidine
1.3-Dibenzoyl-2-methylimidazolidine (2.12):
Following procedure B using 1,3-dibenzoylimidazolidine
(2.5) with methyl iodide as the electrophile gave 1,3-
dibenzoyl-2-methylimidazolidine (2.12) (20%) as needles from
CHCl3, m.p. 150 0 C (Found: C, 73.3; H, 6.3; N, 9.4.
C18H18N22 rec3uii:'es C' 73.5; H, 6.1; N, 9.5 %); vmax(CHBr3)
1625 cm-1; 6 (CDC13) 8.30-7.30 (10 H, m), 5.50 (1 H, q, J=5
Hz), 4.35-3.60 (4 H, m) and 1.38 (3 H, d, J = 5 Hz).
1.2.3-Tribenzoylimidazolidine (2.11) :
1,3-Dibenzoylimidazolidine (2.5) following procedure A
self condensed to give 1,2,3-tribenzoylimidazolidine (2.11)
(90%) as needles from CHC13, m.p. 228C (Found: C, 74.8, H,
5.5; N, 7.4. ^24H20N2^3 rec2uires C, 75.0; H, 5.2; N, 7.3 %);
\> v (CHBr-J 1710, 1625 cm-1; 6 (CDCl,) 8.50-7.30 ( 15 H, m),
max j j
4.00 (4 H, s) and C-2 proton not observed.


28
2.4.5. Lithiation of 1,3-Dibenzoylhexahydropyrimidine
2-Deuterio-l,3-dibenzoylhexahydropyrimidine (2.14):
1.3-Dibenzoyl-hexahydropyrimidine (2.7) following
procedure B with D2O as the electrophile gave 2-deuterio-
1.3-dibenzoylhexahydropyrimidine (2.14) (20%) as needles
from ether, m.p. 95C (Found: C, 73.2; H, 5.8; N, 9.1.
^18H17DN22 rec3u^res c' 73.2; H, 5.8; N, 9.5); ^>max (CHBr)^
1625 cm-1; S (CDCl3) 7.40 (10 H, s), 5.17 (1 H, s), 3.81 (4
H, t J=6 Hz), and 1.80 (2 H, m).
1.2.3-Tribenzoylhexahydropyrimidine (2.13) :
1.3-Dibenzoylhexahydropyrimidine (2.7) following
procedure A without any electrophile gave 1,2,3-
tribenzoylhexahydropyrimidine (2.13) (80%) as needles from
CHCl3, m.p. 225C (Found: C, 75.2; H, 5.7; N, 7.0.
C25H22N23 re{Juires C' 75.4; H, 5.5; N, 7.0 %); ^>max (CHBr^)
1715, 1628 cm-1; S (CDC13) 8.20-7.25 (15 H, m), 4.05-3.30 (4
H, m), 1.90-1.30 (2 H, m) and C-2 proton not observed.
2.4.6. Lithiation of 1,3-Dipivaloylhexahydropyrimidine
2-Deuterio-l,3-dipivaloylhexahydropyrimidine (2.15):
1.3-Dipivaloylhexahydropyrimidine (2.8) following
procedure A with D~0 as electrophile gave 2-deuterio-1,3-
dipivaloylhexahydropy r imidine 1 2.15) : 50 : ) as plates from


29
CH2C12, m.p. 115-116 C (Found: C, 65.8; H, 10.1; N, 10.8.
C,.H0CDN0CU requires C, 65.9; H, 9.8; N, 11.0 %); v
X 4 Z j Z Z IclX
(CHBr3) 1620 cm-1; 6 (CDC13) 5.25 (1 H, s), 3.75 (4 H, t,
J=6 Hz), 1.67 (2 H, m) and 1.26 (18 H, s).
1,3-Dipivaloyl-2-methylhexahydropyrimidine (2.16):
1,3-Dipivaloylhexahydropyrimidine (2.8) following
procedure A with methyl iodide as the electrophile gave 1,3-
dipivaloyl-2-methylhexahydropyrimidine (2.16) (80% based on
recovery of starting material) as needles from CHCl^, m.p.
125C (Found: C, 67.5; H, 10.6; N, 10.3. C]_5H28N22 rec3uires
C, 6 7.2; H, 10.4; N, 10.4 %); (CHB r,) 1630 cm-1; 6
ITla X j
(CDC13) 6.90 (1 H, q, J=6 Hz), 4.40-3.40 (4 H, m), 2.00-1.40
(2 H, m), 1.29 (18 H, s) and 1.18 (3 H, d, J=6 Hz).
2.4.7. Lithiation of 1,3,5-Tribenzoylhexahydro-sym-triazine
2-Deuterio-l,3,5-tribenzoylhexahydro-sym-triazine (2.17) :
1,3,5-Tribenzoyl-hexahydro-sym-triazine (2.9) following
procedure A, but with addition of LDA to (2.9) in THF at
25C, with D20 as the electrophile gave 2-deuterio-l,3,5-
tribenzoylhexahydro-sym-triazine (2.17) (65%) as plates from
CHCl3, m.p. 221C (Found: C, 72.1; H, 5.3; N, 10.3.
C'>4H20DN33 re<3uires C' 72.0; H, 5.0; N, 10.5 %);
v (CHBrJ 1640 cm-1; 6 (CDCl,) 7.54 (15 H, s) and 5.40 (5
m u x j
H, S) .


30
2.4.8. Lithiation of 1,3,5-Tripivaloylhexahydro-sym-
triazine
2-Deuterio-l,3,5-tripivaloylhexahydro-sym-triazine (2.18) :
1,3,5-Tripivaloylhexahydro-sym-triazine (2.10)
following procedure A with D2O as the electrophile gave 2-
deuterio-1,3,5-tripivaloylhexahydro-sym-triazine (2.18)
(85%) as plates from CHCl^, m.p. 135C (Found: C, 63.4; H,
9.6; N, 12.2. ^18H32DN33 ret3uires C, 63.5; H, 9.4; N, 12.3
%); vmo^(CHBr-j) 1630 cm"'*'; 6 (CDCl,) 5.40 (5 H, s) and 1.35
IUa X j j
(27 H, s ) .


CHAPTER 3
CONFORMATIONAL ANALYSIS OF AMIDES
3.1. Introduction
During the last two decades, NMR spectroscopy has
developed into one of the most valuable techniques for
investigating molecular structure and stereochemistry. Not
only can NMR give the extent of equilibrium between
different conformers but can also yield information about
the dynamic behavior of the different conformers at various
temperatures. This is referred to as dynamic nuclear
magnetic resonance (DNMR). The barrier heights or the free
energy of activation of dynamic processes amenable to this
technique conveniently extend just from the border line of
20-25 kcal mole ^ below which compounds become too unstable
to be isolated, to about 5-6 kcal mole ^. Restricted
rotation about the C(0)-N bond in amides is the classical
example of a rate process that can be studied by DNMR.
Activation parameters can be obtained to a greater
accuracy using total line shape analysis. However, a great
number of references are available indicating that the
31


32
coalescence temperature has been used to obtain the free
energy of activation.
3.1.1. Conformational Analysis Using DNMR
Though DNMR has been used to study all types of
compounds like substituted ethanes, amides, carbamates,
thioamides, nitrosoamines, nitriles, aldehydes and ketones,
only amides will be discussed here.
Resonance theory describes the electronic structure of
amides as a hybrid of (3.1a) and (3.1b) suggesting a certain
amount of double-bond character for the C(0)-N bond, and
thus there is a concomitant increase of the rotational
barrier over that in pure single bonds. There is a chance
t M
to observe the rate process by DNMR because R and R reside
t
in different magnetic environments (R being more shielded
than R ) [63JAM3728] in the fixed structure (3.1) but are
time-averaged on rapid rotation. This prediction was first
confirmed for dimethylformamide and dimethylacetamide
[55JCP1363].
R" R"
(3.1a)
(3.1b)


33
3.1.2. DNMR Studies on Monoamides
Of the total number of DNMR studies done on amides, the
major portion has been on monoamides. Initial studies on
dimethylformamide from different groups showed barriers from
-1
which was later attributed to factors
6.3-28.2 kcal mole
like solvent, concentration, temperature and long range
coupling in addition to instrumental errors. However, using
high field and high resolution instruments with specified
solvent and specified concentration, the difficulties are
overcome. For determination of an accurate value for the
free energy of activation, the total line shape analysis
method has always been used.
A great deal of work has been done on the effect of
substituents (both on the nitrogen and on the carbonyl
group), solvent, and concentration on the barrier. In
certain cases stable amide conformers have been isolated in
pure form [66TL4593], such as in the case of (3.2) where a
severe steric interaction raises the barrier by an
additional amount (30-32 kcal mole-1).
C(CH3>3
C3
(3.2a)
(3.2b)


34
3.1.3. DNMR Studies on Polyamides
Restriction of rotation about the C(0)-N bond of amides
has been the subject of intensive study, and the structural
influences on the equilibria and kinetics of the syn-anti
interconversion are well understood for monoamides (scheme
3.1) [68MI1]. However, the same wealth of information is
not available for polyamides. Conformational properties of
polyamides have been obtained from NMR studies of the
conformation of model diamides derived from trans-1,2-
cyclohexane carboxylic acid and different aliphatic amines
[72MM197], and piperazine or N,N'-dimethylethylenediamine
and aliphatic or aromatic carboxylic acids [69MM154].
Signals for the different conformational isomers in diamides
have been assigned using paramagnetic shifts induced by
Eu(fod)^ complexes [72JOC3434].
Scheme 3.1


35
Indeed, the investigation of DNMR spectra involving
more than two different species has been relatively limited.
NMR investigation of thiophene-2,5-dicarboxaldehyde has been
done in liquid crystals [72JCS(P2)755]. Rotational
isomerism of N,N'-dimethyl-a,w-bis(benzoylamino)alkanes
[84JCS(P2)1089] and 1,3,5-trinitrosohexahydro-l,3,5-triazine
[69RC1687] has been studied using variable temperature
NMR spectroscopy. Stereoisomerization of N,N'-diacetyl-
N,N'-dimethylhydrazine using variable temperature ^H NMR
spectroscopy has also been studied and a discussion about
the mechanism of stereoisomerisation was given [75GCI569].
3.1.4. Aims of the work
The goals of this work were (i) to elucidate the
equilibria on some cyclic model systems of bis- and tris-
amides, (ii) to calculate the rotational barriers and (iii)
to deduce the mechanism of rotation based on the spectral
behavior at various temperatures.
3.2. Results and Discussion
The model systems chosen for the bis-amide studies were
1,3-diacylimidazolidines (3.3) and (3.4) and 1,3-
diacylhexahydropyrimidines (3.5) and (3.6). For the tris-
amide studies it was 1,3,5-t.. 1 r Ihexahydro-sym-triazines
(3.7) and (3.8) .


36
(3.3) R = C,Hc
D J
(3.4) R = C(CH3)3
(3.5) R = C.H,
6 5
(3.6) R = C(CH3)3
ROCN NCOR
R
CO
(3.7) R = C,H,
6 5
(3.8) R = C(CH3)3
ROCN NCOR
3.2.1. Conformers of Diamides and Triamides
A single amide bond can exhibit two conformations.
Similarly two amide bonds together can exhibit four
conformations and three amide bonds together can exhibit
eight conformations. However, on deriving these amides by
acylating cyclic di- and triamines (keeping the acyl groups
the same) some of the conformers become indistinguishable.
For example, in compounds (3.3), (3.4) (3.5) and (3.6)
although there are four possible conformers only three are
distinguishable. Furthermore, for compounds (3.7) and (3.8)
of the eight possible conformers, only two of them are
distinguishable. The indistinguishable conformers are
referred to as topomers [ 71G' r; ~ 0 J .


37
Distinguishing the different conforraers experimentally
(in this case using NMR) was not an easy task. To diagnose
this, model compounds were developed to assign chemical
shifts to the different conformations of the compounds (3.3-
3.8) .
3.2.2. Model Compounds for Conformational Analysis of Acyl
Derivatives of Cyclic Secondary Amines Imidazolidine ,~
Hexahydropyrimidine and Hexahydro-sym-triazine
On investigating the different conformers of all the
compounds, the methylene group between the two nitrogen
atoms was found to be either between the two carbonyl
oxygens, or between the R groups of the acyl units or
between one carbonyl oxygen and one R group of the acyl
unit. Although it was known already that the N-alkyl group
syn to the carbonyl is always more shielded than when it is
anti [63JAM3728], model compounds were still used for the
signal assignments.
Since pivaloyl and benzoyl derivatives of amines were
used, comparison was done with similar model systems.
1,3,3-Trimethyl-2-piperidone (3.9) showed the N-methyl
(necessarily syn to the carbonyl) at delta 3.00 ppm


38
[75CJC1682]. By analogy, the syn-methyl in N,N-
dimethylpivalamide (3.10) has been assigned to the signal at
2.96 ppm and the anti-methyl to the signal at 3.21 ppm in
the 1H NMR spectrum obtained at -40C.
(3.9)
(3.11)
IVi0
(3.10)
R = C(CH~),
3 j
I
(3.12)
R = C.H,
HC^''Nsvu
6 5
3 CH3
(3.13)
R = H
(3.14)
R = CH3
In the phenyl series, the model compound N-methyl-
1,2,3,4-tetrahydro-2-isoquinolone (3.11) showed the
(necessarily syn) N-CH^ signal at delta 3.20 ppm [82T539]
N,N-Dimethylbenzamide (3.12) at -26.6C in CB^Bl^ showed
signals at delta 3.38 and 3.53 ppm for the N-CH^ protons
[62JPC540] and in comparison with (3.11), the signal at
delta 3.38 ppm was assigned to methyl syn
to the carbonyl.


9
Fig .
H.C.OCN.
j o
NCOC£Hc
b j
TMS
~i 1 r
8 7 6
4
3
2
T
T
1 0
.i 60 MHz ^H NMR Spectrum of 1,3-Dibenzoylimidazolidine (in CDCl^) at
2 5 0 C .


-i < 1 1 1 1 1 r
8 76543210
Fig .
300 MHz 1H NMR Spectrum of 1,3-Dibenzoylimidazolidine (in CDCl^) at
- 3 0 0 C .


1 1 1 1 1 1 I I I I
98 76 543 210
60 MHz 1H NMR Spectrum of 1,3-Dipivaloylimidazolidine (in CDCl^) at
2 5 0 C .
Fig.


e
c
Fig.
500 MHz ;H NMR Spectrum of 1,3-Dipivaloylimidazolidine (in CDClj) at
-7 0 0 C .


43
In the case of spectra the signals were assigned to
different conformers by referring to model compounds (3.13),
(3.14) and particularly (3.12), in which the N-methyl
carbons syn to the carbonyl group had been always shielded
(31.1, 34.5, 35.2 ppm, respectively) compared to the anti N-
methyl carbons (36.2, 37.5, 38.9 ppm, respectively) [78MI1].
In addition, the intensity and the number of signals were
also used for the signal assignments.
An interesting feature of these results from the model
systems considered both for proton and carbon, is that
groups syn to the carbonyl oxygen are always shielded over
the groups anti to it.
3.2.3. 1,3-Diacylimidazolidines Conformational Equilibria
from h NMR Spectra
At 25C for compound (3.3) (figure 3.1) and for (3.4)
(figure 3.3), a 2H singlet for 2-CH2 and a 4H singlet for
4,5-C2H4 were observed, which demonstrated rapid rotation
about both amide links (Table 3.1). As the temperature was
lowered, these peaks broadened and split and, below -30C
for (3.3) (figure 3.2) and below -80C for (3.4) (figure
3.4), separate signals were observed for each of the three
conformers (Table 3.1). In addition to the above, (3.3)
shows signals for the phenyl protons at 7.56 ppm as a broad
singlet and (3.4) for the t-Bu at 1.28 ppm as a singlet. On


Table
3.1 ^H NMR Chemical Shifts (ppm),
1,3-Diacylimidazolidines (3.3)
J Values
and (3.
(Hz) and
4)
Relative
Population
(%) for
Temp.
compound
2-CH
l2
popn.
4
,5-
c2h
4
popn
R
C
(conforme r)
S
I
(%)
6
M
J
I
(%)
& M
I
2 5a
(3.3)
5.20
2.00b
-
3.88
S
-
4.00
-
7.56 s
10.44
- 3 0 C
(3.3a)
4.95
0.07
3.5
4.03
s
-
0.21
5.3
7.50 m
10.54
(3.3b)
5.17
1.60
80.0
4.03
t
7
3 18
79.5
3.82
t
7
(3.3c)
5.45
0.33
16.5
3.79
s
-
0.61
15.2
2 5"
(3.4)
5.15
2.00b
-
3.85
s
-
4 .00
-
1.28 s
18.00
-7 0'
(3.4a)
5.01
0.55
27.5
4.05
s
-
1.23
30.8
1.24d s
e
(3.4b)
5.12
1.40
70.0
3.93
t
6
2.71
67.7
1.28d s
e
3.86
t
6
(3.4c)
5.27
0.05
2.5
3.72
s
-
0.06
1.5
1.31d s
e
M = multiplicity; t
= triplet; s
= singlet; m
= multiplet.
J =coupling constant
( Hz ) ;
ci b
I = intensity. L 60 MHz spectrum. Intensity reference standard. For low temperature
spectra, total intensity of 2.0 for these peaks taken as standard. c 300 MHz spectrum,
d e
Tentative assignment. Total intensity 18.8, individual intensities not measurable due
to overlap.


45
cooling, these peaks broaden and reappear respectively as a
multiplet near 7.50 ppm for (3.3) and as three singlets at
1.31, 1.28 and 1.24 ppm for (3.4).
Comparing the model compounds for chemical shift
assignment in conformers (a), (b), and (c) (scheme 3.2) of
(3.3) and (3.4), we expect the protons to be at
highest field in (a) where they are syn to both carbonyls
and at lowest field in (c) where they are anti to both
carbonyls. Conversely, conformer (a) should show a singlet
at lower field for the 4,5^2^ protons than the singlet for
(c). In the unsymmetrical conformer (b), the 4,5^2^
protons should display an AA'XX' pattern, with the chemical
shift for A nearer to that of conformer (c) and of X nearer
to conformer (a). The assignments in Table 3.1 followed
these considerations.
The relative proportions of the three conformers
obtained from the relative signal intensities are also shown
in Table 3.1. Those for the 2-CH2 indicate (a):(b):(c) =
3.5:80.0:16.5% for (3.3) and (a):(b):(c) = 27.5:70.0:2.5%
for (3.4). Those for the 4,5-CH2 indicate (a):(b):(c) =
5.3:79.5:15.2% for (3.3) and (a):(b):(c) = 30.8:67.7:1.5%
for (3.4). Since the 2-CH-, signals are separate singlets


46
for the different conformers, they are considered to be more
reliable for isomer proportion deduction than the 4,5-CH2
signals, for which the singlet for the conformers (a) and
(c) overlaps with the AA'XX' double triplets from conformer
(b) .
Rationalizing our results it seems that in the
equilibrium for (3.3) at -30C, conformer (b) was favored
over (a) by 1.51 kcal mole-1 and over (c) by 0.76 kcal
mole ^. However, for (3.4) at -70C, conformer (b) was
favored over (a) by 0.35 kcal mole 1 and over (c) by 1.28
kcal mole-1.
3.2.4. 1,3-Diacylhexahydropyrimidines Conformational
Equilibria from h NMR Spectra
At 25C compounds (3.5) (figure 3.5) and (3.6) (figure
3.7), showed a 2h singlet for the 2-CH2 protons, which
demonstrates that, just as for (3.3) and (3.4), rapid
rotation occurs about both amide links (Table 3.2). At low
temperatures for (3.5) (figure 3.6) the peaks broaden and
split and at -30C separate signals were observed for each
of the three conformers. However, for (3.6) (figure 3.8) at
-103C separate signals were seen only for two conformers.


47
Signal assignments were based on model compounds
discussed earlier. The protons gave an additional signal
around 1.9 ppm. The assignments of Table 3.2 follow these
considerations. For example the assignments for the 2-CH2
protons of (3.5) and (3.6) are as follows; at -30C, (3.5)
showed three signals for the 2-CH2 protons. Using the rule
derived from model compounds that protons syn to the
carbonyl oxygen were shielded, the one to the lowest field
was assigned to (3.5c), the one to the highest field to
(3.5a), and the middle one to (3.5b) (scheme 3.3). On
similar grounds, of the two signals observed for compound
(3.6), the most intense signal was assigned to (3.6b) and
the remaining one being at higher field than that of (3.6b),
was assigned to (3.6a). Assignments for the C^-Cg protons
were made similarly (Table 3.2).
Relative signal intensities and the isomer proportions
from the 2-CH2 signals are shown in Table 3.2. For (3.5),
(a):(b):(c) = 39.7:53.3:7.0% and for (3.6), (a):(b):(c) =
8:92:0%. From the 4,6-CH2 signals, it was not possible to
derive conformer proportions because of additional coupling
to the 5-CH2, and overlapping of signals.


d
TMS
h5c6ocnx^/ncoc6h5
T~
9
r~
8
-~i
0
Fig. i 3
0 MHz ^H NMR Spectrum of 1,3-Dibenzoylhexahydropyrimidine (in C 3)
at 250C .


d
4
3
Fig .
30 MHz ^H NMR Spectrum of 1,3-Dibenzoylhexahydropyrimidine (in CDCl,)
at 30 C.


TMS
( ch3 )^ocn^/ ncoc (ch3 ) 3
d
chci3
d
k-
1 1 r-
9 8 7
6
T
4
3
T
2
1
0
Fig.
60 MHz lH NMR Spectrum of 1,3-Dipivaloylhexahydropyrimidine (in CDC13)


acetone
b
d
b
'U^J
TMS
(J1
T
T
1 T
T
T
T
T
6 5 4
3 2 1 0 5.1
5.0
4.9
3
300 MHz 1H NMR Spectrum of 1,3-Dipivaloylhexahydropyrimidine (in
CD3COCD3) at -10 3 0 C.
Fig.


Table 3.2 NMR Chemical Shifts (ppm) and Relative Population (%) for 1,3-Diacyl-
hexahydropyrimidines (3
.5) and
(3.6)
Temp.
compound
2-CH2
popn.
4(6)-CH2
5-CH
2
R
C
(conforme r)
S(M)
I
(%)
S ( M ) I
S(M)
I
&(M)
I
2 5a
(3.5)
5.17 ( s )
2.00b
-
3.81(t)C 4.00
1.80(m)
2.02
7.4 0 ( m)
10.4
-3 0d
(3.5a)
5.04(s)
0.79
39.7
3.95(m) 4.30e
1.84f(m)
2.01e
7.34(m)
10.5e
(3.5b)
5.20(s)
1.06
53.3
3.95(m)
1.9 3 f ( m)
-
7.3 4 ( m)
-
3.66(m)
(3.5c)
5.57(s)
0.14
7.0
3.66(m)
1.8 4 f ( m)
-
7.34(m)
-
2 5a
(3.6)
5.31(s)
N>
O
O
17
-
3.76(t)C 4.00
1.7 0 ( m)
2.03
1.28(s )
18.00
-10:
(3.6a)
4.99(s)
0.16
8.0
4 41(m) 4.40e
1.78(m)
2.04e
1.16(s )
19.0e
(3.6b)g
5.0 3(s)
1.84
92.0
4 41 ( m )
1.78(m)
-
1.16(s)
-
M = m
Ltiplicity;
t = triplet; s =
singlet; I = intensity
. 3 60 MHz
spectrum. b Intensity
refecence standard; at low temperature total intensity for these peaks taken as 2.0.
c
Being at low field (60 MHz) this signal is seen as an apparent triplet with J = 6 Hz.
d 0 f
300 MHz spectrum. Individual intensities not measurable due to overlap. Tentative
assignment. g No peaks for (3.6c) observed.


53
The equilibrium at -30C for (3.5) favored conformer
(b) over (a) by 0.14 kcal mole-"'" and conformer (b) over (c)
by 0.98 kcal mole ^. However, for (3.6), the equilibrium at
-103C favored conformer (b) over (a) by 0.83 kcal mole-'*'.
3.2.5. 1,3,5-Triacylhexahydro-sym-triazines Conformational
Equilibria from 1H NMR Spectra
At 25C compounds (3.7) (figure 3.9) and (3.8) (figure
3.11) showed a 6H singlet for the three CH2 protons,
demonstrating rapid rotation about all three amide links.
As the temperature was lowered the peaks broadened and
split, and at -30C separate signals were observed for (3.7)
(figure 3.10) for each of the two conformers. However, for
(3.8) only one conformer (x) was observed even for spectra
recorded as low as -110C using acetone-dg as the solvent
(Table 3.3) (scheme 3.4).
Signal assignments shown in Table 3.3 follow the same
rules observed for signal assignment for imidazolidines
(3.3) and (3.4), i.e., the protons syn to the carbonyl
oxygen were shielded. The methylene protons for (3.7) at
-30C showed four singlets, of which three signals were of


b
a
TMS
T I 1 I 1 1 1 1 1 f
9 8 76 54 3 210
60 MHz LH NMR Spectrum of 1,3,5-Tribenzoylhexahydro-sym-1riazine (in
CDC1 ) at 25C.
Fig.
, 9


3 5
Fig. 3.10 300 MHz 1H NMR Spectrum of 1,3,5-Tribenzoyl-
hexahydro-sym-triazine (in CDCl^) at -30C.


60 MHz ^H NMR Spectrum of 1,3,5-Tripivaloylhexahydro-sym-triazine (in
CDC1 ) at 25C .
Fig. . ii


cr 3
Table 3 3
bH NMR Chemical Shifts (ppm) and Relative Population (%) for 1,3,5-
Triacylhexahydro-sym-triazines (3.7) and (3.8)
Temp.
compound
2,4,6
-ch2
popn.
N-substit.
C
(conformer)
S(M)
I
(%)
MM)
I
2 5a
(3.7)
5.30(s)
os
O
O
cr
-
7.4 0 ( s )
15.2
u
o
m
1
(3.7x)
5.38(s )
2.19
36.5
7.4 0 ( m )
d
(3.7y)
5.26(s)
3.81e
63.5
7.4 0 ( m)
d
5.37(s)
5.71 ( s )
2 5a
(3.8)
5.4 0 ( s )
6.00b
-
1.35(s)
27.4
-100'
(3.8x)f
5.39(s)
6.00
100.0
1.3 3 ( s )
27.3
= multiplicity; s = singlet; m = multiplet; I = intensity. a 60 MHz spectrum.
C d
standard reference intensity. 300 MHz spectrum. Total intensity 15.1;
individual intensities not measurable due to overlap. e Total intensities of the
three signals together. b Signals for (3.8y) not observed, even at -110C.


58
equal intensity corresponding to conformer (3.7y). The one
remaining signal was assigned to conformer (3.7x), in which
all methylene protons are identical.
Relative signal intensities and the isomer proportions
from the 2,4,6-CH2 signals are shown in Table 3.3. For
(3.7) (x):(y) = 36.5:63.5% and for (3.8) (x):(y) = 100:0%.
For the equilibrium at -30C (3.7) favored conformer
(y) over (x) by 0.26 kcal mole ^. However, (3.8) was found
to exist exclusively in the (x) conformer.
3,2.6. 1,3-Diacylimidazolidines Conformational Study from
C NMR Spectra
The 75 MHz spectra of (3.3) (figure 3.12) at 25C were
near coalescence, and showed broadened lines for C-2, C-4
and C-5 which became sharp singlets at 60C; (3.4) (figure
3.14) showed sharp singlets for these carbons at 25C. At -
30C for (3.3) (figure 3.13) and -70C for (3.4) (figure
3.15), signals were seen for the individual conformers
(Table 3.4). The signals were assigned to different
conformers based on the model compounds discussed earlier
(see section 3.2.2).


a
a
1 1- 1 1 1 1 1
140 120 100 80 60 40 20 0
25 MHz NMR Spectrum of 1,3-Dibenzoylimidazolidine (in CDCl^) at
60 0 C .
160
Fig. j i2


NMR Spectrum of 1,3-Dibenzoylimidazolidine (in CDCl^) at
Fig. ,13
7 5 MHz
- 3 0 0 C .


a
a b | | b a
(H3C)3COCNvv^ NCOC(CH3)3
cr
i 1 1 1 1 r
160 140 120 100 80 60
n 1
40 20
Fig. 14
25 MHz NMR Spectrum of 1,3-Dipivaloylimidazolidine (in CDC13) at
25C .
*
0


Fig .
i 1 1 1 1 1 r
180 150 120 90 60 30 0
L5 75 MHz 13C NMR Spectrum of 1,3-Dipivaloylimidazolidine (in CDCl3) at
-7 0 0 C.


Table 3.4
C NMR Shifts (S, ppm) for 1,3-Diacylimidazolidines (3.3) and (3.4).
13
Comp .
Temp.
Confor
Imidazolidine
R-substituent
o
ii
u
no .
C
mation
ring
C
6H5 or
c(ch3)3
C2
C4
C5
C1
C2'C6a
c c a
L3'L5
C4
(3.3)
50b
62.0
45.7
45.7
135.1
127.1
128.4
130.6
168.8
2 5b
c
c
c
134.8
127.0
128.3
130.5
168.7
-30d
(3.3a)
60.4
48.0
48.0
134.4a
126.9
127.3
130.8a
e
(3.3b)
62.3
44.2
46.5
134.6a
127.0
128.5
130.9a
169.4
168.8
(3.3c)
e
42.8
42.8
134.7a
127.2
128.7
131.Ia
168.6
(3.4
2 5b
62.3
45.5
45.5
38.8
27.2
175.8
-70d
(3.4a)
61.7
46.6
46.6
38.7a
26.80a
175.3
(3.4b)
63.7
46.5
43.6
38.6a
26.74a
175.8
175.7
(3.4c)
e
e
e
38.5a
26.70a
e
a Tentative assignment. b 25 MHz spectrum. c one broad unresolved peak. d 75 MHz spectrum.
0
Not observed.


64
For compound (3.3) conformers (3.3a), (3.3b) and (3.3c)
showed a total of four signals due to C-4 and C-5 carbons.
Of these, the two intermediate chemical shifts were of equal
intensity and were unambiguously assigned to the conformer
(3.3b). From the rule stated above, that the carbon syn to
the carbonyl oxygen was shielded, the medium intensity peak
at 48.0 ppm was assigned to (3.3a) and the low intensity
peak at 42.8 ppm to (3.3c). (These assignments are in fair
agreement with the conformer populations deduced from the
proton spectra). For the C-2, only two signals were
obtained; the peak of higher intensity was assigned to
(3.3b) and the other one being at a higher field than that
for (3.3b) was assigned to (3.3a). The expected peak for
the least populated isomer (3.3c) was not observed.
Compound (3.4) displayed only three peaks for the 4,5-
carbon atoms: two of equal and high intensity were
unambiguously assigned to (3.4b); the less intense peak at
lower field was assigned to (3.4a), again based on the rule
that the carbon syn to the carbonyl oxygen was shielded.
With conformer (3.4c) being the least populated, (cf proton
spectra) its peaks were not observed. Similarly, for the
C-2 carbon, peaks were found only for (3.4a) and (3.4b).


65
i 3
The C chemical shift assignments of the phenyl group
in (3.3) and the t-butyl group in (3.4) were based on the
difference in intensity of the signals, the off-resonance
spectra, and for R=CgH^ comparison with the spectrum of
(3.12). In compound (3.3), the C-2,6 and C-3,5 carbons of
the phenyl ring showed relatively intense signals (doublets
in off-resonance spectrum), and C-l a low intensity signal
(singlet in off-resonance spectrum). In compound (3.4), the
quaternary carbon of C(CH^)^ showed a low intensity signal
at ca. 38 ppm, and the methyl groups gave a very intense
signal at higher field. The lowest field signal in the
spectra of compounds (3.3) and (3.4) was that of the
carbonyl carbons. The low temperature spectrum, of each of
the compound showed three C=0 signals of which the two of
equal intensity were assigned to the two carbonyl groups in
conformer (b). The signal due to the least populated
conformer, (a) in (3.3) and (c) in (3.4), was not observed.
3.2.7., 1,3-Diacylhexahydropyrimidines Conformational Study
from NMR Spectra
The 75 MHz spectrum of (3.5) (figure 3.16) at 25C was
near coalescence and showed broadened signals for C-2, C-4,
C-5 and C-6 which became sharp signals at 60C; (3.6)
(figure 3.18) shows sharp signals for the ring carbons at


a
, 1 1 1 1 1
200 180 160 140 120 100
1 1 r
80 60 40 20
0
Fig. 3.L6 25 MHz NMR Spectrum of 1,3-Dibenzoylhexahydropyrimidine (in
CDCl^) at 60 C.


a
er^Se
H5C^|fN^fK]^C6H5
0 £ 0
HsW
o
0 c
r y
H5C6 C6H5
IftluyW
g
i
o
180
160
140 120
100 80
60
40
20
L7 75 MHz NMR Spectrum of 1,3-Dibenzoylhexahydropyrimidine (in
CDCl^) at -40C.
Fig.


b
( h3c ) 3coc NCOC ( ch3 ) 3
f e f
i i i 1 1 1 1 1 1 1 r
200 180 160 140 120 100 80 60 40 20 0
L8 25 MHz 13C NMR Spectrum of 1,3-Dipivaloylhexahydropyrimidine (in
CDC1 ) at 25C.


Fig. 3 L9 75 MHz 13C NMR Spectrum of 1,3-Dipivaloylhexahydropyrimidine (in
cd3cocd3) at -100C.


70
25C. At -40C signals for the individual conformers
appeared in the spectrum of (3.5) (figure 3.17). However,
for (3.6) at -70C separate signals were seen only for two
conformers as was described above for the spectrum
(figure 3.19).
Signals were assigned by reference to model compounds
as discussed earlier. The C-5 carbon gave an additional
signal around 24.5 ppm. The assignments of Table 3.5 follow
these considerations. An illustration for the C-2 carbons
of (3.5) and (3.6) is as follows; at -40C (3.5) showed
three signals for the C-2 carbon. Using the rule that the
carbon syn to the carbonyl was the most shielded, the most
downfield signal was assigned to (3.5c), the most upfield
signal to (3.5a) and the remaining one to (3.5b). Based on
similar considerations, of the two signals seen for the C-2
carbon of (3.6), the most intense was assigned to (3.6b).
Since the remaining one was at a higher field than (3.6b),
it was assigned to (3.6a). These assignments agree with
conformer populations deduced from the proton spectra.
Assignments for the C-4-C-6 carbons were made similarly.


Table 3.5
C NMR Shifts (&, ppm) for 1,3-Diacylhexahydropyrimidines (3.5) and (3.6)
13
Temp.
Comp.
Pyrimidine Ring
R-Substituent
o
n
o
C
(confo-
C2
C4
C5
C6
C
6H5 or
c(ch3)3
mation)
C1
C2 C6
C3'C5
C4
25a
(3.5)
59.8
44 3
24.9
44 3
133.2
127.4
128.4
130.3
170.1
jQ
O
1
(3.5a)
52.8
47 3
25.2
47.3
134 3C
127.2
128.4
130.3
169.9
(3.5b)
58.2
47.0
25.2C
41.8
134.0
127.0
128.3
130.2
170.6
133.9
126.8
169.8
(3.5c)
62.8
41.7
24.0C
41.7
133.3
126.5
128.1
130.0
d
25a
(3.6)
58.3
44.9
24.9
44.9
38.7
28.00
176.8
-70b
(3.6a)
58.4
47.1
25.6
47.1
39.1
28.2
176.1
(3.6b)d
58.6
47.1
25.6
43.3
39.1
28.3
176.1
28.1
175.8
a 25
MHz spectrum
. b 75
MHz
spectrum
c
Tentative
assignment. d
Conformer
(3.6c) not
observed.


72
3.2.8. 1,3.§-Triacylhexahydro-sym-triazines Conformational
Study from 1JC NMR Spectra
The 75 MHz spectra of (3.7) (figure 3.19) and (3.8)
(figure 3.21) at 25C showed signals for the three methylene
carbons at 58.5 and 57.3 ppm, respectively. At -70C for
(3.7) (figure 3.20), signals were seen for the individual
conformers. However, for (3.8) only one conformer (x) was
observed even at a temperature as low as -110C. This was
the same result as seen in its ^H spectrum. The signal
assignments for the two conformers (x) and (y) of compound
(3.7) and one conformer (x) of compound (3.8) were also
based on the model compounds discussed earlier. The signal
assignments are shown in Table 3.6.
3.2.9. Kinetic Parameters
The kinetic parameters obtained were the free energy
difference between conformers and the free energy of
activation for the barrier to rotation around the amide
C(0)-N bonds. The free energy differences (AG) were
calculated from the population ratios (of their C-2
methylene protons signals) obtained for each of the amides
from their ^H NMR spectra and are given in table 3.7. Free
energies (AG), which are compensated for the entropy factor
(for the topomers of unsymmetrical isomers), are also given
in table 3.7.


3 20
25 MHZ 13c NMR Spectrum of 1,3,5-Tribenzoylhexahydro-sym tnazine
CDC1J at 25C.
( in
Fig .


t 1 1 1 1 1 1 i i r
180 160 140 120 100 80 60 40 20 0
3.21
1 3
7b MHz C NMR Spectrum of 1,3,5-Tribenzoylhexahydro-sym-triazine (in
CDC13) at -30 C.
Fig.


a
(HoC)oCOC
J J b
d d a
N NCOC(CH
L J b
dCO
bC(CH3)3
3 3
Fig .
13 .
25 MHz C NMR Spectrum of 1,3,5-Tripivaloylhexahydro-sym-trazine
(in CDCl3) at 250C.


(3.8) .
Temp .
Comp.
Triazine
C
(confor
ring
mation )
C2'C4'C6
C1
2 5a
(3.7)
58.5
133.2
-70b
(3.7x)
58.4
133.5
(3.7y)
52.9
132.9
58.3
132.4
62.7
131.8
25a
(3.8)
57.3
38.7
-iooh
(3.8x)
57.9
39.1
a _
h __
r
ci b
25 MHz spectrum. 75 MHz spectrum,
not observed even at -110 0 C.
R- substituent
o
ii
o
C6H5 r
C2 C6
c(ch3)3
C3 C5
C4
127.5
128.5
131.0
170.5
127.9
128.7
131.4
170.4
127.8
128.5
131.3
171.0
127.4
128.3
131.0
170.7
126.9
128.4
130.7
169.5
27.6
176.6
27.8
175.5
Tentative assignment. ^ Conformer (3.8)


Table 3.7
Relative A G (kcal mole ^)a for Different Conformers of Amides
(3.3 3
.8) .
Hexahydro-
Imidazolidines
Hexahydropyrimidines
sym-triazines
conformer
(3.3)
(3.4)
(3.5)
(3.6)
conformer
(3.7)
(3.8)
(a)
1.51
0.35
0.14
0.83
(x)
0.26
0
( 1 18 ) C
(0.09)
(0)
(0.59)
(0)
(0)
(b)
0
0
0
0
(y)
0
b
(0)
(0)
(0.20)
(0)
(0.26)
( c )
0.76
1.28
0.98
b
a
(0.43)
(1.01)
(0.64 )
n
a Cal ilated using the standard equation A G = -RT In K, where K is obtained
fc) c
from cue observed relative population ratios. Not observed in NMR. Values
given in parenthesis are obtained after compensating for the two distinguishable
forms of the conformer (b) in (3.3), (3.4), (3.5) and (3.6) and three
indistinguishable forms of the unsymmetrical conformer (y) in (3.7) and (3.8).


78
In imidazolidines (3.3) and (3.4), (b) was the most
stable conformer both before and after compensating for
entropy. However, the relative stability of conformers (a)
and (c) became interchanged on going from (3.3) to (3.4).
In hexahydropyrimidines (3.5) and (3.6) (b) was the
most stable conformer. However, after the correction for
entropy in (3.5), (a) becomes the most stable conformer. In
(3.6), conformer (c) is not observed at all.
In hexahydro-sym-triazine (3.7) (y) was the most stable
conformer, but after compensating for entropy, (x) became
the most stable conformer. In (3.8) conformer (y) was not
observed at all.
In conclusion, the conformer in which the two tert-
butyl groups were on the same side became either the least
stable conformer or was not observed at all.
The free energy of activation (AG^) for the barrier to
rotation around the amide C(0)-N bonds, was calculated from
the coalescence temperature observed in the 1H NMR spectra,
for the methylene protons (N-CH2-N) (table 3.8). All the
amides showed only one coalescence temperature, except for
compound (3.8) which showed only one conformer even at very
low temperature (-110C).


79
Table 3.8 Coalescence Temperatures and Free Energies of
Activation of Amides (3.3 3.8).
Amide
A v
Coalescence3
A G*
(observed
temperature
(kcal mole
exchange
in N-CH2-
N)
(Tc)
Rotational
Barrierd
(3.3)
(a)-(b)
66
303
14.7
(b)-(c)
84
14.6
(3.4)
(a)-(b)
33
248
12.3
(b)-(c)
45
12.2
(3.5)
(a)-(b)
48
298
14.7
(b)-(c) 111
14.2
( 3.6 ) c
(a)-(b)
12
177
9.0
(b)-(c)
-
-
(3.7)
(x)-(y)
36
263
13.0
99
12.5
(3.8)d
a Only one coalescence temperature was observed,
b Calculated using the equation
A G+/RTc = 22.96 + loge(Tc/A v)
c Only two conformers (a) and (b) were observed,
d Only one conformer (x) was observed.


80
Since imidazolidines and hexahydropyrimidines have
three conformers, two Av values were obtained (one between
conformers (a) and (b) and the other between (b) and (c))
and hence two free energies of activation were obtained for
each of the amides. Both values differed by + 0.5 kcal
mole .
For hexahydro-sym-triazine (3.7) four signals were seen
for the two conformers. The three equal intensity signals
at 5.26, 5.37 and 5.71 ppm were assigned to conformer (y)
and the remaining signal at 5.38 ppm was assigned to
conformer (x) (see Table 3.3). The signal at 5.37 and 5.38
ppm were almost the same, hence for the conversion of (x) to
(y) two Av values were obtained (one between 5.26 and 5.38
ppm and the other between 5.71 and 5.38 ppm). The two
calculated free energies of activation differed by + 0.5
kcal mole-'*' .
The benzamides had higher free energies of activation
than the corresponding pivalamides. The free energy of
activation for 1, 3,5-tribenzoylhexahydro-sym-triazine (3.7)
was lower (by 2 kcal mole ^) than that for the benzoyl
derivatives of imidazolidine (3.3) and hexahydropyrimidine
(3.5). This decrease in activation barrier might possibly
be due to less energetic rotation processes (discussed in
section 3.2.10) .


81
3.2.10. Mechanism of Conformer Interconversion
Amides interconvert by bond rotation, and the
interconversion pathway is unambiguous for monoamides with
only two conformers. However, there has been no mention in
the literature about the two possible directions of rotation
for the conformer interconversi on, clockwise or
anticlockwise. This possibility becomes relevant when a
chiral center is present, either at the a position to the
nitrogen or carbonyl group, or when more than one amide
group is present, such as peptides where the sequence
(individual or concerted) of rotation about the different
amide C(0)-N bonds also becomes an important factor.
Compounds like N-acyl-2-substituted saturated
heterocyclic amines [72CC788, 78JCS(P2)1157, 67CB3397,
75BCSJ553, 77BP1465, 83CJC2572] and 1,3,5-trinitroso-sym-
triazine [78JMR131] have been investigated by DNMR.
However, there has been no mention of the clockwise or
anticlockwise rotation of the amide C(0)-N and the nitroso
N-N bonds, respectively.
From band shape analysis of the exchange broadened
spectra of 1,4-dinitrosopiperazine, cis-2,6-dimethyl-l,4-
dinitrosopiperazine, trans-2,5-dimethy1-1,4-
dinitrosopiperazine and 1,3,5-trinitrosohexahydro-sym-
triazine, the possibility of correlated two bond rotations


82
has been excluded, and the spectra have been found to be
consistent with the exclusive operation of sequential
processes [78JMR131].
Correlated rotations have been found to be the
favorable process in triphenylmethyl cations [68JAM4679], in
certain substituted [2.2.2.2]paracyclophanetetraenes
[84TL4787] and in triarylboranes, methanes and amines
[76ACR26].
In triaryl cations, the most favorable mechanism for
interconversion of propeller conformers has been proposed to
be the three ring flip [68JAM4679]. In triaryl boranes,
methanes and amines, of all the possible rotations the
favorable and the lowest energy rotation has been found
theoretically to be the two ring flip, in which two rings
rotate in one direction while the third rotates in the
opposite direction [76ACR26].
For the amides (3.3-3.8) with more than two conformers
the rotations around the amide C(0)-N bonds could either be;
(A) individual (sequential), or (B) concerted (correlated)
[78JMR131].
Compounds (3.3), (3.4), (3.5) and (3.6) can exist in
three distinct conformers (a), (b) and (c) (scheme 3.2 and
3.3). For each of these amides, mechanism (A) (going along
the sides of the square) interconverts conformers (a) and


83
O
R
R O
(b) O R
(3-3) R = C6H5
(3-4) R = C(CH3)3
R (b) O R (c) R
(3 5) R = C6H5
(3 6) R=C(CH3)3


84
(b), and conformers (b) and (c), but not directly (a) to
(c). On the contrary, mechanism (B) (going along the
diagonal of the square) directly interconverts (a) and (c),
whereas (b) interconverts only with its topomer
[71AG(E)570].
For the tris-amides (3.7) and (3.8) (scheme 3.4),
mechanism (A) (going along the sides of the cube)
interconverts conformers (x) and (y), as well as changing
conformer (y) into its topomers. Mechanism (B) has two
possibilities. Firstly, when two amide bonds rotate and the
third does not (going along the diagonal of the faces of the
cube). This interconverts conformers (x) and (y) as well as
changing conformer (y) into its topomers. Secondly, when
all three amide bonds rotate (going along the diagonal of
the cube). In this case both (x) and (y) merely change into
their corresponding topomers [7lAG(E)570] (scheme 3.4).
At higher temperatures, fast rotation around the amide
C-N bonds should lead to a singlet in the NMR spectrum,
for each methylene between two hetero atoms in the ring,
irregardless of whether mechanism (A) or (B) is operating.
Higher temperature spectra indeed showed singlets for
the C-2 methylene protons of (3.3), (3.4), (3.5) and (3.6).
Similarly, the C-2, C-4 and C-6 methylene protons gave one
singlet for (3.7) and for (3.8).


R
O
(3 7) R = C6H5
(3 8) R=C(CH3)
Scheme 3.4


86
As the temperature was lowered, these signals for
(3.3-3.7) broadened, coalesced and separated as expected
into two or more peaks. Surprisingly, the signal for
compound (3.8) remained as a singlet even at -110C.
Thus it can be assumed that in compound (3.8) the
rotations around the amide C(0)-N bonds could be correlated,
that is, all three amide bonds rotate simultaneously.
However, the possiblity of three sequential rotations with
conformer (y) as a short lived intermediate in the
transitory state can not be ruled out. The two ring flip
mechanism [76ACR26] as seen in R^Z compounds, where Z
represents either B, CH or N, and R represents aryl groups,
can be extended to compound (3.8) where R represents the
pivaloyl group and Z represents the hexahydro-sym-triazine
group.
Since DNMR spectroscopy deals exclusively with the
phenomenon of site exchange among nuclei, and is
uninformative with respect to intermediate states, the
information about transitory states can not be obtained.
However, for the present system it can be extrapolated from,
results that have been obtained on triaryl boranes using
molecular mechanics [76ACR26], and simple 1,3-type
interactions [68CJC2821].


87
Considering only simultaneous (correlated) rotations
for compounds (3.3), (3.4),(3.5) and (3.6), the rotations
around the amide C(0)-N bonds could be either in the same
direction or in opposite directions. For conformers (a) and
(c) if the rotation is in the same direction then in the
transition state the R groups point in the opposite
direction. However, if the rotation is in opposite
directions then in the transitory state the R groups point
in the same direction. Thus from simple 1,3-type
interactions [68CJC2821] same side rotations would be
favored. For conformer (b) the converse is true, that is
opposite side rotations are favored.
On extending similar arguments for the different
conformers of compound (3.7) and (3.8), it is obvious that
there are three possible ways for the simultaneous
rotations: (i) one amide bond in one direction and the other
two in the opposite direction, (ii) two amide bonds in one
direction and the third in the opposite direction and (iii)
all the three amide bonds in one direction, of which (i) and
(ii) are essentially the same.
Conformer (x) which is similar to conformer (b) can not
rotate in the same direction since all the R groups will
point in the same direction in the transitory state which is
not a favorable process. Hence it has to go through either


Full Text

METALLATION, CONFORMATIONAL ANALYSIS, HYDROGEN EXCHANGE AND
REARRANGEMENT IN AMIDES
BY
RAMIAH MURUGAN
A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN
PARTIAL FULFILLMENT OF THE REQUIREMENTS
FOR THE DEGREE OF DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA

To my wife
Sutharchana Devi

ACKNOWLEDGMENTS
I would like to sincerely thank my research director,
Professor A. R. Katritzky, for his advice, guidance,
patience and support through out the last five years. I
would also like to thank Professor W. M. Jones for his
advice, support and blessings during the crucial moments of
life—my marriage.
I would like to thank Professor W. S. Brey, Professor
J. A. Zoltewicz and Dr. R. W. King for their helpful
discussions during the course of this work.
I would also like to thank very much all the members of
our research group past and present of the last five years
for their friendship, support and wonderful discussions.
Special thanks are due to Mr. Jamshed N. Lam, Mr. Steve Cato
and Dr. Gordon Rewcastle for their suggestions after reading
through the manuscript.
I would also like to thank all the faculty and staff of
the Chemistry Department for their understanding and
friendship.
Last, but not least, I would like to thank my family,
especially my daughter, for putting up with me during the
process of writing and typing *-his dissertation.
in

TABLE OF CONTENTS
page
ACKNOWLEDGMENTS iii
LIST OF TABLES vii
LIST OF FIGURES viii
ABSTRACT xi
CHAPTERS
1. GENERAL INTRODUCTION 1
1.1. Structure of the Amide Group 2
1.1.1. Geometry 2
1.1.2. Rotational Barrier 4
1.2. Preparation of Amides 5
1.2.1. Acyclic and Cyclic Amides 6
1.2.2. Vinylogous Amides 7
1.3. Reactivity of Amides 8
1.4. Scope of the Work 10
2. METALLATION OF AMIDES 11
2.1. Introduction 11
2.1.1. Dipole Stabilized Carbanions 13
2.1.2. Carboxamido Group Stabilized Carbanions. 13
2.1.3. Synergistic Effects in Stabilization.... 15
2.1.4. Aim of the Work 16
2.2. Results and Discussion 16
2.2.1. Preparation of Amides 17
2.2.2. Lithiation of 1,3-Diacylimidazolidines.. 18
2.2.3. Lithiation of 1,3-
Diacylhexahydropyr imidines 19
2.2.4. Metallation of 1, 3,5-Triacylhexahydro-
sym-triazines 20
2.3. Conclusions 21
2.4. Experimental 23
2.4.1. Reagents 23
2.4.2. Preparation of Acyl Derivatives of
Imidazolidine, Hexahydropyrimidine and
Hexahydro-sym-tr iazine 23
2.4.3. Lithiation of the Acyl Derivatives of
Imidasolidines, Hexahydropyrimidines and
Hexahydro-sym-tr iazines 26
2.4.4. Lithiation of 1,3-Dibenzoylimidazolidine 27
2.4.5. Lithiation of 1,3-
Dibensoylhexahydr opyr imidine 28

2.4.6. Lithiation of 1,3-
Dipivaloylhexahydro pyrimidine 28
2.4.7. Lithiation of 1, 3 , 5-.Tr ibenzoylhexahydro-
sym-triazine 29
2.4.8. Lithiation of 1,3,5-
Tripivaloylhexahydro-sym-triazine 30
3. CONFORMATIONAL ANALYSIS OF AMIDES 31
3.1. Introduction 31
3.1.1. Conformational Analysis Using DNMR 32
3.1.2. DNMR Studies of Monoamides 33
3.1.3. DNMR Studies of Polyamides 34
3.1.4. Aims of the Work 35
3.2. Results and Discussion 35
3.2.1. Conformers of Diamides and Triamides... 36
3.2.2. Model Compounds for Conformational
Analysis of Acyl Derivatives of Cyclic
Secondary Amines-Imidazolidine,
Hexahydropyrimidine and Hexahydro-sym-
tr iazine 37
3.2.3. 1,3-Diacylimidazolidines Conformational
Equilibria from XH NMR Spectra 43
3.2.4. 1,3-Diacylhexahydropyrimidines ^
Conformational Equilibria from h NMR
Spectra 46
3.2.5. 1,3,5-Triacylhexahydro-sym-tria^ines
Conformational Equilibria from XH NMR
Spectra 53
3.2.6. 1,3-Diacylimidazolidines Conformational
Study from JC NMR Spectra 58
3.2.7. 1,3-Diacylhexahyd ropy rimidines
Conformational Study from JC NMR
Spectra 65
3.2.8. 1,3,5-Triacylhexahydro-symytriazines
Conformational Study from c NMR
Spectra 72
3.2.9. Kinetic Parameters 72
3.2.10.Mechanism of Conformers Interconversion 81
3.3. Conclusions 88
3.4. Experimental 89
3.4.1. Instruments and Methods 89
3.4.2. Preparation of Amides 90
4. HYDROGEN EXCHANGE IN AMIDES 91
4.1. Introduction 91
4.1.1. Hydrogen Deuterium Exchange in
4-Pyridones 92
v

4.1.2.Aim of the Work 94
4.2. Results and Discussion 96
4.2.1. Hydrogen Deuterium Exchange in N-(4-
Pyridinoxymethyl )-4-pyridone 96
4.2.2. Hydrogen Deuterium Exchange in N-
(Phenoxymethyl)-4-pyridone and
N-(Arylthiomethyl)-4-pyridones 102
4.2.3. Hydrogen Deuterium Exchange in
2,6-Dimethyl-4-alkoxypyridine Model
Compounds 105
4.2.4. Hydrogen Deuterium Exchange in 4-
Alkoxypyridine Model compounds 106
4.3. Conclusions 115
4.4. Experimental 117
4.4.1. Methods and Reagents 117
4.4.2. Preparation of N-(4-pyridinoxymethyl)-
4-pyridone 118
4.4.3. Preparation of N-(Phenoxymethyl)-4-
pyridone and N-(Arylthiomethy1)-4-
pyr idone 119
4.4.4. Preparation of N-(4-Pyridylethyl)-
4-pyridone 121
4.4.5. Preparation of 2,6-Dimethyl-4-
alkoxypyri dines 121
4.4.6. Preparation of 4-Alkoxypyridine Model
Compounds 122
5. REARRANGEMENT IN AMIDES - OXYGEN TO NITROGEN
MIGRATION OF ALKYL GROUPS 124
5.1. Introduction 124
5.2. Aim of the Work 126
5.3. Results and Discussion 128
5.3.1. Attempted Rearrangements by Chemical
Methods 136
5.3.2. Elucidation of Mechanism of
Rearrangement by Physical Methods 137
5.4. Conclusions 147
5.5. Experimental 148
5.5.1. Rearrangement of Alkyl Group from
Oxygen to Nitrogen in 4-Pyridones-
General Procedure 149
5.5.2. Preparation of the N-(3 , 5-Dideutero-4-
pyridinoxymethyl)-2,6-dideutero-4-
pyr idone 149
6. SUMMARY 150
BIBLIOGRAPHY 155
BIOGRAPHICAL SKETCH 164
v 1

LIST OF TABLES
Table page
2.1 Formation of a-Lithio Species of Amides and
their Reaction with Electrophiles 22
3.1 NMR Chemical Shifts (ppm), J Values (Hz) and
Relative Population (%) of 1,3-
Diacylimidazolidines (3.3) and (3.4) 44
3.2 NMR Chemical Shifts (ppm) and Relative
Population (%) of 1,3-Diacylhexahydropyrimidines
(3.5) and (3.6) 52
3.3 â– '"H NMR Chemical Shifts (ppm) and Relative
Population (%) of 1,3,5-Triacylhexahydro-sym-
triazines (3.7) and (3.8) 57
3.4 ^C NMR Chemical Shifts (5 ppm) of 1,3-
Diacyl imidazol idines (3.3) and (3.4) 63
3.5 ^C NMR Chemical Shifts (6 ppm) of 1,3-
Diacylhexahydropyrimidines (3.5) and (3.6) 71
3.6 l^C NMR Chemical Shifts (6 ppm) of 1,3,5-
Triacylhexahydro-sym-triazines (3.7) and (3.8).... 76
3.7 Relative AG° (kcal mole ^) for Different
Conformers of Amides (3.3 - 3.8) 77
3.8 Coalescence Temperatures and the Free Energies of
Activation of Amides (3.3 - 3.8) 79
5.1 Mass Spectral Data of the Molecular Ions for the
Rearranged Products from (4.3), (4.4) and a
Mixture of (4.3) and (4.4) 147
5.2 Calculated Mass Spectral Peak Intensities and the
Difference Between the Calculated and
Experimental Mass Spectral Peak Intensities 148
vi i

LIST OF FIGURES
Figure page
1.1 Major Resonance Forms for Amides Showing
Predicted Bond Lengths (A) and Bond Angles 3
1.2 Mean Values of Bond Lengths (A) and Angles in
Crystalline Amides 3
3.1 60 MHz ^H NMR Spectrum of 1,3-
Dibenzoylimidazolidine (in CDCl^) at 25°C 39
3.2 300 MHz 1H NMR Spectrum of 1,3-
Dibenzoylimidazolidine (in CDCl^) at -30°C 40
3 . 3 60 MHz ^H NMR Spectrum of 1,3-
Dip i va loyl imi dazo 1 i d i ne (in CDCl ^ ) at 25°C 41
3 . 4 300 MHz ^H NMR Spectrum of 1,3-
Dipivaloylimidazolidine (in CDCl^) at -70°C 42
3.5 60 MHz ^H NMR Spectrum of 1,3-
Dibenzoylhexahydropyrimidine (in CDCl^) at 25°C. 48
3.6 300 MHz ^H NMR Spectrum of 1,3-
Dibenzoylhexahydropyrimidine (in CDCl-,) at
-30 °C I 49
3.7 60 MHz ^H NMR Spectrum of 1,3-
Dipivaloylhexahydropyrimidine (in CDCl-,) at
25 0C T 50
3.8 300 MHz ^H NMR Spectrum of 1,3-
Dipivaloylhexahydropyrimidine (in CDCl-,) at
-103 °C 7 51
3.9 60 MHz ^H NMR Spectrum of 1,3,5-
Tribenzoylhexahydro-sym-triazine (in CDCl-,) at
2 5 0 C T 54
3.10 300 MHz ^H NMR Spectrum of 1,3,5 —
Tribenzoylhexahydro-sym-triazine (in CDCl-,) at
-30 0C T 55
3.11 60 MHz â– ''H NMR Spectrum of 1,3,5-
Tripivaloylhexahydro-sym-triazine (in CDCl-,) at
2 5 0 C 7 56
v i i i

3.12 25 MHz 13C NMR Spectrum of 1,3-
Dibenzoylimidazolidine (in CDCl^) at 60°C 59
3.13 75 MHz ^3C NMR Spectrum of 1,3-
Dibenzoylimidazolidine (in CDCl^) at -30°C 60
3.14 25 MHz 13C NMR Spectrum of 1,3-
Dipivaloylimidazolidine (in CDCl-^) at 25°C 61
3.15 75 MHz 13C NMR Spectrum of 1,3-
Dipivaloylimidazolidine (in CDCl^) at -70°C 62
3.16 25 MHz ^3C NMR Spectrum of 1,3-
Dibenzoylhexahydropyrimidine (in CDCl^) at 60°C. 66
3.17 75 MHz ^3C NMR Spectrum of 1,3-
Dibenzoylhexahydropyr imidine (in CDCl ,) at
-40 0C f 67
3.18 25 MHz 13C NMR Spectrum of 1,3-
Dipivaloylhexahydropyrimidine (in CDCl,) at
25 0C 68
3.19 75 MHz 13C NMR Spectrum of 1,3-
Dipivaloylhexahydropyrimidine (in CDCl,) at
-100°C T 69
3.20 25 MHz 33C NMR Spectrum of 1,3,5-
Tribenzoylhexahydro-sym-triazine (in CDCl,) at
25 0C T 73
3.21 75 MHz â– '"3C NMR Spectrum of 1,3,5-
Tribenzoylhexahydro-sym-triazine (in CDCl,) at
-30 0 C T 74
3.22 25 MHz 13C NMR Spectrum of 1,3,5-
Tripivaloylhexahydro-sym-triazine (in CDCl,) at
250C . . 1 75
4.1 60 MHz H NMR Spectrum of N-(4-
Pyridinoxymethyl)-4-pyridone (in DMSO-dg) 98
4.2 60 MHz 1H NMR Spectrum of N-(4-
Pyridinoxymethyl)-4-pyridone (in NaOD-DMSO-dfi)
After Exchange at 25°C 99
4.3 60 MHz ^H NMR Spectrum of N-(4-
Pyridinoxymethyl)-4-pyridone (in NaOD-DMSO-dfi)
After Exchange at 40°C 100
IX

4.4 60 MHz 1H NMR Spectrum of 2-(4-
Pyridinoxy ) ethanol (in DMSO-dg) 109
4.5 60 MHz 1H NMR Spectrum of 2—(4—
Pyridinoxy) ethanol (in CD,ONa-CD,OD-DMSO-d.-) at
25°C 7 7 110
4.6 60 MHz 1H NMR Spectrum of 2—(4-
Pyridinoxy)ethanol (in CD.,ONa-CD,OD-DMSO-dfi )
After Exchange at 70°C Ill
4.7 60 MHz 1H NMR Spectrum of 4-(2-
Aminophenoxy)pyridine (in CD^ONa-DMSO-dg) 112
4.8 60 MHZ 1H NMR Spectrum of 4-(2-
Aminophenoxy)pyridine (in CD,ONa-DMSO-d,-) After
Exchange at 70°C 113
4.9 Base catalyzed Hydrogen Deuterium Exchange in
Different N- and O-substituted 4-Pyridones 116
5.1 Mass Spectrum of (a) N-(4-Pyridinoxymethyl)-
4-pyridone (b) N-(4-Pyridinoxymethyl)-2,6-
dideutero-4-pyridone and (c) N-(3,5-Dideutero-4-
pyridinoxymethyl)-2,6-dideutero-4-pyridone 130
5.2 60 MHz ^H NMR Spectrum of N-(4-
Pyridinoxymethyl)-4-pyridone (in DMSO-dg) 132
5.3 60 MHz ^H NMR Spectrum of the Major Product of
Rearrangment - Bis(N-4-pyridonyl)methane (in
DMSO-dg ) 133
5.4 60 MHz ^H NMR Spectrum of the Minor Product
Obtained - N-(4-Pyridyl)-4-pyridone (in DMSO-dg) 134
5.5 Mass Spectrum of the Rearranged Product Obtained
from N-( 4-Pyr idinoxymethyl)-4-pyr idone 144
5.6 Mass Spectrum of the Rearranged Product Obtained
from N-(3,5-Dideutero-4-pyridinoxymethyl)-2,6-
dideute ro-4-pyr idone 145
5.7 Mass Spectrum of the Rearranged Product Obtained
from a Mixture of N-(4-Pyridinoxymethyl)-4-
pyridone and N-(3,5-Dideutero-4-
pyridinoxymehtyl)-2,6-dideutero-4-pyridone 146
x

Abstract of Dissertation Presented to the. Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy
METALLATION, CONFORMATIONAL ANALYSIS, REARRANGEMENT AND
HYDROGEN EXCHANGE IN AMIDES
BY
RAMIAH MURUGAN
MAY, 1987
Chairman: Alan R. Katritzky
Major Department: Chemistry
Amides are known to stabilize a carbanion a to the
nitrogen. The synergistic effect of amide groups on
carbanion stability was previously unknown. Thus,
metallation of 1,3-diacylimidazolidines, 1,3-
diacylhexahydropyrimidines and 1,3,5-triacylhexahydro-sym-
triazines has been investigated. The results show no
substantial additional stabilization by the second amide
function. This might be due to steric crowding caused by
the alkyl or aryl group of the acyl units.
Little was known about restricted rotation around C-N
bonds of bis- and trisamides. A ^H and ^C variable
temperature NMR study of acyl derivatives of cyclic
secondary amines, imidazolidines, hexahydropyrimidines and
hexahydro-sym-triazines, has been performed. Conformer
populations were determined at different temperatures and
their barriers to rotation around the amide C-N bond
xi

calculated from their coalescence temperatures. A possible
mechanism of conformational interconversion was predicted
from the observed spectral change with temperature.
Base catalyzed hydrogen exchange on various N- and 0-
substituted 4-pyridones, including vinylogous amides, was
investigated. Exchange of the 2,6-protons of N-aryloxy- and
N-arylthiomethyl-4-pyridones was five times faster than that
of N-methyl-4-pyridone, indicating the participation of the
heteroatom in the exchange reaction. This participation is
very clear in N-(4-pyridinoxymethyl)-4-pyridone which
exchanges the pyridone 2,6-protons in addition to the
pyridine 3,5-protons at temperatures between 40-50°C.
Studies of model compounds such as 2—(4—
pyridinoxymethyl)ethanol, confirm this explanation.
The mechanism for the thermal rearrangement of alkyl
groups from oxygen to nitrogen in 4-pyridones had been
proposed but not proved. A mechanistic study of the thermal
rearrangement using the labelled compound N-(3,5-dideutero-
4-pyridinoxymethyl)-2,6-dideutero-4-pyridone and its
unlabelled analogue was investigated. Based on the product
ratios obtained by mass spectrometry the rearrangement was
found to be intermolecular.
XI 1

CHAPTER 1
GENERAL INTRODUCTION
For nearly two centuries the study of amides has proved
to be a rapidly expanding and intriguing area for
investigation. Not only is the amide moiety an important
constituent of many biologically significant compounds but
an understanding of its formation, properties and reactions
is essential for the dynamic growth of peptide chemistry.
This holds great promise for major discoveries essential to
human well being. Besides their biological importance,
amides are of fundamental chemical interest because of their
distinct physical and chemical properties related to the
conjugation between the nitrogen lone pair electrons and the
carbonyl rc bond. It is appropriate to survey briefly the
chemistry of amides prior to the discussion of this work.
The following discussion on amides can not hope to be
comprehensive but is intended to give some idea of the
trends observed in this work.
1

2
1.1. Structure of the Amide Group
The physical structure of the amide group has been the
subject of much recent work. Reviews on the molecular and
electronic structure [70MI1] and nuclear magnetic resonance
(NMR) properties [70CR517] summarize much of the new
developments including the shape and stereochemistry of the
amide group and spectroscopic properties.
(1.1)
1.1.1. Geometry
The molecular structure of the amide group in both the
condensed and gaseous phases is fairly well established.
However, several complicating features need to be taken into
consideration when interpreting physical measurements on
these compounds. One of these features is the partial
double bond character of the C(0)-N bond resulting from
delocalization of the nitrogen lone pair electrons into the
n-system of the carbonyl bond. There are two extreme
valence bond forms, zero conjugation (1.2a) and complete
conjugation (1.2b) as shown in Figure 1.1.

3
(1.2b)
Fig. 1.1 Major Resonance Forms for Amides Showing Predicted
Bond Lengths (Á) and Bond Angles [79MI1].
X-ray diffraction studies of crystalline amides [70MI1]
show a fairly constant geometry for the amide group. All the
heavy atoms of the amide functionality are essentially in a
plane. The mean values of the bond lengths and the bond
angles are given in (1.3) (Figure 1.2).
Fig. 1.2
1.44
o
0.95
0
Mean Values of Bond Lengths (A) and Angles in
Crystalline Amides [79MI1].
The gas phase microwave and electron diffraction
studies [70M11], [74BCSJ631] compared to X-ray diffraction

4
studies of crystalline amides show that the bond angles
remain essentiality the same but the C-0 bond length is
reduced to 1.19-1.20 Á with concomitant lengthening of the
C-N bond to 1.36-1.37 Á. This implies that there is a
greater contribution from structure (1.2a) in the gas phase
than in the solid phase.
1.1.2. Rotational Barrier
One of the most fundamental concepts in all
investigations of structure is conformational analysis. In
amides the consequence of partial double-bond character is
the existence of conformational isomers (1.4) and (1.5),
arising from the lack of free rotation about the C(0)-N
bond. The existence of these isomers has been established
by dipole moment measurement [64JAM337], infrared and Raman
spectroscopic studies [70MI1] and by nuclear magnetic
resonance (NMR).
cis (E) trans (Z)
(1.4)
(1.5)

5
Amides have been intensively studied by NMR [70CR517].
Though most of these studies have dealt with rotational
isomerization about the C(0)-N bond, considerable attention
has also been given to chemical shifts, J couplings, proton
exchange and association of the amides.
The effect of solvent and concentration on the free
energy of activation (barrier) has been studied [65JCP3320,
7OMI1]. The barrier increased with increase in solvent
polarity. Similarly, the barrier is also increased with
concentration. In both cases the ground state was expected
to be stabilized by polar solvents and by dipole-dipole
association at higher concentrations.
The effect on the barrier of substituents on both the
nitrogen and the carbonyl group has been investigated and a
number of references are available [70CR517, 74JAM2260,
67JAM4300].
1.2. Preparation of Amides
The amide linkage can be assembled in several ways, and
this is reflected in the variety of methods available for
the synthesis of amides [70MI1], their cyclic analogues the
lactams [70MI1], and the vinylogous amides the 4-pyridones
[74MI1].

6
1.2.1. Acyclic and Cyclic Amides
The most common synthetic pathway for amides themselves
is that of bond formation between a carbonyl-carbon atom and
an amino-nitrogen atom, and this is achieved by treatment of
either ammonia or a primary or a secondary amine with an
acylating agent. This yields a primary, secondary, or
tertiary amide, respectively. The other common pathway for
amide formation is the introduction of a carbonyl group into
an unsaturated amino compound, for example, partial
hydration of either a nitrile or an imidoyl derivative,
producing the primary or secondary amide, respectively. The
imidoyl derivative itself can in principle be obtained by
alkylation of the nitrile. Methods of N-alkyl or N-aryl
bond formation (other than direct replacement of the amido-
H) principally require rearrangements such as in the Schmidt
or Beckmann reactions. Synthesis of amides by formation of
the bond between an alkyl or aryl group and the carbonyl
carbon atom is the most difficult method to achieve and
requires more specific reagents such as ketenes,
isocyanates, and isocyanides. Neither direct oxidation nor
reduction of suitable precursors has wide applicability in
amide synthesis.
The synthesis of lactams (cyclic amides) generally
follows the same procedures as for acyclic amides except

7
where special factors such as ring size and ease of reaction
are concerned. Further modification of the parent lactam can
be achieved by alkylation of the nitrogen atom, and
sometimes of the carbon a to the carbonyl group using
conditions similar to those for acyclic amide alkylation.
The new method available for a-metallation of amides (a to
nitrogen) followed by electrophilic addition giving cx-
electrophile substituted amides [84CR471]. This was one of
the methods used for preparing a-metalloamine synthetic
equivalents (for further details see Chapter 2).
1.2.2. Vinylogous Amides
4-Pyridones can be prepared in two basic ways, by ring
closure reactions and by the transformation of other ring
compounds. For example, in the latter case 4-pyrones can be
transformed into 4-pyridones just by treating the
corresponding 4-pyrones with the required amines. However,
the ring closure reactions yielding 4-pyridones have many
more possiblities, using (i) a triketone or a ketoaldehyde
and ammonia [65JAM3186], (ii) 8-diketones and aromatic
Schiff bases [69BCSJl357 ] , (iii) 8-diketones and
benzonitrile [69BCSJ2389], (iv) di-l-propynyl ketone and
primary amines (60A1409J, and (v) primary and secondary
enamines, prepared from ethyl acetoacetate or 6-diketones,
with diketene [69M132].

8
1.3. Reactivity of Amides
Since all three atoms in the O-C-N chain are
potentially reactive, amides become versatile organic
compounds. This is primarily due to the delocalization of
the n electrons along the O-C-N chain. Hence the ground-
state structure of amide is a hybrid of the two resonance
forms (1.6a) and (1.6b). Although versatility often means
complexity, simplification here can be achieved by
recognizing that the majority of reactions of amides fall
into two classes. The first involves nucleophilic attack by
the oxygen atom, or occasionally by the nitrogen atom, on
either positively charged or neutral electrophilic reagents.
Here the resonance form (1.6b) is usually the more
appropriate reactive species. The second, and less common
process involves nucleophilic addition to the amide carbonyl
group of (1.6a). Most other reactions of amides such as
dehydration, elimination, deamination, etc., are sequential
to these two processes.
(1.6a)
(1.6b)

9
Because of n electron delocalization along the O-C-N
chain, the electrophilic properties of the carbonyl carbon
atom are attenuated. Hence amides are much less reactive
electrophiles than carboxylic esters. Enhancement of
polarization of the C=0 bond, either by protonation or
complexation of the oxygen atom, is usually necessary before
such a reaction can occur. Since amides are relatively weak
bases, with protonation and complexation occuring on oxygen,
they should also be feeble nucleophiles with oxygen being
the most nucleophilic site. This explains why neutral
amides react only with the more powerful electrophilic
reagents forming, initially, the O-substituted derivative.
Although N-substituted compounds are commonly isolated from
reaction mixtures, they usually originate from
rearrangements of the O-substituted derivatives and
therefore represent the thermodynamically stable product
[7OMI1] (for further details see chapter 5). Direct N-
substitution occurs only in special circumstances, either
when powerful electrophilic species such as diazoalkanes are
used or when the reaction is carried out in the presence of
a strong base, which creates the amide conjugate base as the
reactive species. For example, N-alkylation is conveniently
achieved by treating a lactam successively with sodium
hydride and alkyl halide in benzene.
Amides usually get hydrolyzed with N-acyl bond fission
to regenerate the parent carbo.vlic acid and an amine.

10
Since the initial step requires nucleophilic addition to the
carbonyl group and with amines particularly amine anions,
being poor leaving groups, it is not surprising that this
reaction is often sluggish. Water itself, for example, is
virtually inert and many amides can be recrystallized from
this solvent. Hydrolysis is much easier either under
alkaline conditions, where the more powerful HO- nucleophile
is available, or under acidic conditions, where the
protonation of the substrate assists both nucleophilic
attack by H2O and expulsion of the amine. Hydrolysis of
lactams is similar, but is generally easier because of ring
strain. However, the vinylogous amide, 4-pyridone, is quite
stable under the acidic or basic conditions normally used
for the hydrolysis of amides [74MI1].
1.4. Scope of the Work
The main objectives of this work were (i) to
investigate the synergistic effect of amide functionality on
the a-metallation of amides, (ii) to study the
conformational behavior (equilibria and kinetics) of bis¬
and tris-amides using NMR spectroscopy, (iii) to elucidate
the mechanism of the rearrangement of an imidate to an amide
in a vinylogous amide, and (iv) to study the base catalyzed
hydrogen deuterium exchange behavior of different 0- and N-
substituted vinylogous amides.

CHAPTER 2
METALLATION OF AMIDES
2.1. Introduction
The main aim of the metallation studies on amides was
for the transformation of amines into a-substituted amines.
Therefore, before discussing the objective of this work a
brief discussion is given on the different methods available
for amine transformation. The classical methods for the
preparation and transformation of amines employ (i)
nucleophilic substitution by nitrogen, (ii) nucleophilic
addition to a carbon nitrogen double bond and (iii) radical
substitution at carbon adjacent to nitrogen (scheme 2.1).
+
N Y N E
N
/ I I
N —
I
Scheme 2.1
Recent methods however, involve introducing an
activating group on the nitrogen atom and then removing the
proton from the carbon adjacent to the nitrogen using metal
11

12
alkyls, to generate a-metallo amine synthetic equivalents.
Then addition of an electrophile followed by the removal of
activating group gives the a-electrophile substituted amine
(scheme 2.2).
H
N—H
Scheme 2.2
M
+
+
t
(2.1)
A number of species have been used as activating
groups. In a recent review [84CP.471] the different groups
used for this transformation have been discussed, it also
compares the advantages and disadvantages of the different
groups which arise either from the initial introduction of
the group or removal after the transformation. In all the
groups discussed the main idea behind the activation was
their ability to stabilize an —carbanion by dipole
stabilization.

13
2.1.1. Dipole Stabilized Carbanions
A carbanion is considered to be dipole stabilized when
it is adjacent to a heteroatom which is the positive end of
a dipole (Scheme 2.2). The group Z can provide
stabilization in the transition state leading to (2.1) by
complexation with the metal of the base, by dipole
stabilization, and/or by resonance delocalization [84CR471].
Mechanism of metalation has been reviewed [84CR471]. In
addition to dipole stabilization in the lithiation of amides
by IR observation in a stopped-flow spectrometer and syn
substitution indicate, complexation plays a major role in
the reaction (see (2.2) of Scheme 2.3).
2.1.2. Carboxamido Group Stabilized Carbanions
The observation that dipole stabilized carbanions (2.2)
can be formed from amides and undergo electrophilic
substitution as shown in scheme 2.3 led to investigations of
a number of systems in which the activating function Z
contains a carbonyl group [78CR275, 79AG(E)239, 81JOC4108].
The carbonyl group should be efficiently added to and
cleaved from the amine, as well as being resistant to
nucleophilic addition by the alkyl lithium base which is
required to form the carbanionic intermediate (2.2).

14
O
R
H
sec-BuLi
â–º
CH2R
o
CHR
ch2r
Scheme 2.3
1
O" Li
I I
r/c^S^hr
I
CH2R
(2.2)
Various substituents adjacent to the carbonyl have been
investigated in different amides and the 1,1-diethylpropyl
group was found to be the best of all those considered
[81JOC4316].
Alhough a great number of acyl groups have been used in
the transformation of amines into a-substituted amines,
there has been no investigation of whether there is
synergistic effect, with two or more amide functionalities,
on the stabilization of a carbanion.

15
2.1.3. Synergistic Effects in Stabilization
Dipole stabilized anions of type RR'C NR"-X=Y are known
for a wide variety of groups X=Y [77TL1839,78CR275 ] .
However, little is known about the synergistic effect of
such stabilization in derivatives of type RC (NR'-X=Y)2.
Recently, it has been demonstrated [83T4133] that lithiation
of methylenebispyrazóles, to give metallated derivatives of
type (2.3), is indeed somewhat easier than the formation of
the corresponding monocyclic analogues (2.4).
CHLi
CH2Li
N.
n
CH2Li
(2.3)
(2.4a)
(2.4b)
The classic example of the synergistic effect has been
the work on cyclohexane-1,3-dithiane which has been greatly
exploited in organic synthesis [74JAM1807, 77JAM8262,
6 5AG(E)107 5, 6 5AG(E)1077, 75JOC231J.

16
2.1.4. Aim of the Work
The aim was to study the a-metallation behavior of a
series of compounds containing the structural feature
CH2(NRCOR')2.
2.2. Results and Discussion
Cyclic 1,3-diamines and 1,3,5-triamines were chosen as
the starting compounds and the acyl derivatives of these
compounds were prepared for the study. The acyl unit was
either a benzoyl or a pivaloyl group.
The compounds prepared for the study were - 1,3-
dibenzoylimidazolidine (2.5), 1,3-dipivaloylimidazolidine
(2.6), 1,3-dibenzoylhexahydropyrimidine (2.7), 1,3-
dipivaloylhexahydropyrimidine (2.8), 1,3,5-
tribenzoylhexahydro-sym-triazine (2.9) and 1,3,5-
tripivaloylhexahydro-sym-triazine (2.10) .
NCOR
CO
R
(2.5) R = C6H5
(2.6) R = C(CH3)3
^^NCOR
CO
R
(2.7) R = C,H.
D J
(2.8) R = C(CH3)3
CO
R
(2.9)R = C6H5
(2.10)R = C(CH3)3

17
2-.2.1. Preparation of Amides
Compounds (2.5) and (2.6) were prepared from 1,2-
ethylene diamine, formalin and benzoyl chloride or pivaloyl
chloride, respectively (scheme 2.4) . Compounds (2.7) and
(2.8) were prepared from 1,3-propanediamine, formalin and
benzoyl chloride or pivaloyl chloride, respectively (scheme
2.4). However, compounds (2.9) and (2.10) were prepared
from sym-trioxane and benzonitrile or pivalonitrile,
respectively (scheme 2.5).
H0N(CH0) NH0 + HCHO
¿ Z n Z
1.NaOH
2.RCOC1
(2.5)
R = C6H5
n=2
(2.6)
R = C(CH3)3
CM
II
c
Scheme 2.4
(2.7)
R = C,H,
6 5
n=3
(2.8)
R = C(CH3)3
n=3
RCN
h3o*
CO
R
(2.9) R = C&H5
(2.10) R = C(CH3)3
Scheme 2.5

18
2.2.2. Lithiation of 1,3-Diacylimidazolidines
Lithiation of (2.5) with lithium diisopropylamide (LDA)
in tetrahydrofuran (THF) at -78°C gave a dark brown solution
of a carbanion. Under most conditions, the very reactive
carbanion reacted with more of (2.5) acting as an
electrophile, to give the self condensation product (2.11).
Formation of (2.11) was also confirmed by the appearance of
a ketone carbonyl signal in the NMR. Addition of LDA to
a mixture of (2.5) and an electrophile in THF still gave
(2.11). Use of benzaldehyde or para-tolualdehyde as the
electrophile gave the corresponding benzyl alcohol, along
with starting material, as observed from ^H and 13C NMR
spectra, and dimers of compound (2.5) as observed from mass
spectrometry.
The use of amide (2.6) was an attempt to avoid self
condensation by the introduction of steric crowding around
the carbonyl group. However, this method failed as (2.6)
did not react with LDA, even at 0°C. Evidently the tert-
butyl group increased the steric crowding not only around
the carbonyl but also around the C-2 carbon, thus hindering
the approach of the base LDA to the C-2 hydrogen. Similar
explanations have also been given for 1,4-dibenzoyl-2,3-
dimethylquinoxalines not reacting with LDA [84JCS(Pi)1949 ] .

19
Use of less nucleophilic tert-butyl1ithium for
deprotonation instead of LDA gave the expected product after
treatment with an electrophile. By this procedure the C-2
methylated compound (2.12) was obtained from compound (2.5)
using methyl iodide as the electrophile. However, the
expected product was not isolated with compound (2.6) and
methyl iodide.
(2.11) E = COC6H5
(2.12) E = CH3
ncoc6h5
CO
2.2.3. Lithiation of 1,3-Diacylhexahydropyrimidines
Lithiation of (2.7) with LDA also afforded a dark
colored solution indicating the formation of the carbanion,
but again on work-up only the self condensation product
(2.13) was obtained. The same product (2.13) was also
obtained on adding LDA to a solution of (2.7) and an
electrophile in THF. When benzaldehyde or para-tolualdehyde
was used as the electrophile, the corresponding benzyl
alcohol was formed, as evidenced by and NMR. Use of
tert-butyl1ithium as the base with compound (2.7) gave the
expected carbanion which was trapped with Dn0 to give
(2.14) .

20
A more stable carbanion was obtained from (2.8) in THF
at -78°C with LDA, and this was trapped with D^O to give
(2.15), and with methyl iodide to give (2.16). The ^H NMR
spectrum of (2.15) showed four signals with chemical shifts
identical to the starting material (2.8), however, the
intensity of the signal for the C-2 proton was one fourth of
the signal for the C-4 and C-6 protons.
(2.13)
R = C,H-
0 j
E =
COC,H,
0 j
-^^NCOR
(2.14)
R = C6H5
E =
D
^tr^E
(2.15)
R = C(CH3)3
E =
D
CO
(2.16)
R = C(CH3)3
E =
ch3
R
2.2.4. Metallation of 1,3,5-Triacylhexahydro-sym-triazines
Low solubility of (2.9) in THF and DME below 0°C
prevented the usual procedure with LDA as base. However,
LDA addition at 25°C gave the carbanion which was trapped
with D2O to give (2.17). Metallation under polar conditions
was attempted, but treatment of (2.9) with dimsyl sodium
followed by an electrophile gave only starting material
back .

21
Lithiation of (2.10) in THF at -78°C with LDA gave the
carbanion, which was trapped with D2O to give (2.18).
(2.17) R = C6H5 E = D
(2.18) R = C(CH3)3 E = D
2.3. Conclusions
Lithiation studies with 1,3-diacylimidazolidines, 1,3-
diacylhexahydropyrimidines and 1,3,5-triacylhexahydro-sym-
triazines (Table 2.1) indicate that no substantial
additional increase in carbanion stability occurs as a
result of the introduction of the second dipolar stabilizing
group. This might be due to the fact that the conformer
favoring the double stabilization was not the predominant
conformer (discussed in chapter 3). Within the amides
studied the carbanions derived from the benzoyl derivatives
(2.5), (2.7) and (2.9) were found to be less stable, with
(2.5) being the least. However, carbanions derived from
pivaloyl derivatives (2.8) and (2.10) were found to be more
stable with (2.8) being the most. This might have been due
to the increase in steric crowding around the amide C=0
bonds, making them less susceptible for nucleophilic

22
Table 2.1
Formation of a-Lithio Species of Amides and
their Reaction with Electrophiles
Amide
Procedure3
Electrophile
Product
Yield (%)
(2.5)
A
-
( 2.11) b
90
(2.5)
B
CH3I
(2.12)
20
(2.7)
A
-
( 2.13 ) b
80
(2.7)
B
D2°
(2.14)
20
(2.8)
A
d2o
(2.15)
50
(2.8)
A
CH3I
(2.16)
80
(2.9)
A
d2o
(2.17)
65
(2.10)
A
d20
(2.18)
85
a For a description of General Procedure A and B see
Expe rimental.
b The same product was also obtained in presence of
electrophiles.

23
addition reactions. In addition, ring size was also found
to be a factor. Five-membered ring was found to be more
influenced by the steric nature of the acyl unit than the
six-membered.
2.4. Experimental
Melting points were recorded on a Bristoline hot-stage
microscope and were uncorrected. Proton NMR spectra were
recorded on a Varian EM 360L spectrometer using internal
Me^Si as the reference. IR spectra were obtained on a
Perkin-Elmer 283 B spectrophotometer.
2.4.1. Reagents
Tetrahydrofuran (THF) was refluxed over and distilled
from sodium benzophenone ketyl. n-BuLi (1.6 M in hexane)
and t-BuLi (1.7 M in pentane) were standardised by titration
[80CC87]. Diisopropylamine was refluxed over and distilled
from CaH^.
2.4.2. Preparation of Acyl Derivatives of Imidazolidines,
Hexahydropyrimidines and Hexahydro-sym-triazines
Preparation of 1,3-dibenzoylimidazolidine (2.5):
Ethylenediamine (5 g, 0.08 M) and formaldehyde (6 g,
37% solution) at 100°C were stirred for 0.5 h. The viscous

24
colorless liquid was then kept at 55-60°C. Benzoyl chloride
(20 g, 0.14 M) was added dropwise over 30 min. while
maintaining a pH of 8-10 with 10% NaOH solution (75 mL).
The mixture was then stirred for 1 h at 25°C. The 1,3-
dibenzoylimidazolidine separated out and was recrystallized
from acetone (10 g, 40%) as plates, m.p. 140°C
( lit. [ 73JHC439 ] , m.p. 140-141°C); \> ( CHB r, ) 1628 cm-1; 5
max j
(CDC13) 3.88 (4 H, s), 5.19 (2 H, s), and 7.55 (10 H, s).
Preparation of 1,3-dipivaloylimidazolidine (2.6):
Ethylenediamine (5 g, 0.08 M), formaldehyde (6 g, 37%
solution) and water (50 mL) were stirred at 100°C for 1 h.
To the viscous colorless liquid, aqueous sodium hydroxide
(32 g, 0.8 M in 120 mL of water) was added. The mixture was
cooled to between -10 and -20°C and trimethylacetyl chloride
(19.2 g, 0.16 M) added dropwise. After further stirring for
1 h, 1,3-dipivaloylimidazolidine (9 g, 50%), separated. The
crude solid was washed with water and recrystallized from
chloroform, to give prisms, m.p. 141°C (Found: C, 64.7; H,
10.1; N, 11.4. ^i3H24N2^2 rec3u;'-res C, 64.9; H, 10.1; N,
11.6%); v = (CHBr,) 1620 cm-1; 6 (CDCl,) 1.28 (18 H, s),
ma x j j
3.79 (4 H, s), and 5.05 (2 H, s).
Preparation of 1,3-dibenzoylhexahydropyrimidine (2.7):
Propane-1,3-diamine (15 g, 0.20 M), water (150 mL) and
formaldehyde (3~ , 25 mL 1 • ■r r i. r •; e m 100nC for 2 h.
Sodium hydroxide (2.5 M, 75 mL) was added at 25°C and then

25
benzoyl chloride (28 g, 0.20 M) dropwise. After stirring
for another 1 h, 1,3-dibenzoylhexahydropyrimidine (15 g,
25%) separated. Crystallization from ether-chloroform gave
plates, m.p. 94-95°C (lit.[67AJC1643], m.p. 92-96°C); v
lúa X
(CHBr3)1625 cm-1; 6 (CDC13) 1.80 (2 H, m), 3.81 (4 H, t, J=6
Hz), 5.17 (2 H, s) and 7.40 (10 H, s).
Preparation of 1,3-dipivaloylhexahydropyrimidine (2.8):
Propane-1,3-diamine (3.7 g, 0.05 M), formaldehyde (37%
25 mL) and water (150 mL) were stirred at 100°C for 2h.
Sodium hydroxide (2.5 M, 70 mL) was added at -40°C, and then
pivaloyl chloride (12.1 g, 0.10 M) was added dropwise.
After stirring the mixture at 0°C for 1 h, column
chromtography (alumina and ether) gave 1,3-
dipivaloylhexahydropyrimidine (4 g, 32%) which crystallized
as plates (from ether), m.p. 115°C (Found: C, 65.9; H,
10.0; N, 11.3. C]_4H26N2°2 requires C, 66.1; H, 10.3; N,
11.0%); v (CHBr,) 1620 cm*1; S (CDCl,) 1.28 (18 H, s),
Iua X j j
1.70 (2 H, m), 3.76 (4 H, t, J=6 Hz) and 5.31 (2 H, s).
Preparation of 1,3,5-tribenzoylhexahydro-sym-triazine (2.9):
Compound (2.9) was prepared as reported earlier
[76S467], it formed prisms from ether-chloroform, m.p. 221°C
(lit. [76S467], m.p. 220-223°C); \> (CHBr,) 1640 cm"1; 6
- max 3
(CDC13) 5.30 (6 H, s), 7.40 (15 H. s).

26
Preparation of 1,3,5-tripivaloylhexahydro-sym-triazine
(2.10) :
Compound (2.10) was prepared following the literature
method [7 6 S 4 6 7 ] for (2.9) in 45% yield as needles from
ether-chloroform, m.p. 134-136°C (Found: C, 63.8; H, 9.9; N,
12.2. ci8H33N3°3 requires C, 63.7; H, 9.7; N, 12.3 %);
v (CHBr,) 1630 cm-1; 6 (CDCl,) 1.35 (27 H, s) and 5.40 (6
Illa X j j>
H, S) .
2.4.3. Lithiation of the Acyl Derivatives of Imidazolidines,
Hexahydropyrimidines and Hexahydro-sym-triazines
General procedure A:
LDA (1 mmol) was prepared by adding dropwise di¬
isopropylamine (0.14 mL, 1 mmol) to n-butyllithium in hexane
(1 mmol) at -20°C under nitrogen. Stirring was continued
until it became cloudy (0.5 h) and then dry THF (5 mL) was
added. The mixture was then cooled to -78°C and the amide
(1 mmol) in dry THF (10 mL) was added. Stirring was
continued for 1 h at -78°C and for 10 h more at 20°C. Water
(1 mL) was added, and solvents removed at 40-50°C/20 mmHg.
The residue in methylene chloride (50 mL) was washed with
saturated aqueous NaCl (10 mL) and water (10 mL) and then
dried (sodium sulphate) and evaporated at 40-50°C/20 mmHg.
Products were separated by column chromatography.

27
General procedure B:
Similar to procedure A except that t-butyl1ithium was
used instead of LDA.
2.4.4. Lithiation of 1,3-Dibenzoylimidazolidine
1.3-Dibenzoyl-2-methylimidazolidine (2.12):
Following procedure B using 1,3-dibenzoylimidazolidine
(2.5) with methyl iodide as the electrophile gave 1,3-
dibenzoyl-2-methylimidazolidine (2.12) (20%) as needles from
CHCl3, m.p. 150 0 C (Found: C, 73.3; H, 6.3; N, 9.4.
C18H18N2°2 rec3uires C' 73.5; H, 6.1; N, 9.5 %); vmax(CHBr3)
1625 cm-1; 6 (CDC13) 8.30-7.30 (10 H, m), 5.50 (1 H, q, J=5
Hz), 4.35-3.60 (4 H, m) and 1.38 (3 H, d, J = 5 Hz).
1.2.3-Tribenzoylimidazolidine (2.11) :
1,3-Dibenzoylimidazolidine (2.5) following procedure A
self condensed to give 1,2,3-tribenzoylimidazolidine (2.11)
(90%) as needles from CHC13, m.p. 228°C (Found: C, 74.8, H,
5.5; N, 7.4. ^24H20N2^3 rec3u:'-res C, 75.0; H, 5.2; N, 7.3 %);
\> v (CHBr-J 1710, 1625 cm-1; 6 (CDCl,) 8.50-7.30 ( 15 H, m),
IUaX j j
4.00 (4 H, s) and C-2 proton not observed.

28
2.4.5. Lithiation of 1,3-Dibenzoylhexahydropyrimidine
2-Deuterio-l,3-dibenzoylhexahydropyrimidine (2.14):
1.3-Dibenzoyl-hexahydropyrimidine (2.7) following
procedure B with D2O as the electrophile gave 2-deuterio-
1.3-dibenzoylhexahydropyrimidine (2.14) (20%) as needles
from ether, m.p. 95°C (Found: C, 73.2; H, 5.8; N, 9.1.
^18H17DN2°2 rec3u^res c' 73.2; H, 5.8; N, 9.5); ^>max (CHBr)^
1625 cm-1; S (CDC13) 7.40 (10 H, s), 5.17 (1 H, s), 3.81 (4
H, t J=6 Hz), and 1.80 (2 H, m).
1.2.3-Tribenzoylhexahydropyrimidine (2.13) :
1.3-Dibenzoylhexahydropyrimidine (2.7) following
procedure A without any electrophile gave 1,2,3-
tribenzoylhexahydropyrimidine (2.13) (80%) as needles from
CHCl3, m.p. 225°C (Found: C, 75.2; H, 5.7; N, 7.0.
C25H22N2°3 re<3uires C' 75.4; H, 5.5; N, 7.0 %); ^max (CHBr^)
1715, 1628 cm-1; S (CDC13) 8.20-7.25 (15 H, m), 4.05-3.30 (4
H, m), 1.90-1.30 (2 H, m) and C-2 proton not observed.
2.4.6. Lithiation of 1,3-Dipivaloylhexahydropyrimidine
2-Deuterio-l,3-dipivaloylhexahydropyrimidine (2.15):
1.3-Dipivaloylhexahydropyrimidine (2.8) following
procedure A with D~0 as electrophile gave 2-deuterio-1,3-
dipivaloylhexahydropyrimidine 1 2.15) â– : 50 : ) as plates from

29
CH2C12, m.p. 115-116 °C (Found: C, 65.8; H, 10.1; N, 10.8.
C, . j-DN.,0-, requires C, 65.9; H, 9.8; N, 11.0 %); v
14 Z j Z Z Iücl X
(CHBr3) 1620 cm-1; 6 (CDC13) 5.25 (1 H, s), 3.75 (4 H, t,
J=6 Hz), 1.67 (2 H, m) and 1.26 (18 H, s).
1,3-Dipivaloyl-2-methylhexahydropyrimidine (2.16):
1,3-Dipivaloylhexahydropyrimidine (2.8) following
procedure A with methyl iodide as the electrophile gave 1,3-
dipivaloyl-2-methylhexahydropyrimidine (2.16) (80% based on
recovery of starting material) as needles from CHCl^, m.p.
125°C (Found: C, 67.5; H, 10.6; N, 10.3. C]_5H28N2°2 rec3ui res
C, 6 7.2; H, 10.4; N, 10.4 %); vm (CHB r,) 1630 cm-1; 6
lila X j
(CDC13) 6.90 (1 H, q, J=6 Hz), 4.40-3.40 (4 H, m), 2.00-1.40
(2 H, m), 1.29 (18 H, s) and 1.18 (3 H, d, J=6 Hz).
2.4.7. Lithiation of 1,3,5-Tribenzoylhexahydro-sym-triazine
2-Deuterio-l,3,5-tribenzoylhexahydro-sym-triazine (2.17) :
1,3,5-Tribenzoyl-hexahydro-sym-triazine (2.9) following
procedure A, but with addition of LDA to (2.9) in THF at
25°C, with D20 as the electrophile gave 2-deuterio-l,3,5-
tribenzoylhexahydro-sym-triazine (2.17) (65%) as plates from
CHCl3, m.p. 221°C (Found: C, 72.1; H, 5.3; N, 10.3.
C'>4H20DN3°3 re<3uires C' "72.0; H, 5.0; N, 10.5 %);
v , (CHBrJ 1640 cm-1; 6 (CDCl,) 7.54 (15 H, s) and 5.40 (5
m q x j
H, S) .

30
2.4.8. Lithiation of 1,3,5-Tripivaloylhexahydro-sym-
triazine
2-Deuterio-l,3,5-tripivaloylhexahydro-sym-triazine (2.18) :
1,3,5-Tripivaloylhexahydro-sym-triazine (2.10)
following procedure A with D2O as the electrophile gave 2-
deuterio-1,3,5-tripivaloylhexahydro-sym-triazine (2.18)
(85%) as plates
from
chci3,
m. p . 13 5 0 C
(Found:
C, 63.4; H,
9.6; N, 12.2.
C18H32
DN3°3
requires C,
63.5; H,
9.4; N, 12.3
WCHBr3>
1630
-1
cm ;
6 (CDC13) 5.
40 (5 H,
s) and 1.35
(27 H, s).

CHAPTER 3
CONFORMATIONAL ANALYSIS OF AMIDES
3.1. Introduction
During the last two decades, NMR spectroscopy has
developed into one of the most valuable techniques for
investigating molecular structure and stereochemistry. Not
only can NMR give the extent of equilibrium between
different conformers but can also yield information about
the dynamic behavior of the different conformers at various
temperatures. This is referred to as dynamic nuclear
magnetic resonance (DNMR). The barrier heights or the free
energy of activation of dynamic processes amenable to this
technique conveniently extend just from the border line of
20-25 kcal mole â– *", below which compounds become too unstable
to be isolated, to about 5-6 kcal mole-'*'. Restricted
rotation about the C(0)-N bond in amides is the classical
example of a rate process that can be studied by DNMR.
Activation parameters can be obtained to a greater
accuracy using total line shape analysis. However, a great
number of references are available indicating that the
31

32
coalescence temperature has been used to obtain the free
energy of activation.
3.1.1. Conformational Analysis Using DNMR
Though DNMR has been used to study all types of
compounds like substituted ethanes, amides, carbamates,
thioamides, nitrosoamines, nitriles, aldehydes and ketones,
only amides will be discussed here.
Resonance theory describes the electronic structure of
amides as a hybrid of (3.1a) and (3.1b) suggesting a certain
amount of double-bond character for the C(0)-N bond, and
thus there is a concomitant increase of the rotational
barrier over that in pure single bonds. There is a chance
t M
to observe the rate process by DNMR because R and R reside
t
in different magnetic environments (R being more shielded
than R ) [63JAM3728] in the fixed structure (3.1) but are
time-averaged on rapid rotation. This prediction was first
confirmed for dimethylformamide and dimethylacetamide
[55JCP1363].
R" R"
(3.1a)
(3.1b)

33
3.1.2. DNMR Studies on Monoamides
Of the total number of DNMR studies done on amides, the
major portion has been on monoamides. Initial studies on
dimethylformamide from different groups showed barriers from
-1
which was later attributed to factors
6.3-28.2 kcal mole
like solvent, concentration, temperature and long range
coupling in addition to instrumental errors. However, using
high field and high resolution instruments with specified
solvent and specified concentration, the difficulties are
overcome. For determination of an accurate value for the
free energy of activation, the total line shape analysis
method has always been used.
A great deal of work has been done on the effect of
substituents (both on the nitrogen and on the carbonyl
group), solvent, and concentration on the barrier. In
certain cases stable amide conformers have been isolated in
pure form [66TL4593], such as in the case of (3.2) where a
severe steric interaction raises the barrier by an
additional amount (30-32 kcal mole-1).
C(CH3>3
C3
(3.2a)
(3.2b)

34
3.1.3. DNMR Studies on Polyamides
Restriction of rotation about the C(0)-N bond of amides
has been the subject of intensive study, and the structural
influences on the equilibria and kinetics of the syn-anti
interconversion are well understood for monoamides (scheme
3.1) [68MI1]. However, the same wealth of information is
not available for polyamides. Conformational properties of
polyamides have been obtained from NMR studies of the
conformation of model diamides derived from trans-1,2-
cyclohexane carboxylic acid and different aliphatic amines
[72MM197], and piperazine or N,N'-dimethylethylenediamine
and aliphatic or aromatic carboxylic acids [69MM154].
Signals for the different conformational isomers in diamides
have been assigned using paramagnetic shifts induced by
Eu(fod)^ complexes [72JOC3434].
Scheme 3.1

35
Indeed, the investigation of DNMR spectra involving
more than two different species has been relatively limited.
NMR investigation of thiophene-2,5-dicarboxaldehyde has been
done in liquid crystals [72JCS(P2)755]. Rotational
isomerism of N,N'-dimethyl-a,w-bis(benzoylamino)alkanes
[84JCS(P2)1089] and 1,3,5-trinitrosohexahydro-l,3,5-triazine
[69RC1687] has been studied using variable temperature
NMR spectroscopy. Stereoisomerization of N,N'-diacetyl-
N,N'-dimethylhydrazine using variable temperature ^H NMR
spectroscopy has also been studied and a discussion about
the mechanism of stereoisomerisation was given [75GCI569].
3.1.4. Aims of the work
The goals of this work were (i) to elucidate the
equilibria on some cyclic model systems of bis- and tris-
amides, (ii) to calculate the rotational barriers and (iii)
to deduce the mechanism of rotation based on the spectral
behavior at various temperatures.
3.2. Results and Discussion
The model systems chosen for the bis-amide studies were
1,3-diacylimidazolidines (3.3) and (3.4) and 1,3-
diacylhexahydropyrimidines (3.5) and (3.6). For the tris-
amide studies it "as 1,3 , 3-1: Tcvlhexahydro-sym-triazines
(3.7) and (3.8) .

36
(3.3) R = C,Hc
b j
(3.4) R = C(CH3)3
(3.5) R = C.H,
6 5
(3.6) R = C(CH3)3
ROCN NCOR
R
CO
(3.7) R = C,H,
6 5
(3.8) R = C(CH3)3
ROCN NCOR
3.2.1. Conformers of Diamides and Triamides
A single amide bond can exhibit two conformations.
Similarly two amide bonds together can exhibit four
conformations and three amide bonds together can exhibit
eight conformations. However, on deriving these amides by
acylating cyclic di- and triamines (keeping the acyl groups
the same) some of the conformers become indistinguishable.
For example, in compounds (3.3), (3.4) (3.5) and (3.6)
although there are four possible conformers only three are
distinguishable. Furthermore, for compounds (3.7) and (3.8)
of the eight possible conformers, only two of them are
distinguishable. The indistinguishable conformers are
referred to as topomers [ 71G ■ f •“0 ) .

37
Distinguishing the different conforraers experimentally
(in this case using NMR) was not an easy task. To diagnose
this, model compounds were developed to assign chemical
shifts to the different conformations of the compounds (3.3-
3.8) .
3.2.2. Model Compounds for Conformational Analysis of Acyl
Derivatives of Cyclic Secondary Amines - Imidazolidine ,~
Hexahydropyrimidine and Hexahydro-sym-triazine
On investigating the different conformers of all the
compounds, the methylene group between the two nitrogen
atoms was found to be either between the two carbonyl
oxygens, or between the R groups of the acyl units or
between one carbonyl oxygen and one R group of the acyl
unit. Although it was known already that the N-alkyl group
syn to the carbonyl is always more shielded than when it is
anti [63JAM3728], model compounds were still used for the
signal assignments.
Since pivaloyl and benzoyl derivatives of amines were
used, comparison was done with similar model systems.
1,3,3-Trimethyl-2-piperidone (3.9) showed the N-methyl
(necessarily syn to the carbonyl) at delta 3.00 ppm

38
[75CJC1682]. By analogy, the syn-methyl in N,N-
dimethylpivalamide (3.10) has been assigned to the signal at
2.96 ppm and the anti-methyl to the signal at 3.21 ppm in
the 1H NMR spectrum obtained at -40°C.
(3.9)
(3.11)
(3.10)
R = C(CH~),
3 j
I
(3.12)
R = C.H,
H„C^''Nsvu
6 5
3 CH3
(3.13)
R = H
(3.14)
R = CH3
In the phenyl series, the model compound N-methyl-
1,2,3,4-tetrahydro-2-isoquinolone (3.11) showed the
(necessarily syn) N-CH^ signal at delta 3.20 ppm [82T539]
N,N-Dimethylbenzamide (3.12) at -26.6°C in CB^Bl^ showed
signals at delta 3.38 and 3.53 ppm for the N-CH^ protons
[62JPC540] and in comparison with (3.11), the signal at
delta 3.38 ppm was assigned to methyl syn to the carbonyl

9
Fig . i
*t 1 r
8 7 6
-i 1 r
3 2 1
0
.i 60 mHz ^H NMR Spectrum of 1,3-Dibenzoylimidazolidine (in CDCl^) at
2 5 0 C .

T
3
2
1
Fig .
300 MHz 1H NMR Spectrum of 1,3-Dibenzoylimidazolidine (in CDCl^) at
- 3 0 0 C .

1 1 1 1 1 1 1 I I I
98 76 543 210
60 MHz ^H NMR Spectrum of 1,3-Dipivaloylimidazolidine (in CDCl^) at
2 5 0 C .
Fig.

e
c
Fig .
500 MHz ;H NMR Spectrum of 1,3-Dipivaloylimidazolidine (in CDClj) at
-7 0 0 C .

43
In the case of spectra the signals were assigned to
different conformers by referring to model compounds (3.13),
(3.14) and particularly (3.12), in which the N-methyl
carbons syn to the carbonyl group had been always shielded
(31.1, 34.5, 35.2 ppm, respectively) compared to the anti N-
methyl carbons (36.2, 37.5, 38.9 ppm, respectively) [78MI1].
In addition, the intensity and the number of signals were
also used for the signal assignments.
An interesting feature of these results from the model
systems considered both for proton and carbon, is that
groups syn to the carbonyl oxygen are always shielded over
the groups anti to it.
3.2.3. 1,3-Diacylimidazolidines Conformational Equilibria
from h NMR Spectra
At 25°C for compound (3.3) (figure 3.1) and for (3.4)
(figure 3.3), a 2H singlet for 2-CH2 and a 4H singlet for
4,5-C2H4 were observed, which demonstrated rapid rotation
about both amide links (Table 3.1). As the temperature was
lowered, these peaks broadened and split and, below -30°C
for (3.3) (figure 3.2) and below -80°C for (3.4) (figure
3.4), separate signals were observed for each of the three
conformers (Table 3.1). In addition to the above, (3.3)
shows signals for the phenyl protons at 7.56 ppm as a broad
singlet and (3.4) for the t-Bu at 1.28 ppm as a singlet. On

Table
3.1 ^H NMR Chemical Shifts (ppm),
1,3-Diacylimidazolidines (3.3)
J Values
and (3.
(Hz) and
4)
Relative
Population
(%) for
Temp.
compound
2-CH
l2
popn.
4
,5-
c2h
4
popn
R
°C
(conforme r)
6
I
(%)
8
M
J
I
(%)
8 M
I
2 5a
(3.3)
5.20
2.00b
-
3.88
S
-
4.00
-
7.56 s
10.44
- 3 0 C
(3.3a)
4.95
0.07
3.5
4.03
s
-
0.21
5.3
7.50 m
10.54
(3.3b)
5.17
1.60
80.0
4.03
t
7
3 . 18
79.5
3.82
t
7
(3.3c)
5.45
0.33
16.5
3.79
s
-
0.61
15.2
2 5 1
(3.4)
5.15
2.00b
-
3.85
s
-
4 .00
-
1.28 s
18.00
-7 0'
(3.4a)
5.01
0.55
27.5
4.05
s
-
1.23
30.8
1.24d s
e
(3.4b)
5.12
1.40
70.0
3.93
t
6
2.71
67.7
1.28d s
e
3.86
t
6
(3.4c)
5.27
0.05
2.5
3.72
s
-
0.06
1.5
1.31d s
e
M = multiplicity; t
= triplet; s
= singlet; m
= multiplet.
J =coupling constant
( Hz ) ;
ci b
I = intensity. L 60 MHz spectrum. Intensity reference standard. For low temperature
spectra, total intensity of 2.0 for these peaks taken as standard. c 300 MHz spectrum,
d e
Tentative assignment. Total intensity 18.8, individual intensities not measurable due
to overlap.

45
cooling, these peaks broaden and reappear respectively as a
multiplet near 7.50 ppm for (3.3) and as three singlets at
1.31, 1.28 and 1.24 ppm for (3.4).
Comparing the model compounds for chemical shift
assignment in conformers (a), (b), and (c) (scheme 3.2) of
(3.3) and (3.4), we expect the protons to be at
highest field in (a) where they are syn to both carbonyls
and at lowest field in (c) where they are anti to both
carbonyls. Conversely, conformer (a) should show a singlet
at lower field for the 4,5^2^ protons than the singlet for
(c). In the unsymmetrical conformer (b), the 4,5^2^
protons should display an AA'XX' pattern, with the chemical
shift for A nearer to that of conformer (c) and of X nearer
to conformer (a). The assignments in Table 3.1 followed
these considerations.
The relative proportions of the three conformers
obtained from the relative signal intensities are also shown
in Table 3.1. Those for the 2-CH2 indicate (a):(b):(c) =
3.5:80.0:16.5% for (3.3) and (a):(b):(c) = 27.5:70.0:2.5%
for (3.4). Those for the 4,5-CH2 indicate (a):(b):(c) =
5.3:79.5:15.2% for (3.3) and (a):(b):(c) = 30.8:67.7:1.5%
for (3.4). Since the 2-CH-, signals are separate singlets

46
for the different conformers, they are considered to be more
reliable for isomer proportion deduction than the 4,5-CH2
signals, for which the singlet for the conformers (a) and
(c) overlaps with the AA'XX' double triplets from conformer
(b) .
Rationalizing our results it seems that in the
equilibrium for (3.3) at -30°C, conformer (b) was favored
over (a) by 1.51 kcal mole-1 and over (c) by 0.76 kcal
mole ^. However, for (3.4) at -70°C, conformer (b) was
favored over (a) by 0.35 kcal mole 1 and over (c) by 1.28
kcal mole-1.
3.2.4. 1,3-Diacylhexahydropyrimidines Conformational
Equilibria from h NMR Spectra
At 25°C compounds (3.5) (figure 3.5) and (3.6) (figure
3.7), showed a 2h singlet for the 2-CH2 protons, which
demonstrates that, just as for (3.3) and (3.4), rapid
rotation occurs about both amide links (Table 3.2). At low
temperatures for (3.5) (figure 3.6) the peaks broaden and
split and at -30°C separate signals were observed for each
of the three conformers. However, for (3.6) (figure 3.8) at
-103°C separate signals were seen only for two conformers.

47
Signal assignments were based on model compounds
discussed earlier. The protons gave an additional signal
around 1.9 ppm. The assignments of Table 3.2 follow these
considerations. For example the assignments for the 2-CH2
protons of (3.5) and (3.6) are as follows; at -30°C, (3.5)
showed three signals for the 2-CH2 protons. Using the rule
derived from model compounds that protons syn to the
carbonyl oxygen were shielded, the one to the lowest field
was assigned to (3.5c), the one to the highest field to
(3.5a), and the middle one to (3.5b) (scheme 3.3). On
similar grounds, of the two signals observed for compound
(3.6), the most intense signal was assigned to (3.6b) and
the remaining one being at higher field than that of (3.6b),
was assigned to (3.6a). Assignments for the C^-Cg protons
were made similarly (Table 3.2).
Relative signal intensities and the isomer proportions
from the 2-CH2 signals are shown in Table 3.2. For (3.5),
(a):(b);(c) = 39.7:53.3:7.0% and for (3.6), (a):(b):(c) =
8:92:0%. From the 4,6-CH2 signals, it was not possible to
derive conformer proportions because of additional coupling
to the 5-CH2, and overlapping of signals.

Fig. i . '3
óO MHz ^H NMR Spectrum of 1,3-Dibenzoylhexahydropyrimidine (in C 3)
at 250C.

4
3
^ . O
3Ü0 MHz ^H NMR Spectrum of 1,3-Dibenzoylhexahydropyrimidine (in CDCl,)
at - 30 °C.
Fig .

TMS
( ch3 )£OCN^/ ncoc (ch3 ) 3
d
chci3
1 1 r-
9 8 7
6
T
4
3
T
2
1
0
Fig.
60 MHz lH NMR Spectrum of 1,3-Dipivaloylhexahydropyrimidine (in CDC13)

i 300 MHz 1H NMR Spectrum of 1,3-Dipivaloylhexahydropyrimidine (
CD3COCD3) at -10 3 0 C.
Fig.

Table 3.2 NMR Chemical Shifts (ppm) and Relative Population (%) for 1,3-Diacyl-
hexahydropyrimidines (3
.5) and
(3.6)
Temp.
compound
2-CH2
popn.
4(6)-CH2
5-CH
2
R
°C
(conforme r)
MM)
I
(%)
MM) I
S(M)
I
MM)
I
2 5a
(3.5)
5.17 ( s )
2.00b
-
3.81(t)C 4.00
1.80(m)
2.02
7.4 0 ( m)
10.4
1
OJ
o
Cl
(3.5a)
5.04(s)
0.79
39.7
3.95(m) 4.30e
1.84f(m)
2.01e
7.34(m)
10.5e
(3.5b)
5.20(s)
1.06
53.3
3.95(m)
1.9 3 f ( m)
-
7.3 4 ( m)
-
3.66(m)
(3.5c)
5.57(s)
0.14
7.0
3.66(m)
1.8 4 f ( m)
-
7.34(m)
-
2 5a
(3.6)
5.31(s)
N>
O
O
17
-
3.76(t)C 4.00
1.7 0 ( m)
2.03
1.28(s )
18.00
-10:
(3.6a)
4.99(s)
0.16
8.0
4 . 41(m) 4.40e
1.78(m)
2.04e
1.16(s )
19.0e
(3.6b)g
5.0 3(s)
1.84
92.0
4 . 41 ( m )
1.78(m)
-
1.16(s)
-
M = m
Ltiplicity;
t = triplet; s =
singlet; I = intensity
. 3 60 MHz
spectrum. b Intensity
refer?nce standard; at low temperature total intensity for these peaks taken as 2.0.
c
Being at low field (60 MHz) this signal is seen as an apparent triplet with J = 6 Hz.
d 0 f
300 MHz spectrum. Individual intensities not measurable due to overlap. Tentative
assignment. g No peaks for (3.6c) observed.

53
The equilibrium at -30°C for (3.5) favored conformer
(b) over (a) by 0.14 kcal mole-"'" and conformer (b) over (c)
by 0.98 kcal mole ^. However, for (3.6), the equilibrium at
-103°C favored conformer (b) over (a) by 0.83 kcal mole-'*'.
3.2.5. 1,3,5-Triacylhexahydro-sym-triazines Conformational
Equilibria from 1H NMR Spectra
At 25°C compounds (3.7) (figure 3.9) and (3.8) (figure
3.11) showed a 6H singlet for the three CH2 protons,
demonstrating rapid rotation about all three amide links.
As the temperature was lowered the peaks broadened and
split, and at -30°C separate signals were observed for (3.7)
(figure 3.10) for each of the two conformers. However, for
(3.8) only one conformer (x) was observed even for spectra
recorded as low as -110°C using acetone-dg as the solvent
(Table 3.3) (scheme 3.4).
Signal assignments shown in Table 3.3 follow the same
rules observed for signal assignment for imidazolidines
(3.3) and (3.4), i.e., the protons syn to the carbonyl
oxygen were shielded. The methylene protons for (3.7) at
-30°C showed four singlets, of which three signals were of

b
a
TMS
T I 1 —I 1 1 1 1 1 f
9 8 76 54 3 210
60 MHz LH NMR Spectrum of 1,3,5-Tribenzoylhexahydro-sym-1riazine (in
CDC1 , ) at 25°C.
Fig.
, . 9

5 5
Fig. 3.10 300 MHz iH NMR Spectrum of 1,3,5-Tribenzoyl-
hexahydro-sym-triazine (in CDCl^) at -30°C.

a
(H3C)3COC
NCOC(CH3)3
c(ch3)3
b
en
(T>
CHC1 -
A-
J
T~ | | 1 1 r
9 8 7 6 5 4
1 1 r
3 2 1
Fig. . . II
60 MHz ^H NMR Spectrum of 1,3,5-Tripivaloylhexahydro-sym-triazine (in
CDC1,) at 25°C.
j
0

cr 3
Table 3 . 3
^H NMR Chemical Shifts (ppm) and Relative Population (%) for 1,3,5-
Triacylhexahydro-sym-triazines (3.7) and (3.8)
Temp.
compound
2,4,6
-ch2
popn.
N-substit.
°C
(conformer)
6 ( M )
I
(%)
MM)
I
2 5a
(3.7)
5.30(s)
os
O
O
cr
-
7.4 0 ( s )
15.2
u
o
m
1
(3.7x)
5.38(s )
2.19
36.5
7.4 0 ( m )
d
(3.7y)
5.26(s)
3.81e
63.5
7.4 0 ( m)
d
5.37(s )
5.71 ( s )
2 5a
(3.8)
5.4 0 ( s )
6.00b
-
1.35(s)
27.4
-100'
(3.8x)f
5.39(s)
6.00
100.0
1.3 3 ( s )
27.3
= multiplicity; s = singlet; m = multiplet; I = intensity. a 60 MHz spectrum.
C d
standard reference intensity. 300 MHz spectrum. Total intensity 15.1;
individual intensities not measurable due to overlap. e Total intensities of the
three signals together. ^ Signals for (3.8y) not observed, even at -110°C.

58
equal intensity corresponding to conformer (3.7y). The one
remaining signal was assigned to conformer (3.7x), in which
all methylene protons are identical.
Relative signal intensities and the isomer proportions
from the 2,4,6-CH2 signals are shown in Table 3.3. For
(3.7) (x):(y) = 36.5:63.5% and for (3.8) (x):(y) = 100:0%.
For the equilibrium at -30°C (3.7) favored conformer
(y) over (x) by 0.26 kcal mole ^. However, (3.8) was found
to exist exclusively in the (x) conformer.
3,2.6. 1,3-Diacylimidazolidines Conformational Study from
ÓC NMR Spectra
The 75 MHz spectra of (3.3) (figure 3.12) at 25°C were
near coalescence, and showed broadened lines for C-2, C-4
and C-5 which became sharp singlets at 60°C; (3.4) (figure
3.14) showed sharp singlets for these carbons at 25°C. At -
30°C for (3.3) (figure 3.13) and -70°C for (3.4) (figure
3.15), signals were seen for the individual conformers
(Table 3.4). The signals were assigned to different
conformers based on the model compounds discussed earlier
(see section 3.2.2).

a
a
H,-C,OCNv
5 6
NCOC,H,
b 5
—1 1 1 ' ' r
160 140 120 100 80 60 40
o . 12
Fig.
25 MHz NMR Spectrum of 1,3-Dibenzoylimidazolidine (in CDCl^) at
60 0 C .
20
0


a
( H3C ) 3COCN^/ ncoc ( CH3
3
I 1 1 1 1 r
160 140 120 100 80 60
~i '
40 20 0
Fig. 3 L 4
25 MHz NMR Spectrum of 1,3-Dipivaloylimidazolidine (in CDCl3> at
25°C .

Fig .
t 1 1 1 1 1 r
180 150 120 90 60 30 0
L5 75 MHz 13C NMR Spectrum of 1,3-Dipivaloylimidazolidine (in CDCl3) at
-7 0 0 C.

Table 3.4 13C NMR Shifts (&, ppm) for 1, 3-Diacylimidazolidines (3.3) and (3.4).
Comp .
Temp.
Confor¬
Imidazolidine
R-substituent
o
ii
u
no .
°C
mation
ring
C
6H5 or
c(ch3)3
C2
C4
C5
C1
C2'C6a
c c a
L3'L5
C4
(3.3)
50b
62.0
45.7
45.7
135.1
127.1
128.4
130.6
168.8
2 5b
c
c
c
134.8
127.0
128.3
130.5
168.7
-30d
(3.3a)
60.4
48.0
48.0
134.4a
126.9
127.3
130.8a
e
(3.3b)
62.3
44.2
46.5
134.6a
127.0
128.5
130.9a
169.4
168.8
(3.3c)
e
42.8
42.8
134.7a
127.2
128.7
131.Ia
168.6
(3.4
2 5b
62.3
45.5
45.5
38.8
27.2
175.8
-70d
(3.4a)
61.7
46.6
46.6
38.7a
26.80a
175.3
(3.4b)
63.7
46.5
43.6
38.6a
26.74a
175.8
175.7
(3.4c)
e
e
e
38.5a
26.70a
e
Tentative assignment. b 25 MHz spectrum. c one broad unresolved peak. d 75 MHz spectrum.
Not obse rved.

64
For compound (3.3) conformers (3.3a), (3.3b) and (3.3c)
showed a total of four signals due to C-4 and C-5 carbons.
Of these, the two intermediate chemical shifts were of equal
intensity and were unambiguously assigned to the conformer
(3.3b). From the rule stated above, that the carbon syn to
the carbonyl oxygen was shielded, the medium intensity peak
at 48.0 ppm was assigned to (3.3a) and the low intensity
peak at 42.8 ppm to (3.3c). (These assignments are in fair
agreement with the conformer populations deduced from the
proton spectra). For the C-2, only two signals were
obtained; the peak of higher intensity was assigned to
(3.3b) and the other one being at a higher field than that
for (3.3b) was assigned to (3.3a). The expected peak for
the least populated isomer (3.3c) was not observed.
Compound (3.4) displayed only three peaks for the 4,5-
carbon atoms: two of equal and high intensity were
unambiguously assigned to (3.4b); the less intense peak at
lower field was assigned to (3.4a), again based on the rule
that the carbon syn to the carbonyl oxygen was shielded.
With conformer (3.4c) being the least populated, (cf proton
spectra) its peaks were not observed. Similarly, for the
C-2 carbon, peaks were found only for (3.4a) and (3.4b).

65
i 3
The C chemical shift assignments of the phenyl group
in (3.3) and the t-butyl group in (3.4) were based on the
difference in intensity of the signals, the off-resonance
spectra, and for R=CgH^ comparison with the spectrum of
(3.12). In compound (3.3), the C-2,6 and C-3,5 carbons of
the phenyl ring showed relatively intense signals (doublets
in off-resonance spectrum), and C-l a low intensity signal
(singlet in off-resonance spectrum). In compound (3.4), the
quaternary carbon of C(CH^)^ showed a low intensity signal
at ca. 38 ppm, and the methyl groups gave a very intense
signal at higher field. The lowest field signal in the
spectra of compounds (3.3) and (3.4) was that of the
carbonyl carbons. The low temperature spectrum, of each of
the compound showed three C=0 signals of which the two of
equal intensity were assigned to the two carbonyl groups in
conformer (b). The signal due to the least populated
conformer, (a) in (3.3) and (c) in (3.4), was not observed.
3.2.7., 1,3-Diacylhexahydropyrimidines Conformational Study
from NMR Spectra
The 75 MHz spectrum of (3.5) (figure 3.16) at 25°C was
near coalescence and showed broadened signals for C-2, C-4,
C-5 and C-6 which became sharp signals at 60°C; (3.6)
(figure 3.18) shows sharp signals for the ring carbons at

a
—, 1 1 1 1 1—
200 180 160 140 120 100
1 ' 1 r
80 60 40 20
0
Fig. 3.L6 25 MHz NMR Spectrum of 1,3-Dibenzoylhexahydropyrimidine (in
CDCl^) at 60 °C.

a
er^Se
H5C^|fN^fK]^C6H5
0 £ 0
HsW
o
0 c
r y
H5C6 C6H5
IKImyW
g
M^MW/tyWiiiWWillllilH^^
“I
0
180
160
140 120
100 80
60
40
20
L7 75 MHz ^C NMR Spectrum of 1,3-Dibenzoylhexahydropyrimidine (in
CDCl^) at -400C.
Fig.

b
(H3C ) 3COC NCOC ( CH3 ) 3
f e f
i i i 1 1 1 1 1 1 1 r
200 180 160 140 120 100 80 60 40 20 0
L8 25 MHz 13C NMR Spectrum of 1,3-Dipivaloylhexahydropyrimidine (in
CDC1 ,) at 25°C.

Fig. ' L9 75 MHz 13C NMR Spectrum of 1,3-Dipivaloylhexahydropyrimidine (in
cd3cocd3) at -100°C.

70
25°C. At -40°C signals for the individual conformers
appeared in the spectrum of (3.5) (figure 3.17). However,
for (3.6) at -70°C separate signals were seen only for two
conformers as was described above for the spectrum
(figure 3.19).
Signals were assigned by reference to model compounds
as discussed earlier. The C-5 carbon gave an additional
signal around 24.5 ppm. The assignments of Table 3.5 follow
these considerations. An illustration for the C-2 carbons
of (3.5) and (3.6) is as follows; at -40°C (3.5) showed
three signals for the C-2 carbon. Using the rule that the
carbon syn to the carbonyl was the most shielded, the most
downfield signal was assigned to (3.5c), the most upfield
signal to (3.5a) and the remaining one to (3.5b). Based on
similar considerations, of the two signals seen for the C-2
carbon of (3.6), the most intense was assigned to (3.6b).
Since the remaining one was at a higher field than (3.6b),
it was assigned to (3.6a). These assignments agree with
conformer populations deduced from the proton spectra.
Assignments for the C-4-C-6 carbons were made similarly.

Table 3.5
C NMR Shifts (&, ppm) for 1,3-Diacylhexahydropyrimidines (3.5) and (3.6)
13
Temp.
Comp.
Pyrimidine Ring
R-Substituent
o
ii
o
°C
(confo-
C2
C4
C5
C6
C
6H5 or
c(ch3)3
mation)
C1
C2 ' C6
C3'C5
C4
25a
(3.5)
59.8
44 . 3
24.9
44 . 3
133.2
127.4
128.4
130.3
170.1
_C
O
1
(3.5a)
52.8
47 . 3
25.2C
47.3
134 . 3C
127.2°
128.4°
130.3°
169.9
(3.5b)
58.2
47.0
25.2C
41.8
134.0°
127.0°
128.3°
130.2°
170.6
133.9
126.8
169.8
(3.5c)
62.8
41.7
24.0C
41.7
133.3°
126.5°
128.1°
130.0°
d
25a
(3.6)
58.3
44.9
24.9
44.9
38.7
28.00
176.8
-70b
(3.6a)
58.4
47.1
25.6
47.1
39.1
28.2°
176.1
(3.6b)d
58.6
47.1
25.6
43.3
39.1
28.3°
176.1
28.1°
175.8
a 25
MHz spectrum
. b 75
MHz
spectrum
c
Tentative
assignment. d
Conformer
(3.6c) not
observed.

72
3.2.8. 1,3.5-Triacylhexahydro-sym-triazines Conformational
Study from C NMR Spectra
The 75 MHz spectra of (3.7) (figure 3.19) and (3.8)
(figure 3.21) at 25°C showed signals for the three methylene
carbons at 58.5 and 57.3 ppm, respectively. At -70°C for
(3.7) (figure 3.20), signals were seen for the individual
conformers. However, for (3.8) only one conformer (x) was
observed even at a temperature as low as -110°C. This was
the same result as seen in its ^H spectrum. The signal
assignments for the two conformers (x) and (y) of compound
(3.7) and one conformer (x) of compound (3.8) were also
based on the model compounds discussed earlier. The signal
assignments are shown in Table 3.6.
3.2.9. Kinetic Parameters
The kinetic parameters obtained were the free energy
difference between conformers and the free energy of
activation for the barrier to rotation around the amide
C(0)-N bonds. The free energy differences (AG°) were
calculated from the population ratios (of their C-2
methylene protons signals) obtained for each of the amides
from their ^H NMR spectra and are given in table 3.7. Free
energies (AG°), which are compensated for the entropy factor
(for the topomers of unsymmetrical isomers), are also given
in table 3.7.

3 . 20
25 MHZ 13c NMR Spectrum of 1,3,5-Tribenzoylhexahydro-sym tnazine
CDC1^) at 25°C.
( in
Fig .

180 160 140 120 100 80 60 40 20 0
3.21
1 3
7b MHz C NMR Spectrum of 1,3,5-Tribenzoylhexahydro-sym-triazine (in
CDC13) at -30 °C.
Fig.

a
(HoC)oCOC
J J b
d d a
N NCOC(CH
L J b
dCO
bC(CH3)3
3 3
Fig .
7
13 .
25 MHz C NMR Spectrum of 1,3,5-Tripivaloylhexahydro-sym-tríazine
(in CDCl3) at 250C.

(3.8) .
Temp .
Comp.
Triazine
°C
(confor¬
ring
mation )
C2'C4'C6
C1
2 5a
(3.7)
58.5
133.2
-70b
(3.7x)
58.4
133.5C
(3.7y)
52.9
132.9C
58.3
132.4C
62.7
131.8C
25a
(3.8)
57.3
38.7
-iooh
(3.8x)
57.9
39.1
a _
h __
r
ci t)
25 MHz spectrum. 75 MHz spectrum,
not observed even at -110 0 C.
R- substituent
o
ii
o
C6H5 °r
C2 ’ C6
c(ch3)3
C3 ' C5
C4
127.5
128.5
131.0
170.5
127,9C
128.7C
131.4C
170.4
127,8C
128.5C
131.3C
171.0
127.4C
128.3°
131.0C
170.7
126.9C
128.4C
130.7C
169.5
27.6
176.6
27.8
175.5
Tentative assignment. ^ Conformer (3.8)
-j

Table 3.7
Relative A G° (kcal mole ^)a for Different Conformers of Amides
(3.3 - 3
.8) .
Hexahydro-
Imidazolidines
Hexahydropyrimidines
sym-triazines
conformer
(3.3)
(3.4)
(3.5)
(3.6)
conformer
(3.7)
(3.8)
(a)
1.51
0.35
0.14
0.83
(x)
0.26
0
( 1 . 18 ) C
(0.09)
(0)
(0.59)
(0)
(0)
(b)
0
0
0
0
(y)
0
b
(0)
(0)
(0.20)
(0)
(0.26)
( c )
0.76
1.28
0.98
b
a
(0.43)
(1.01)
(0.64 )
n
a Ca ' ilated using the standard equation A G° = -RT In K, where K is obtained
fc) c
from cue observed relative population ratios. Not observed in NMR. Values
given in parenthesis are obtained after compensating for the two distinguishable
forms of the conformer (b) in (3.3), (3.4), (3.5) and (3.6) and three
indistinguishable forms of the unsymmetrical conformer (y) in (3.7) and (3.8).

78
In imidazolidines (3.3) and (3.4), (b) was the most
stable conformer both before and after compensating for
entropy. However, the relative stability of conformers (a)
and (c) became interchanged on going from (3.3) to (3.4).
In hexahydropyrimidines (3.5) and (3.6) (b) was the
most stable conformer. However, after the correction for
entropy in (3.5), (a) becomes the most stable conformer. In
(3.6), conformer (c) is not observed at all.
In hexahydro-sym-triazine (3.7) (y) was the most stable
conformer, but after compensating for entropy, (x) became
the most stable conformer. In (3.8) conformer (y) was not
observed at all.
In conclusion, the conformer in which the two tert-
butyl groups were on the same side became either the least
stable conformer or was not observed at all.
The free energy of activation (AG^) , for the barrier to
rotation around the amide C(0)-N bonds, was calculated from
the coalescence temperature observed in the 1H NMR spectra,
for the methylene protons (N-CH2-N) (table 3.8). All the
amides showed only one coalescence temperature, except for
compound (3.8) which showed only one conformer even at very
low temperature (-110°C).

79
Table 3.8 Coalescence Temperatures and Free Energies of
Activation of Amides (3.3 - 3.8).
Amide
A v
Coalescence3
A G*
(observed
temperature
(kcal mole
exchange
in N-CH2-
N)
(Tc)
Rotational
Barrier^3
(3.3)
(a)-(b)
66
303
14.7
(b)-(c)
84
14.6
(3.4)
(a)-(b)
33
248
12.3
(b)-(c)
45
12.2
(3.5)
(a)-(b)
48
298
14.7
(b)-(c) 111
14.2
( 3.6 ) c
(a)-(b)
12
177
9.0
(b)-(c)
-
-
(3.7)
(x)-(y)
36
263
13.0
99
12.5
(3.8)d
a Only one coalescence temperature was observed,
b Calculated using the equation
A G+/RTc = 22.96 + loge(Tc/A v)
c Only two conformers (a) and (b) were observed,
d Only one conformer (x) was observed.

80
Since imidazolidines and hexahydropyrimidines have
three conformers, two Av values were obtained (one between
conformers (a) and (b) and the other between (b) and (c))
and hence two free energies of activation were obtained for
each of the amides. Both values differed by + 0.5 kcal
mole 1.
For hexahydro-sym-triazine (3.7) four signals were seen
for the two conformers. The three equal intensity signals
at 5.26, 5.37 and 5.71 ppm were assigned to conformer (y)
and the remaining signal at 5.38 ppm was assigned to
conformer (x) (see Table 3.3). The signal at 5.37 and 5.38
ppm were almost the same, hence for the conversion of (x) to
(y) two Av values were obtained (one between 5.26 and 5.38
ppm and the other between 5.71 and 5.38 ppm). The two
calculated free energies of activation differed by + 0.5
kcal mole-'*' .
The benzamides had higher fr«ee energies of activation
than the corresponding pivalamides. The free energy of
activation for 1, 3,5-tribenzoylhexahydro-sym-triazine (3.7)
was lower (by 2 kcal mole ^) than that for the benzoyl
derivatives of imidazolidine (3.3) and hexahydropyrimidine
(3.5). This decrease in activation barrier might possibly
be due to less energetic rotation processes (discussed in
section 3.2.10) .

81
3.2.10. Mechanism of Conformer Interconversion
Amides interconvert by bond rotation, and the
interconversion pathway is unambiguous for monoamides with
only two conformers. However, there has been no mention in
the literature about the two possible directions of rotation
for the conformer interconversi on, clockwise or
anticlockwise. This possibility becomes relevant when a
chiral center is present, either at the a position to the
nitrogen or carbonyl group, or when more than one amide
group is present, such as peptides where the sequence
(individual or concerted) of rotation about the different
amide C(0)-N bonds also becomes an important factor.
Compounds like N-acyl-2-substituted saturated
heterocyclic amines [72CC788, 78JCS(P2)1157, 67CB3397,
75BCSJ553, 77BP1465, 83CJC2572] and 1,3,5-trinitroso-sym-
triazine [78JMR131] have been investigated by DNMR.
However, there has been no mention of the clockwise or
anticlockwise rotation of the amide C(0)-N and the nitroso
N-N bonds, respectively.
From band shape analysis of the exchange broadened
spectra of 1,4-dinitrosopiperazine, cis-2,6-dimethyl-l,4-
dinitrosopiperazine, trans-2,5-dimethy1-1,4-
dinitrosopiperazine and 1,3,5-trinitrosohexahydro-sym-
triazine, the possibility of correlated two bond rotations

82
has been excluded, and the spectra have been found to be
consistent with the exclusive operation of sequential
processes [78JMR131],
Correlated rotations have been found to be the
favorable process in triphenylmethyl cations [68JAM4679], in
certain substituted [2.2.2.2]paracyclophanetetraenes
[84TL4787] and in triarylboranes, methanes and amines
[76ACR26].
In triaryl cations, the most favorable mechanism for
interconversion of propeller conformers has been proposed to
be the three ring flip [68JAM4679]. In triaryl boranes,
methanes and amines, of all the possible rotations the
favorable and the lowest energy rotation has been found
theoretically to be the two ring flip, in which two rings
rotate in one direction while the third rotates in the
opposite direction [76ACR26].
For the amides (3.3-3.8) with more than two conformers
the rotations around the amide C(0)-N bonds could either be;
(A) individual (sequential), or (B) concerted (correlated)
[78JMR131].
Compounds (3.3), (3.4), (3.5) and (3.6) can exist in
three distinct conformers (a), (b) and (c) (scheme 3.2 and
3.3). For each of these amides, mechanism (A) (going along
the sides of the square) interconverts conformers (a) and

83
O
R
R O
(b) O R
(3-3) R = C6H5
(3-4) R = C(CH3)3
R (b) O R (c) R
(3 5) R = C6H5
(3 6) R=C(CH3)3

84
(b), and conformers (b) and (c), but not directly (a) to
(c). On the contrary, mechanism (B) (going along the
diagonal of the square) directly interconverts (a) and (c),
whereas (b) interconverts only with its topomer
[71AG(E)570].
For the tris-amides (3.7) and (3.8) (scheme 3.4),
mechanism (A) (going along the sides of the cube)
interconverts conformers (x) and (y), as well as changing
conformer (y) into its topomers. Mechanism (B) has two
possibilities. Firstly, when two amide bonds rotate and the
third does not (going along the diagonal of the faces of the
cube). This interconverts conformers (x) and (y) as well as
changing conformer (y) into its topomers. Secondly, when
all three amide bonds rotate (going along the diagonal of
the cube). In this case both (x) and (y) merely change into
their corresponding topomers [7lAG(E)570] (scheme 3.4).
At higher temperatures, fast rotation around the amide
C-N bonds should lead to a singlet in the NMR spectrum,
for each methylene between two hetero atoms in the ring,
irregardless of whether mechanism (A) or (B) is operating.
Higher temperature spectra indeed showed singlets for
the C-2 methylene protons of (3.3), (3.4), (3.5) and (3.6).
Similarly, the C-2, C-4 and C-6 methylene protons gave one
singlet for (3.7) and for (3.8).

R
O
(37) R = C6H5
(3 8) R=C(CH3)
Scheme 3.4

86
As the temperature was lowered, these signals for
(3.3-3.7) broadened, coalesced and separated as expected
into two or more peaks. Surprisingly, the signal for
compound (3.8) remained as a singlet even at -110°C.
Thus it can be assumed that in compound (3.8) the
rotations around the amide C(0)-N bonds could be correlated,
that is, all three amide bonds rotate simultaneously.
However, the possiblity of three sequential rotations with
conformer (y) as a short lived intermediate in the
transitory state can not be ruled out. The two ring flip
mechanism [76ACR26] as seen in R^Z compounds, where Z
represents either B, CH or N, and R represents aryl groups,
can be extended to compound (3.8) where R represents the
pivaloyl group and Z represents the hexahydro-sym-triazine
group.
Since DNMR spectroscopy deals exclusively with the
phenomenon of site exchange among nuclei, and is
uninformative with respect to intermediate states, the
information about transitory states can not be obtained.
However, for the present system it can be extrapolated from,
results that have been obtained on triaryl boranes using
molecular mechanics [76ACR26], and simple 1,3-type
interactions [68CJC2821].

87
Considering only simultaneous (correlated) rotations
for compounds (3.3), (3.4),(3.5) and (3.6), the rotations
around the amide C(0)-N bonds could be either in the same
direction or in opposite directions. For conformers (a) and
(c) if the rotation is in the same direction then in the
transition state the R groups point in the opposite
direction. However, if the rotation is in opposite
directions then in the transitory state the R groups point
in the same direction. Thus from simple 1,3-type
interactions [68CJC2821] same side rotations would be
favored. For conformer (b) the converse is true, that is
opposite side rotations are favored.
On extending similar arguments for the different
conformers of compound (3.7) and (3.8), it is obvious that
there are three possible ways for the simultaneous
rotations: (i) one amide bond in one direction and the other
two in the opposite direction, (ii) two amide bonds in one
direction and the third in the opposite direction and (iii)
all the three amide bonds in one direction, of which (i) and
(ii) are essentially the same.
Conformer (x) which is similar to conformer (b) can not
rotate in the same direction since all the R groups will
point in the same direction in the transitory state which is
not a favorable process. Hence it has to go through either

88
(i) or (ii) which are the same. For conformer (y) however,
either of the mechanisms (i) (or (ii)) or (iii) would
produce the same transitory state. So conformer (y) can
rotate by either of the two possible mechanisms.
3.3. Conclusions
Low temperature and NMR spectra were reported
for 1,3-diacylimidazolidines, 1,3-
diacylhexahydropyrimidines, and 1,3,5-triacylhexahydro-sym-
triazines. Peaks for the individual conformers found were
assigned by using model compounds, from relative
intensities, and by internal consistencies.
Conformer populations, the energy difference and the
energy barrier for their interconversion between them were
deduced (Table 3.7 and Table 3.8). A mechanism for their
interconversion was proposed.
Conformer populations and the energy difference between
the conformers indicate that the conformer in which the two
tert-butyl groups point towards each other is the least
populated and hence the least stable. This was most
pronounced in compounds (3.6) and (3.8) where such a
conformer was not observed at all.

89
All the compounds showed only one coalescence
temperature for the N-Ci^-N signal in their ^H NMR spectra.
The free energy of activation for the benzamide was higher
than that for the corresponding pivalamides in all the
compounds studied.
In conclusion, the mechanism of rotation around the
amide bonds in bis- and tris-amides can be sequential or
correlated depending upon the interactions that the molecule
experiences during the rotation.
3.4. Experimental
3.4.1. Instruments and Methods
Sample solutions for NMR measurements were prepared
directly in 5 mm NMR tubes, dissolving approximately 50 mg
of the compound in 3-4 mL of the solvent. The solvent used
was always CDCl-^ except when temperatures lower than -75°C
[for (3.6) and (3.8)] were used. In these cases CD^COCD^
was used as the solvent. Tetramethylsilane was used as the
internal reference. The solvents used for the model systems
taken from the literature were either CCl^ [for (3.13) and
(3.14)], CDC1, [for (3.9), (3.10) and (3.11)] or CH-Br., [for
J L, Lt
(3.12)].

90
Room temperature NMR spectra were recorded on a
Varían EM 360L spectrometer, and room temperature and high
temperature NMR spectra were recorded on a Jeol FX 100
spectrometer. Low temperature "'"H and spectra were
recorded on a Nicolet NT 300 spectrometer.
3.4.2. Preparation of Amides
The synthesis of saturated heterocyclic amides (3.3),
(3.4), (3.5), (3.6), (3.7) and (3.8) was discussed in the
experimental part of chapter 2.

CHAPTER 4
HYDROGEN EXCHANGE IN AMIDES
4.1. Introduction
Proton transfer reactions are of extensive academic
interest not only for their mechanism but also in the
preparation of labelled compounds which are becoming
increasingly important in reaction mechanism studies of both
chemical and biological systems. While a great deal of
attention has been given to carbon acids such as ketones and
nitrocompounds [61JAM3688, 63JAM3890, 71JAM2225, 71JAM2231],
work on heterocyclic compounds has been less extensive
[74AHC1, 73AHC137].
Acid or base catalysed hydrogen exchange is not
possible under aqueous conditions with simple amides because
they are easily hydrolysed. However, hydrogen exchange in
amides can be achieved by the use of strong bases like
alkyllithiums followed by quenching with D2O or CH^OD
[78CR275]. On the other hand, 4-pyridones, which are
vinylogous amides, are stable to acids as well as bases and
exchange studies on them are possible in aqueous media.
91

92
4.1.1. Hydrogen Deuterium Exchange in 4-Pyridones
Hydrogen-deuterium (H/D) exchange can be catalyzed both
by acids as well as bases. With N- and 0- substituted 4-
pyridones both acid [68JCS(B)866, 64RTC186, 67CC1047,
67JCS(B)1226, 68CPB715] as well as base catalyzed
[65JAM3365, 64TL3083, 69JOC589] exchanges have been
reported. Generally acid catalyzed exchange requires much
harsher conditions than the base catalyzed reaction.
4.1.1.1. Acid catalysis of hydrogen exchange in 4-pyridones
Acid catalyzed hydrogen-deuterium exchange occurs at
the 3- and 5- positions of 4-pyridones (4.1 - 4.4) at 170°C.
4-Alkoxypyridine (4.5) behave similarly. However, 4-
methoxypyridine (4.6) does not exchange under these
conditions but undergoes a rearrangement of the methyl group
from oxygen to nitrogen [67JCS(B)1226].
(4.1) (4.2) (4.3) (4.4)

93
OCH,
CH.
OCH,
h3c^% n^ch3
(4.5)
s,
•N-
(4.6)
BF'
H3
(4.7)
4.1.1.2. Base catalysis of hydrogen exchange in 4-pyridones
Base catalyzed hydrogen-deuterium exchange, on the
other hand, takes place at the 2- and 6- positions of N-
alkyl-4-pyridones (4.2) and (4.4) at 100°C and at the same
positions of 4-methoxy-l-methylpyridinium tetrafluoroborate
(4.7) [6 5JAM3 3 6 5, 64TL3083, 69JOC589] at 40°C.
For comparison, the hydrogen-deuterium exchange of the
parent system, pyridine, (i) in CH30H-CH30- solution at
16 5 0 C [69JAM5501 ], or (ii) in D20-0D_ at 200°C [67JAM3358]
or (iii) in ND3~NaND2 at -25°C [68RSO601] displays the
reactivity order 2(6) < 3(5) < 4. The least reactivity of
the proton adjacent to nitrogen has been ascribed to
decrease in s-character of the C2-H bond and to
electrostatic repulsion between the coplanar nitrogen and
the electron pair of the adjacent anion being formed
[69JAM5501]. The effects of halogen substituents in the
pyridine ring on the rates of H/D exchange have been studied
[66JAM4766]. A halogen at the 3-position accelerates
exchange at the 4-position whiJe ? halogen at the 4-position
accelerates exchange at the 3(5)-positions [74AHC1].

94
4-Alkoxypyridines are susceptible to alkyl-oxygen
cleavage of the alkoxy group by an SN2 mechanism [69JOC589]
and can also undergo isomerization at elevated temperatures
to the thermodynamically more stable N-alkyl-4-pyridones
[66CC631]. Mechanistic studies of the cleavage of alkyl
pyridyl ethers revealed that 4-methoxypyridine (5.6) with
CD^OD-CD^O at 165°C showed exchange at the 3,5-positions of
the pyridine ring in addition to the expected ether cleavage
[70JOC3462].
4.1.2. Aim of the Work
Further to the investigation of the synergistic effect
of amide groups, described in chapter 2, compounds with
amide functions in a ring were also considered. Bis(N-2-
pyridonyl)me thane (4.8) and bis(N-4-pyridonyl)me thane (4.9)
were chosen for this study. Compound (4.8) was prepared
from 2-pyridone and methylene chloride under phase transfer
conditions. However, similar reaction with 4-pyridone gave
N-(4-pyridinoxymethyl)-4-pyridone (4.10) (Scheme 4.1)
instead of (4.9), but compound (4.10) on heating at 200°C
rearranged to (4.9). A detailed investigation of the
mechanism of this rearrangement is discussed in chapter 5.

95
Base catalyzed hydrogen deuterium exchange on these
compounds (4.8 - 4.10) was investigated under aqueous
conditions since the pyridones were known to be stable to
aqueous basic conditions [74M11]. The exchanges were done
in DMSO-dg solvent and with NaOD as the base and were
followed by ^"H NMR. Compound (4.8) showed exchange only at
the 6-position of the 2-pyridone rings, similarly (4.9)
showed exchange only at the 2,6-positions of the 4-pyridone
rings. Interestingly, compound (4.10) showed exchange at
pyridine 3,5-positions in addition to the expected exchange
at the pyridone 2,6-positions at ambient temperature.
However, none of these compounds (4.8 - 4.10) showed any
exchange at the N-CH0-N in (4.8) and (4.9) or at the N-CH-,-0
in (4.10) positions.

H
+ ch2ci2
Scheme 4.1
(4.10)
Although the original objectives were therefore not
attained in that the N-Cf^-N groups remained inert, the
observation of ambient temperature exchange at pyridine 3,5-
positions of compound (4.10) lead to the investigation of
the hydrogen-deuterium exchange of various N-substituted 4-
pyridones and O-substituted 4-oxypyridines using NMR. In
addition there was interest in deuterium labelled
substituted pyridines. The main aim of this work was to
find out the mechanism of this facile exchange in compound
(4.10).
4.2. Results and Discussion
4.2.1. Hydrogen-Deuterium Exchange in N-(4-
Pyridinoxymethyl)-4-pyridone
The base catalyzed H/D ^ ' !' 'nge with NaOD for compound
(4.10)was performed in DMSO-d^. The spectrum of the
starting compound (4.10) is shown in Figure 4.1; signal

97
assignments followed from simple model compounds,
multiplicity and coupling constant values. Of the four
doublets and a singlet seen the singlet was assigned to the
N-Cf^-O protons. The doublets at 6.16 and 7.96 ppm were
assigned to the pyridone 3,5 and 2,6 protons, respectively
and the doublets at 7.10 and 8.50 ppm were assigned to the
pyridine 3,5 and 2,6 protons, respectively. The
disappearance of the signal at 7.96 ppm at 25°C showed the
expected exchange at the 2,6-positions of the pyridone
(Figure 4.2). For N-methyl-4-pyridone similar exchange at
pyridone 2,6-positions has been reported at 100°C
[65JAM3365]. On warming up to 30-40°C the signal at 7.10
ppm began to decrease in intensity indicating an exchange at
the 3- and 5- positions of the pyridine ring (Figure 4.3).
For 4-methoxypyridine similar exchange at pyridine 3,5-
positions has been reported at 165°C [70JOC3462]. No
further exchange was observed either on continuing at this
temperature or on further increase in the temperature.
The fact that 4-methoxypyridine does not show exchange
of the 3,5-positions at ambient temperature [70JOC3462],
suggests that the exchange might be proceeding either by an
inter- or intramolecular abstraction of the proton by the
anion formed at the pyridone 2(6) position.

o
9 8765 43 2
fig- • 1- ¿O MHz ^ H NMR Spectrum of N-( 4-Py r i d i noxyme thy 1)-4-py r idone (in
DMSO-d,)
b

bO MHz ^H NMR Spectrum of N-(4-Pyridinoxymethy1)-4-pyridone (in NaOD
DMSO-dg) After Exchange at 25°c.

60 MHz LH NMR Spectrum of N-(4-Pyridinoxymethy1)-4-pyridone (in NaOD-
DMSO-dr) After Exchange at 40°C.
b
o
100

101
So it was believed that the base catalysed H/D exchange
of compound (4.10) could have happened through either: (i)
an intramolecular seven-membered intermediate (4.11), or
(ii) an intramolecular five-membered intermediate (4.12), or
(iii) a direct abstraction of proton by simple inductive
effect similar to that observed for chloropyridines
[66JAM4766] and 4-methoxypyridine [70JOC3462]. In case
(iii), the direct abstraction of proton may be caused either
with an increased inductive electron withdrawing or a
decrease in mesomeric electron donation by oxygen.
(4.11)
0
H
(4.12)
The five-membered intermediate (4.12) was ruled out on
the basis that no exchange was observed at the N-CHn-0
methylene protons of (4.10). The same was found to be true
for the H/D exchange behavior on different model systems to
test (ii) as discussed lote1 : " ¡:his chapter.

102
The seven-membered cyclic intermediate of (i) seemed
2
unlikely because with four sp hybridized atoms there will
be a severe strain in the ring, also entropy does not favor
this intermediate (4.11).
However, model compounds were prepared to test all the
three possible mechanisms (i), (ii) and (iii).
4.2.2. Hydrogen-Deuterium Exchange in N-(Phenoxymethyl)-4-
pyridone and Ñ-(Arylthiomethyl)-4-pyridones
To test mechanisms (i) and (ii), N-(phenoxymethyl)-4-
pyridone (4.13) and N-(4-methylthiophenylmethyl)-4-pyridone
(4.14), were prepared from 4-pyridone and chloromethylphenyl
ether and 4-pyridone and chloromethyl-(4-methylphenyl)
sulfide, respectively (scheme 4.2).
Ar
(4.13)
Ar = C6H5
X = 0
Scheme 4.2
(4.14)
Ar = 4-CHqC,H.
3 6 4
X = S
(4.15)
Ar = 4-NO„C,H.
2 6 4
X = S

103
Hydrogen-deuterium exchange studies on (4.13) followed
by 1H NMR showed, as expected, exchange at the 2,6-hydrogens
of the pyridone ring at 25°C. On increasing the temperature
to 50°C or more no exchange in the phenyl ring hydrogens was
observed. Similarly hydrogen-deuterium exchange of (4.14)
occurred as expected at the methylene hydrogens at 25°C and
on warming up to 40°C the 2,6-hydrogens of the pyridone ring
also exchanged. Prolonged heating at this temperature or
increasing the temperature did not show any exchange in the
4-methylphenyl ring hydrogens.
This lead to the belief that the aryl ring has to be a
pyridine ring in order for an exchange to occur. Thus a
study of the hydrogen-deuterium exchange behavior of N-(4-
nitrophenylthiomethyl)-4-pyridone (4.15) was attempted in
which we expect the 4-nitrophenyl ring to behave like the 4-
pyridyl ring. Compound (4.15) was prepared from 4-pyridone
and chloromethyl (4-nitrophenyl) sulfide (scheme 4.2).
However, compound (4.15) on H/D exchange in DMSO-dg and NaOD
and followed by ^H NMR, showed signal broadening. This was
due to the radical anion formed by an aromatic nitro
compound in the presence of a carbanion as has been reported
in the literature [66JOC248], The formation of a dark red
color together with the disappearance of the methylene

104
singlet and the reduction in the intensity of the pyridone
2,6-proton signal indicated exchange at these sites. The 4-
nitrophenylthio group being a better leaving group, on
continuing the exchange, the compound underwent SN2
displacement, and 4-nitrophenyl thiol was isolated from the
reaction mixture.
Hence N-(4-pyridylethyl)-4-pyridone (4.16) was prepared
from 4-pyridone and 4-vinylpyridine (scheme 4.3) in order to
test mechanism (i). However, compound (4.16) in DMSO-dg on
treatment with NaOD and followed by ^H NMR showed the
aliphatic CH2-CH2 signals to disappear and vinylic signals
began to appear and they increased in intensity with time.
This indicated that the starting materials were formed as
has been observed for similar N-protected compounds
[84TL1223].
(4.16)

105
4.2.3. Hydrogen-Deuterium Exchange in 2,6-Dimethyl-4-
alkoxypyridine Model Compounds
In order to test mechanism (iii) and (ii) 4-
benzoylmethoxy-2,6-dimethyl-4-pyridone (4.17) and bis(2,6-
dimethyl-4-pyridinoxy)methane (4.18) were prepared.
Compound (4.17) was prepared from a-bromoacetophenone
and 2,6-dimethyl-4-pyridone and compound (4.18) from 2,6-
dimethyl-4-pyridone and methylene chloride under phase
transfer conditions (scheme 4.4).
0
+ RCH2C1
Scheme 4.4
h3c/^n/x-ch3
(4.17) R = C,H,CO-
o 5
(4.18) R = 4-(2,6-Di¬
me thy lpyr idinoxy ) -
Compound (4.17) in DMSO-dg and NaOD and followed by
NMR showed exchange only at the methylene protons and
continuing the exchange led to the SN2 displacement of the
2,6-dimethyl-4-pyridone. Compound (4.18) was found to be
stable under these conditions. However, no exchange at the
pyridine 3,5-positions was observed; on prolonging the
conditions for a long time, the methyl groups began to show
an exchange.

106
A drawback in these model systems was that though the
pyridine ring was present, the methyl groups present at the
2,6-positions may retard the exchange, as has been observed
in exchange studies with 3-substituted pyridines
[74JCS(P2)1363 ] . As a result, model systems without 2,6-
methyl groups in the pyridine ring were considered.
4.2.4. Hydrogen-Deuterium Exchange in 4-Alkoxypyridine
Model Compounds
In order to test mechanism (iii), with an increase in
the inductive electron withdrawal or a decrease in the
mesomeric electron donation by oxygen, the following model
compounds were prepared. 4-Pyridyl benzoate (4.19) and 4-
phenoxypyridine (4.20) mainly with an increase in the
electron withdrawal by oxygen, due to the resonance effect
happening in the opposite direction with the carbonyl and a
phenyl group, respectively. And 2-(4-pyridinoxy)ethanol
(4.21) and 4-(2-aminophenoxy)pyridine (4.22) mainly with a
decrease in the mesomeric electron donation by oxygen, due
to an intramolecular hydrogen bonding between the -OH and
oxygen and -NH2 and oxygen, respectively.
Compound (4.19) was prepared from 4-pyridone and
benzoyl chloride (scheme 4.5) and compound (4.20) from 4-
chloropyridine hydrochloride and phenol (scheme 4.6).

107
4-Pyridyl benzoate (4.19) in DMSO-d^ and NaOD and
followed by NMR showed hydrolysis while 4-phenoxypyridine
(4.20) did not show any exchange.
coc6h5
H
Scheme 4.5
(4.19)
(4.20)
(4.21)
(4.22)
/R
o
R = C,Hc
b o
R = CH2CH2OH
R = 2-NH0C,H,
2 6 4
Scheme 4.6
Compound (4.21) was prepared from 4-chloropyridine
hydrochloride and ethylene glycol and compound (4.22) was
prepared similarly from 4-chloropyridine hydrochloride and
2-aminophenol (scheme '.6'.

108
The ^H NMR spectrum of 2-(4-pyridinoxy)ethanol (4.21)
in DMSO-dg showed a multiplet between 3.70-4.30 ppm for the
CH2-CH2 protons and a broad signal at 4.35 ppm for -OH. The
doublet at 7.10 ppm and a broad singlet at 8.55 ppm were
assigned to the pyridine 3,5- and 2,6-protons, respectively
(Figure 4.4). On adding CD^ONa the multiplet between 3.70-
4.30 ppm narrowed, the signal at 8.55 ppm became a doublet
(indicating that in neutral solution for (4.21) the acidic -
OH proton is equilibrating between the hydroxyl oxygen and
the nitrogen) and as expected the broad singlet at 4.35 ppm
disappeared (Figure 4.5). On increasing the temperature the
aliphatic multiplet began to disappear and a new aliphatic
singlet peak began to appear indicating the ether cleavage
of (4.21) and formation of ethylene glycol. However, at
85°C the doublet at 7.10 ppm began to decrease in intensity
with an increase in intensity of the signal at 8.55 ppm
indicating the exchange at pyridine 3,5-positions (Figure
4.6).
4-(2-Aminophenoxy)pyridine (4.22) (Figure 4.7) in
CD^ONa/CD^OD/DMSO-dg and followed by ^H NMR showed a
decrease in intensity of the pyridine 3,5-protons signal
with an increase in the signal intensity of the pyridine
2,6-protons (Figure 4.8). This indicated an exchange at the
pyridine 3,5-positions. The expected ether cleavage

“1 r-
10 9
8
5
2
1
Fig. 4.4
60 MHz
1
H NMR Spectrum of 2-(4-Pyridinoxy)ethanol
(in DMSO-dg).
o -1

98 7654 3 210
Fig. .5 60 MHz ^H NMR Spectrum of 2-(4-Pyridinoxy)ethanol (in CD^ONa-CD^OD-
DMSO-d,) at 25°C.
b
110

Fig- hú MHc NMR Spectrum of 2-( 4-Pyridinoxy) ethanol (in CD-.ONa-CD,ONa-
DMSO-dg) After Exchange at 70°C. J
111

IK b
60 MHz ^H NMR Spectrum of 4-(2-Aminophenoxy)pyridine (in CD^ONa
DMSO-d,) .
o

113

114
reaction was also observed here. This observation of
exchange at pyridine 3,5-positions with compounds (4.21) and
(4.22) was similar to that observed for compound (4.10) (at
35-40°C) but at a higher temperature (85°C).
This observation led to the conclusion that in compound
(4.10) the exchange at the pyridine 3,5-positions was
proceeding by mechanism (i). The fact that 4-
methoxypyridine did not show any exchange similar to (4.10),
(4.21) and (4.22) showed that there was an interaction
between the lone pair on oxygen attached to the pyridine
ring and the easily exchangeable proton at the y-position of
the O-substituent.
Experimental evidence for the assistance by the oxygen
for the proton removal was obtained by comparing the
hydrogen-deuterium exchange behavior of compound (4.10) and
N-methyl-4-pyridone (4.2) [65JAM3365] under identical
conditions. Compound (4.10) was found to exchange in DMSO-
dg and NaOD five times faster than (4.2). Hence in the
exchange of compound (4.10) the effect has to be an enhanced
inductive electron withdrawal by oxygen and the transition
state involved may be as shown in (4.23).

115
O
k
• i
B
(4.23)
4.3. Conclusions
From the results obtained for the base catalyzed
hydrogen deuterium exchange behavior of N-substituted 4-
pyridones and O-substituted 4-oxypyridines (Figure 4.9) the
following points can be said:
(1) A heteroatom at the |3-position of the N-alkyl
substitution enhances the H/D exchange rate for the 2,6-
positions in N-alkyl-4-pyridones.
(2) A heteroatom at the y-position of the O-alkyl
substitution with exchangeable hydrogen or a y-acidic C-H
enhances the hydrogen exchange rate for the 3,5-positions in
4-alkoxypyridines.
(3) In general by manipulating the substituents on nitrogen
in N-alkyl-4-pyridones and oxygen in 4-oxypyridines base
catalyzed hydrogen exchange can be achieved either at the
2,6-positions or at the 3,5-positions at ambient
tempe ratures.

116
Figure 4.9 Base Catalyzed Hydrogen-Deuterium Exchange in
Different N- and O-Substituted 4-Pyridones
(the exchanging positions are indicated by
* mark)
(4.19)
(4.20) (4.21)
(4.22)

117
4.4. Experimental
Melting points were recorded on a Bristoline hot-stage
microscope and are uncorrected. The NMR spectra were
recorded on a Varian 360L spectrometer using TMS as the
internal reference and NMR spectra were recorded on a
JEOL FX 100 spectrometer and Varian XL 200 spectrometer
using the solvent (DMSO-dg) peak as the reference. The IR
spectra were obtained on a Perkin-Elmer 283 B
spectrophotometer
4.4.1. Method and Reagents
All hydrogen-deuterium exchanges have been done with
excess NaOD (1 M) in dimethylsulfoxide-dg as solvent unless
indicated. All exchanges were followed using the decrease
in the peak intensity of the exchanging proton coupled with
the disappearance of the coupling of the exchanging proton
with the vicinal proton (^H NMR) and were confirmed with
NMR which showed a decrease in signal intensity of the
carbon to which the exchanging proton is attached.
General procedure for hydrogen-deuterium exchange: The
pyridone (25-30 mg) was taken in a 5 mm NMR tube and was
dissolved in 0.3 mL of DMSO-d,. To this NaOD or CD,OD

118
(0.20-0.25 mL, 1 M) was added and the ^H NMR spectra were
recorded periodically. For higher temperature exchange the
NMR tubes were heated in an oil bath maintained at the
required temperature.
Chloromethyl phenyl ether, b.p. 90-95°C (20mm)
(lit.[77CI127], b.p. 87-89°C (16mm)), chloromethyl phenyl
sulfide, b.p. 85-90 °C (5mm) (lit.[77JOC3094), b.p. 83°C
(1.5mm)), 2,6-dimethyl-4-pyridone, m.p. 224°C
(lit.[50JOC337], m.p. 225°C), N-methyl-4-pyridone (4.3),
m.p. 95°C (lit.[65JAM3365], m.p. 92-93°C) and 4-
pyridylbenzoate (4.19), m.p. 82°C (1it.[59JCS2844], m.p. 79-
80°C) were prepared by literature methods. 4-
Methoxypyridine (4.6), b.p. 80-85°C (20-25mm)
(lit.[68JAM1569], b.p. 80-82°C (15-20mm)), was prepared from
4-methoxypyridine-N-oxide following an analogous procedure
[53JOC534]. 4-Pyridone (4.1) and 4-methoxypyridine-N-oxide
were obtained from Aldrich.
4.4.2. Preparation of N-(4-Pyridinoxymethyl)-4-pyridone
4-Pyridone (4.75 g 0.05 mole), benzyltriethyl-ammonium
chloride (0.57 g 0.0025 mole), potassium carbonate (6.9 g
0.05 mole) and potassium hydroxide (84% 3.5 g) were
vigorously stirred and refluxed in methylene chloride (300
mL) . After 48 h the CH-,C1-, was filtered off, the residue
extracted with hot Ct^Cl-, and combined with the filtrate.

119
It was dried with anhydrous MgSO^, filtered and the solvent
evaporated to give 1.18 g (25%) of (4.10): m.p. 199-201°C;
IR (CHBr^) 1650 cm-1; 1H NMR (DMSO-dg) 6 6.00 (s, 2H), 6.16
(d, 2H, J=8 Hz), 7.10 (d, 2H, J=6 Hz), 7.96 (d, 2H, J=8 Hz),
8.50 (d, 2H, J = 6 Hz). Anal, caled, for C1 1H1 qN202 . H20: C,
60.0; H, 5.5; N, 12.7. Found: C, 60.1; H, 5.6; N, 12.7.
4.4.3. Preparation of N-(Phenoxymethyl)-4-pyridone and N-
(Arylthiomethyl)-4-pyridones
Preparation of N-(phenoxymethyl)-4-pyridone (4.13)
4-Pyridone (2.38 g 0.025 mole), benzyltriethyl-ammonium
chloride (0.575 g 0.0025 mole), potassium hydroxide (3.6 g
84%) and chloromethyl phenyl ether [81TL1973] (3.56 g 0.025
mole) were vigorously stirred and refluxed in methylene
chloride (300 mL) . After 48 h was filtered off and
the resude extracted with hot CH2CI2/ combined with the
filtrate and dried with anhydrous MgSO^. This was then
filtered and solvent evaporated to give 2.5 g (50%) of
(4.13): m.p. 149-151°C; IR (CHBr3) 1630 cm 1;
dg) 6 5.90 (s, 2H), 6.25 (d, 2H, J=7 HZ), 7.25
(d, 2H, J=7 Hz). Anal, caled, for C]_-^H]_ ]_NOo :
5.5; N, 7.0. Found: C, 71.5; H, 5.6; N, 6.7.
1H NMR (DMSO-
(m, 5H), 7.95
C, 71.6; H,

120
Preparation of N-(4-methy1phenylthio)-4-pyridone (4.14)
To a solution of 4-pyridone (2.38 g 0.025 mole)
dissolved in absolute ethanol (50 mL), was added sodium
(0.58 g 0.025 mole). After the metal had dissolved, 4-
methylphenyl chloromethyl sulfide [77JOC3094] (4.31 g 0.025
mole) was added and the mixture refluxed for 12 h. After
cooling to 25°C it was poured into water and extracted with
chloroform (3x50 mL). The CHCl^ extract was dried with
anhydrous MgSO^, filtered and removal of the solvent gave
3.5 g (60%) of (4.14): m.p. 105°C; IR(CHBr3) 1620 cm-1; 1H
NMR (CDC13) S 2.32 (s, 3H), 4.98 (s, 2H), 6.33 (d, 2H, J=9
Hz), 7.10-7.48 (m, 6H). Anal, caled, for C^H-^NOS: C,
67.50; H, 5.66; N, 6.06. Found: C, 67.84; H, 5.83; N, 5.96
Preparation of N-(4-nitrophenylthio)-4-pyridone(4.15)
Prepared following the same procedure as described for
(4.14) but using 4-nitrophenyl chloromethyl sulfide
[77JOC3094] gave 2.6 g (40%) of (4.15): m.p. 118-120°C;
IR(CHB r 3 ) 1615, 1525 , 1330 cm-1; 1H NMR (DMSO-dg) 6 5.80 (s
2H), 6.18 (d, 2H, J=8 Hz), 7.75-8.10 (m, 4H), 8.45 (d, 2H,
J=9 Hz). Anal, caled, for ci2H10N2°3S: C, 54.90; H, 3.82;
N, 10.69. Found C, 54.50; H, 3.83; N, 10.36.

121
4.4.4. Preparation of N-(4-Pyridylethyl)-4-pyridone (4.16)
4-pyridone (0.95 g 0.01 mole) and 4-vinylpyridine (1.05
g 0.01 mole) taken in lOmL of ethanol were refluxed for 10
h. The reaction mixture was cooled and ether was added to
the mixture to give 1.8 g (90%) of compound (4.16): m.p. 78-
8 0 0 C; IR (CHBr3) 1620 cm-1; 1H NMR (CDC13) 6 3.12 (t, 2H J = 7
Hz), 4.22 (t, 2H J=7 Hz), 6.40 (d, 2H J=7 Hz), 7.22 (d, 2H
J=5 Hz), 7.50 (d, 2H J=7 Hz), 8.70 (d, 2H J=5 Hz). Anal,
caled, for C12H12N20: C, 72.00; H, 6.00; N, 14.00. Found C,
72.12; H, 6.23; N, 13.91.
4.4.5. Preparation of 2,6-Dimethyl-4-alkoxypyridines
Preparation of 2,6-dimethyl-4-pyridyl phenacyl Ether (4.17)
Prepared following the same procedure as described for
(4.14) but using phenacyl bromide in place of 4-methylphenyl
chloromethyl sulfide, gave 4.5 g (75%) of compound (4.17):
m.p. 2 2 5 0 C; IR (CHB r 3) 1690 cm-1; 1H NMR (DMSO-dg) 5 2.80
(s, 6H), 6.20 (s, 2H), 7.68 (s, 2H), 7.75-8.45 (m, 5H).
Anal, caled, for ci5H]_5N02: C' 74-69; h, 6.22; N, 5.81.
Found: C, 74.55; H, 6.48; N, 5.68.

x22
Preparation of bis(2,6-dimethyl-4-pyridinoxy)methane (4.18)
Prepared following the same procedure as described for
compound (4.10) but using 2,6-dimethyl-4-pyridone in place
of 4-pyridone, gave 5.5 g (85%) of compound (4.18): m.p. 73
750C; IR (CHBr3) 1590 cm'1; XH NMR (CDC13) 6 2.58 (s, 12H),
5.93 (s, 2H), 6.91 (s, 4H). Anal, caled, for 5H]_ 8N2°2: C
69.77; H, 6.98; N, 10.85. Found C, 69.55; H, 7.15; N,
10.68.
4.4.6. Preparation of 4-Alkoxypyridine Model Compounds
Preparation of 4-phenoxypyridine (4.20)
4-Chloropyridine hydrochloride (3.0 g 0.02 mole) was
dissolved in dimethyl sulfoxide (40 mL) and phenol (1.88 g
0.02 mole) and sodium hydroxide pellets (2.0 g) were added
and heated gently at 100°C overnight. The mixture was
cooled and poured into ice and water (300 g) and extracted
with ether many times until the ether layer is colorless.
The ether extracts were all combined and dried with
anhydrous magnesium sulfate, filtered and the solvent
evaporated, gave 3.0 g (88 %) of compound (4.20):m.p. 45°C
(lit.[31CB1049], m.p. 4 4-4 6 0 C ) ; IR (CHB r 3) 1230 cm"1; XH
NMR(CDC13) S 6.60-7.50 (m, 7H), 8.50 (d, 2H J=5 Hz). Anal,
caled, for C^HgNO : C. 77.1°: H, 5.26: 'I, 8.19. Found: C,
77.52; H, 5.31; N, 8.12.

123
Preparation of 2-(4-pyridinoxy)ethanol (4.21)
The same procedure as described above for compound
(4.20) except phenol was replaced by ethylene glycol, gave
2.0 g (72 %) of compound (4.21): m.p. 118-120°C; IR (CHB r ^ )
3650 cm-1; 1H NMR (DMSO-dg) S 3.70-4.30 (m, 4H), 4.35 (bs,
1H), 7.10 (d, 2H J=5 Hz), 8.55 (bs, 2H). Anal, caled, for
C7HgN02 : C, 60.43 ; H, 6.48 ; N, 10.07. Found: C, 60.55;
H, 6.69; N, 9.89.
Preparation of 4-(2-aminophenoxy)pyridine (4.22)
The same procedure as described above for compound
(4.20) was used except phenol was replaced by 2-aminophenol,
to give 2.85 g (76 %) of compound (4.22): m.p. 98°C; IR
(CHBr3 ) 3365, 3290 cm-1; 1H NMR (DMSO-dg) 6 3.75 (b, 2H),
6.50-7.20 (m, 6H), 8.40 (d, 2H J=5 Hz). Anal, caled, for
("11H10^2^ : 70.97; H, 5.38; N, 15.05. Found: C, 70.65;
H, 5.52; N, 14.95.

CHAPTER 5
REARRANGEMENT IN AMIDES - OXYGEN TO NITROGEN
MIGRATION OF ALKYL GROUPS
5.1. Introduction
An amide (5.1) is generally more stable than its
isomeric imidate (5.2), as evidenced by chemical, physical
and spectral investigations [63AHC311, 650R1, 67HCA725,
65T1681, 64AHC36]. The greater stability of the amide has
been rationalized on the basis of it-stabi 1 ization energy
[65T2257, 67JAM4300, 66JOC3007] and a-framework
stabilization energy [63MI1]. However, for heterocyclic
analogues of amides, such as pyridones, the difference in
energy between the amide and the imidate form is smaller
[68JAM1569], The equilibrium between the amide and the
imidate can be catalyzed thermally or by acids or alkyl
halides.
_r f r
C N * C N
(5.1) (5.2)
The thermal rearragement of 2-methoxypyridine to N-
methyl-2-pyridone has been shown to be intermolecular
[57JAM3160, 65JCS4911]. Although the earlier workers have
124

125
found the reaction to be catalyzed by benzoyl peroxide and
that old samples of 2-methoxypyridine rearrange at a much
faster rate than fresh samples (probably due to
hydroperoxide formation) [57JAM3160], the later workers
found very minor changes in the rate by adding benzoyl
peroxide or benzoquinone to the reaction mixtures
[65JCS4911]. For 4-methoxypyridine the oxygen to nitrogen
methyl migration (Scheme 5.1) has been suggested to go
through an intermolecular ion-pair type of intermediate
[64MI1, 65JCS4911]. Acid and alkyl halides have been used
as catalysts for oxygen to nitrogen migration [65JCS4911].
R
Scheme 5.1
Although oxygen to nitrogen migrations are generally
thermodynamically favored, steric interactions can cause the
O-substituted derivatives to predominate at equilibrium.
For example, 4-methoxy-2,6-diphenylpyridine is more stable
than 2,6-diphenyl-l-methyl-4-pyridone because of 1,2,6-
steric interactions [68JAM1569]. Oxygen to nitrogen
migrations have also been accomplished by heating with
mercuric bromide and other Lewis acids [67CC122]. Oxygen to

126
nitrogen migration in 2-substituted pyridines with
allyloxy-, methallyloxy- and crotyloxy- groups have been
reported to go through a Claisen rearrangement to give N-
and 3-substituted 2-pyridones [64JOC892]. An attempted
rearrangement of 4-allyloxypyridine was unsuccessful
[63JOC2885], however, in a benzfused system, 4-
allyloxyquinoline, oxygen to nitrogen migration has been
reported to go via a Claisen rearrangement [65JOC1986].
Although the thermal rearrangement of alkyl groups from
oxygen to nitrogen in 4-alkoxypyridines has been proposed to
be intermolecular [65JCS4911], there has been no conclusive
experimental evidence.
5.2. Aim of the Work
The alkyl group migrates from oxygen to nitrogen in 4-
alkoxypyridines by heat and the migration has been found to
be catalyzed by acids and alkyl halides [65JCS4911].
Although the mechanism in alkyl halide catalysis has been
found to be intermolecular for the alkyl group migration
from oxygen to nitrogen in 4-alkoxypyridines [68JAM1569]
there has been no experimental evidence for the purely
thermal uncatalyzed rearrangements. For simple acyclic

127
imidates, the thermal rearrangement of groups from oxygen to
nitrogen known as Chapman rearrangement has been shown to be
intramolecular for the aryl group migration and
intermolecular for the alkyl group migration [70MI1,
61CR179, 72CC303].
As indicated earlier in Chapter 4, the thermal
rearrangement of N-(4-pyridinoxymethyl)-4-pyridone (5.3) to
bis N-(4-pyridonyl)me thane (5.4) together with the
availability of deuterium labelled compounds of (5.3) led to
this work discussed in this chapter.
(5.3)
(5.4)
The aim of the present work was to study the nature of
the thermal migration of the alkyl group in this selected 4-
alkoxypyridine (5.3) and its suitably deuterated derivative,
and use NMR and mass spectroscopic techniques to analyse the
products, in particular to distinguish between inter- and
intramolecular rearrangement.

128
5.3. Results and Discussion
The nature of migration, inter- or intramolecular, is
generally elucidated by crossover experiments [85MI1], The
use of deuterated derivative in crossover experiments
coupled with analysis of products by mass spectrometry makes
it an elegant procedure to study the inter- or
intramolecularity of the rearrangement [68JAM1569].
Choosing the compounds for crossover experiments
requires (i) the two compounds must react at very similar
rates, (ii) the migrating groups must have essentially equal
reactivity towards either of the two reactants and (iii)
quantitative estimation of any mixed products which are
formed. The points (i) and (ii) were uniquely attained by
labelling the starting compound both at the migrating as
well as the non-migrating groups. Point (iii) was overcome
by analysing the products by a mass spectrometer.
Here compounds chosen for the study were N-(4-
pyridinoxymethyl)-4-pyridone (5.3) and its tetradeuterated
derivative N-(3,5-dideutero-4-pyridinoxymethy1)-2,6-
dideutero-4-pyridone (5.5).

129
O
(5.5)
Compound (5.3) and (5.5) were obtained as indicated in
chapter 4. The exchange on compound (5.3) has to be carried
out at 50°C to get compound (5.5), for if the exchange was
carried out at room temperature it mainly gave N-(4-
pyridinoxymethyl)-2,6-dideutero-4-pyridone (the mass
spectrum (Figure 5.1) showed it to be 90% dideuterated).
The mass spectrum of compound (5.5) showed it to be 30%
tetradeuterated (Figure 5.1) (for further details about this
exchange on compound (5.3) see chapter 4).
On heating at 200°C the alkyl group in compound (5.3)
rearranges from oxygen to nitrogen forming bis N-(4-
pyridonyl)methane (5.4) as the major product along with two

mass speculum of (a) N-(4-Pyridinoxymethyl) ^ Pyr^°n®:>^r^n^jgutero_4_
Pyridinoxymethyl)-2,6-dideute ro-4-pyr1done and (c) N-(3f5 Dideutero
pyridinoxymethy1)-2,6-dideutero-4-pyridone.
Fig. 5.L Mass Spectrum
130

131
minor products, N-(4-pyridyl)-4-pyridone (5.6) and 4-
pyridone (scheme 5.2). The products were separated by
column chromatography and identified by the usual analytical
methods. For (5.6) the melting point and spectral data
agreed with its literature values [76RC2167]. The NMR
spectrum of the starting material (5.3) and the products
(5.4) and (5.6) are given in Figures 5.2, 5.3 and 5.4
respectively.
(5.3)
(5.4) (5.6)
Scheme 5.2
Since compound (5.3) has an N-substituted-4-pyridone
ring it can, by resonance, act similar to an allyl group
(5.7) and can undergo a cationic aza-Claisen rearrangement
to (5.8), which are recently reported to be of great
synthetic utility [83JAM6622, 83JAM6629], followed by
another aza-Cope (Claisen) rearrangement to give bis N-(4-

o
Fig .
60 MHz ^H NMR Spectrum of N-(4-Pyridinoxymethyl)-4-pyridone (in
DMSO-d,)
b
132

Pig, 3 ¿o MHc ^H NMR Spectrum of the Major Product of Rearrangement Bis(N
4-pyrLdony1)me thane (in DMSO-dg).
133

Fig. 4 60 MHz ^H NMR Spectrum of the Minor Product Obtained - N-(4-Pyridyl)-
4-pyridone (in DMSO-d^).
134

135
pyridonyl)methane (
possible only after
the two rings, that
.4). The second
a rotation around
is from (5.8) to
0
rearrangement is
the bond connecting
(5.10 (scheme 5.3).
(5.8)
(5.4)
Scheme 5.3
From the thermolysis mixture of (5.3), no intermediate
like (5.9) was isolated which should have been formed if it
had gone through a Claisen rearrangement, unless the second
Claisen rearrangement was much faster than the tautomeric
equilibration process.

136
From examples reported in reviews on the Claisen
rearrangement (77S589, 750R1], of the two double bonds
required for the rearrangement one was a non-aromatic double
bond. Only two examples were reported in which the two
double bonds were in the aromatic ring: benzyl phenyl ether
and diphenylmethyl phenyl ether. On heating in suitable
solvents such as quinoline these two compounds have been
found to undergo homolysis rather than a Claisen
rearrangement [60JCS1286].
5.3.1. Attempted Rearrangements by Chemical Methods
Zinc chloride (Lewis acid) and 4-toluenesulfonic acid
(acid) were found to catalyze the oxygen to nitrogen
migration in compound (5.3). Zinc chloride catalyzed the
rearrangement and reduced the rearrangement temperature by
40°C whereas 4-toluenesulfonic acid catalyzed the
rearrangement even in refluxing benzene. Acids and Lewis
acids catalysis is common for Claisen rearrangements
[83JAM6622, 77S589, 750R1] as well as oxygen to nitrogen
migration of alkyl groups in pyridones [65JCS4911, 67CC122].
An attempt was made to test the possiblity of Claisen
rearrangement by introducing a phenyl ring in place of the
pyridine ring. Such a compound N-(phenoxymethyl)-4-pyridone

137
(5.11) was prepared as indicated earlier in chapter 4,
however (5.11) on thermolysis gave either the starting
material back or uncharacterizable tarry products.
5.3.2. Elucidation of Mechanism of Rearrangement by Physical
Methods
In either compound (5.3) or (5.5) only if the cleavage
was between -O-Cf^- it can lead to the rearranged product
unless it was a radical reaction, which was found not to be
the case since the reaction was catalyzed by Lewis acids.
That was why with compound (5.5) products of the type (5.12)
and (5.13) were not formed, as seen from the 200 MHz NMR
spectrum.
(5.12)
(5.13)

138
A detailed analysis of the 200 MHz 1H NMR spectra of
the products obtained from the thermolysis of (i) compound
(5.3), (ii) compound (5.5) and (iii) an equimolar mixture of
compounds (5.3) and (5.5) did not reveal any clue to the
inter- or intramolecular nature of the migration.
Hence, in order to distinguish the inter- or intra-
molecularity of the reaction, the products were analyzed by
mass spectrometry. From the molecular ion peak intensities,
it should be possible to say if the migration was inter- or
intramolecular. For example, if for compound (5.3) the
molecular ion of the rearranged product is M, then for
compound (5.5) it would be M+4. Now if the migration was
just intramolecular then molecular ion peaks of M and M+4
would be seen. On the other hand if it was intermolecular
then molecular ion peaks at M, M+2 and M+4 would be
observed. An exact picture would be also to consider the
isotope peak intensities of the molecular ions. So an
analysis of peak intensities in the region of 202 to 208 in
the mass spectra of products obtained on heating at 200°C
from (i) compound (5.3) alone (Scheme 5.4), (ii) compound
(5.5) alone (Scheme 5.4) and (iii) compounds (5.3) and (5.5)
together (Scheme 5.5), would reveal the inter- or
intramolecularity of the reaction.

139
9
O
(5.4)
The mass spectral data for the molecular ion of the
products of the three reactions are given in Table 5.1.
From entries (i) and (ii) of Table 5.1 it is seen that only
entry (ii) has peaks from m/z 205 - 208. So if the
rearrangement was occurring intramolecularly then the peaks
from m/z 205 - 208 would also have the same ratio of peak
intensities. From Table 5.1 the peak intensities were
calculated for an intramolecular migration in (iii) for

o
o
o
(5.3)
m/e 202
m/e 206
m/e 204 m/e 204
(Inter molecular)
Scheme 5.5
140

141
compound (5.5) with reference to (ii) and keeping the peak
intensity of m/z 205 as the standard. The values are given
in entry (i) of Table 5.2. Subtracting entry (i) of Table
5.2 from entry (iii) of Table 5.1 gave the values given in
entry (ii) of Table 5.2. From Table 5.1 the peak
intensities were calculated for an intramolecular migration
in (iii) for compound (5.3) with reference to (i) and
keeping the peak intensity of m/z 402 in entry (ii) of Table
5.2 as the standard. The values are given in entry (iii) of
Table 5.2. Subtracting entry (iii) from (ii) in Table 5.2
gave the difference between the calculated, based on an
intramolecular migration, and the experimentally observed
peak intensities. The magnitude of the difference in
intensities reveal that there was an appreciable increase in
intensity for the M+2 peak clearly indicating that the
rearrangement was intermolecular.
The magnitude of difference (2.6) for the peak at m/z
204 was found to be 23% of the intensity calculated for an
intramolecular rearrangement for the same peak at m/z 204.
The same results were also obtained by considering a
complete intermolecular rearrangement and calculating the
intensities. If the rearrangement was completely (100%)
intermolecular then the products formed for entry (iii) of
Table 5.1 would be as indicated below:

142
(5.3)
+
monodeuterated compound
— >
monodeuterated
product
+ (5.4)
(5.3)
+
dideuterated compound
— >
monodeute rated
product
+ dideuterated
prodct
(5.3)
+
trideuterated compound
— >
monodeuterated
prodcut
+ dideuterated
prodcut
(5.3)
+
(5.5)
— >
dideuterated product
The mono-, di- and trideuterated compounds mentioned
above are the partially deuterated compounds present along
with compound (5.5). From the products formed as shown
above it is clear that no tri- or tetradeuterated compounds
are formed. So peaks at m/z 205 and 206 should have
intensity only as that for the M+l and M+2 peaks of the
molecular ion peak at m/z 204 which was calculated to be
12.8% and 1.1%, respectively of the intensity of molecular
ion peak at m/z 204.
Considering the peak intensity (13.7) for m/z 204 in
entry (iii) of Table 5.1 as 100, the equivalent of 12.8% was
calculated to be 1.7. Now subtracting this value of 1.7 for
m/z 205 from the corresponding peak intensity in entry (iii)
of Table 5.1 the value 9.1 was obtained.

143
From the calculated value for 100% intermolecular
migration (1.7) and the excess intensity observed (9.1 -
obtained by subtracting the calculated value (1.7) from the
experimentally observed value (10.8) given in entry (iii) of
Table 5.1 for the peak at m/z 205) it was found that the
excess in intensity was 81% of the calculated value.
Compounds (5.3) and (5.5) are solids and the
rearrangement occurred at 200°C when the solids began to
melt. At this stage there exists a possiblity of
inhomogenity in the mixtrue. Since intermolecular
migrations are very much dependent on the environment around
a molecule the inhomogeneity in the melt of the mixture
might explain the formation of intermolecularly rearranged
product only to a lesser extent as seen above from the
calculations done.
Another strong evidence against an intramoleuclar
rearrangement was that the product (5.9) was not detected in
the mass spectrometer. If this product was formed then
there would have been peaks observed at m/z 201 (with loss
of hydrogen atom) and at m/z 187 (with loss of methyl
group), which was not observed in the mass spectrum of the
product (Figrue 5.5).

144
Fig.
iee
.5 Mass Spertrum of the flea Cranged Product Obtained
from N-(4-Pyridinoxymethyl)-4-pyridone.

145
Fig. 5.6 Mass Spectrum of the React anaed Product Obtained
from N-(3,5-Dideutero-4-pyridinoxymethyl)— 2,6 —
dideute ro-4-pyridone.

146
Fig.
iee 108
5.7 Mass Spectrum of the Rearranged Product Obtained
from a Mixture of m-'1-pyridinoxymethyl)-4-
pyridone and N—(3-5 clicleu.tsro 4 — py r idi noxyme th .■ 1
2,6—dideutero—4—pyridone.

147
Table 5.1 Mass Spectral Peak Intensities of the Molecular
Ionsa for the Rearranged Products from (5.3),
(5.5) and a Mixture of (5.3) and (5.5).
m/z
202
203
204
205
206
207
208
(i)b
85.3
13.7
1.5
—
-
—
-
(ii)C
2.9
14.6
27.5
30.1
17.4
6.1
1.5
(iii)d
52.4
14.3
13.7
10.8
6.9
1.9
—
a The peak intensities are given in percentage to the total
intensity of all the peaks between m/z 202 - 208 found in
a thermolysis product.
b Thermolysis product of compound (5.3) alone.
c Thermolysis product of compound (5.5) alone.
d Thermolysis product of a mixture of compounds
(5.3) and (5.5) together.
5.4. Conclusions
The thermal rearrangement of alkyl group, for an
alkoxypyridine, from oxygen to nitrogen had been
experimentally established to be intermolecular which was
similar to the acid as well as the alkyl halide catalyzed
alkyl migrations [65JCS4911].
This work also indicates how powerful a tool a labelled
compound could be in deciferinci *-he mechanism of a reaction.

148
Table 5.2 Calculated Mass Spectral Peak Intensities9 and
the Difference Between the Calculated and
Experimental Mass Spectral Peak Intensities.
m/z
202
203
204
205
206
207
208
(i)b
1.6
5.5
10.3
10.8
6.5
2.7
0.7
(ii)C
50.8
8.8
3.4
-
0 . 4
-0.8
-0.7
, . . . ,d
(in )
50.8
7.9
0.8
-
-
-
-
Difference
0.9
2.6
0.4
-0.8
-0.7
a See foot note 'a' for Table 5.1.
b Calculated for an intramolecular migration from (ii) of
Table 5.1 and m/z 205 peak in (iii) of Table 5.1 as
reference.
Obtained by subtracting entry (i) of this table from
entry (iii) of Table 5.1.
b Calculated for an intramolecular migration from entry
(i) of Table 5.1 and m/z 202 peak in (ii) of this Table
as reference.
5.5. Experimental
Melting points were recorded on a Bristoline hot-stage
microscope and are uncorrected. The ^H NMR spectra were
recorded on a Varian 360L spec+rometef using TMS as the

149
internal reference and NMR spectra were recorded on a
JEOL FX 100 spectrometer and Varían XL 200 spectrometer
using the solvent (DMSO-dg) peak as the reference. The IR
spectra were obtained on a Perkin-Elmer 283 B
spectrophotometer.
5.5.1. Rearrangement of Alkyl Group from Oxygen to Nitrogen
in 4-Pyridones - General Procedure
The pyridone (5.3) or (5.5) or a mixture of (5.3) and
(5.5) (200 mg) was heated at 200°C for 25 minutes after
which the dark mass was stirred with chloroform and
filtered, gave 160 mg (80%) of the corresponding bis N-(4-
pyridonyl(methane: m.p. >350°C and used directly for mass
spectral analysis (Figures 5.5, 5.6 and 5.7).
5.5.2. Preparation of N-(3,5-Dideutero-4-pyridinoxymethyl)-
2,6-dideutero-4-pyridone (5.5)
The pyridone (5.3) (100 mg) was dissolved in DMSO-dg
(0.5 mL) and sodium deuteroxide (1M ImL) was added to this
solution. The mixture was kept overnight at 50°C, cooled
and then poured into ice cold deuterium oxide (2 mL). The
solid formed was filtered and dried, giving 92 mg (90%) of
pyridone (5.5). This was directly used for the
rearrangement and the mass spectrum (Figure 5.4) showed the
product to be 30% tetradeuterated.

CHAPTER 6
SUMMARY
A general introduction about the structure and
properties of amides pertaining to this work was given in
chapter 1. Preparation of acyclic, cyclic and vinylogous
amides was discussed. The scope of this work was also
mentioned.
The synergistic effect of amide groups for a-
metallation was discussed in chapter 2. 1,3-
Diacylimidazolidines, 1,3-diacylhexahydropyrimidines and
1,3,5-triacylhexahydro-sym-triazines were reacted with
lithiating reagents and this was followed by treatment with
electrophiles. However, they did not show any additional
increase in carbanion stability compared with those reported
for N-acylpyrrolidines and N-acylpiperidines, respectively.
The fact that the second amide group did not bring about any
substantial additional stabilization of the carbanion might
have been either due to (i) the most favored conformation of
the diacyl amines had the R group of one of the acyl unit
sterically hindering the attack at the methylene of the N-
CH2-N unit or (ii) the conformer favoring the double
150

151
stabilization was not the predominant conformer. 1,3-
Dipivaloylimidazolidine did not react under lithiating
conditions. However, 1,3-dibenzoylimidazolidine, 1,3-
dibenzoyl- and 1,3-dipivaloylhexahydropyrimidine, 1,3,5-
Tribenzoylhexahydro-sym-triazine and 1,3,5-
tripivaloylhexahydro-sym-triazine showed reaction under
lithiating conditions.
In chapter 3 the NMR study (equilibria and kinetics) of
bis- and tris-amides was discussed. 1,3-
Dibenzoylimidazolidine, 1,3-dipivaloylimidazolidine and 1,3-
dibenzoylhexahydropyrimidine showed signals in their low
temperature 1H NMR spectra for all of the three conformers.
However, even at very low temperatures, 1,3-
dipivaloylhexahydropyrimidine showed signals for only two
conformers. The signal for the conformer with two pivaloyl
groups on the same side was not observed.
In 1,3,5-tribenzoylhexahydro-sym-triazine the two
conformers were observed in the low temperature ^H NMR
spectrum. However, even at very low temperatures for 1,3,5-
tripivaloylhexahydro-sym-triazine only one conformer was
observed (in agreement with that observed for 1,3-
dipivaloylhexahydropyrimidine).
In conformer population the NMR spectra of all
amides agreed with their corresponding "'"H NMR spectral data

152
except that the signals for the least populated conformers
were not observed.
The relative energy difference between the different
conformers was calculated from the population ratios
obtained. All amides except 1,3,5-tripivaloylhexahydro-sym-
triazine showed only one coalescence temperature. The
energy of activation for the barrier to rotation around
amide C(0)-N bonds was calculated from the coalescence
temperature. The energy, in general, for benzamides, was
around 15 kcal mole ^ and for pivalamides, around 10 kcal
mole â– *â– .
The mechanism of rotation of the amide groups from
their spectral behavior was discussed. The rotations will
be either individual or concerted (same or different
direction). For 1,3,5-tripivaloylhexahydro-sym-triazine,
only one conformational isomer (the symmetrical) was
observed indicating that in that molecule the rotation
around the amide C(0)-N bonds may be concerted (or
correlated) or the rotations may be sequential with the
unsymmetrical conformational isomer as a short lived
intermediate in the transition state of the topomerization
process of the symmetrical conformational isomer.
Furthermore, it was speculated for 1,3,5—
tripivaloylhexahydro-sym-triazine, the least energetic
process for topomerization of the symmetrical conformational

153
isomer would be that in which two amide bonds rotate in one
direction while the third one rotates in the opposite
direction.
The hydrogen-deuterium (H/D) exchange behavior of
different N- and 0- substituted vinylogous amides, such as
the 4-pyridones, was discussed in chapter 4. The main aim
was to explain the ambient temperature hydrogen deuterium
exchange at the 3,5-positions of the pyridine ring in N-(4-
pyridinoxymethyl)-4-pyridone. A number of N-substituted 4-
pyridones and 0-substituted 4-oxypyridines were
investigated.
It was found that a heteroatom (0, S) at the (3-position
of the N-alkyl side chain increased the H/D exchange rate of
the 2,6-protons five fold compared to N-methyl-4-pyridone.
And also a heteroatom with an exchangeable hydrogen or an
acidic C-H at the y-position of the 0-alkyl side chain
increased the H/D exchange rate of the 3,5-protons compared
to 4-methoxypyridine.
The mechanistic study of alkyl group migration from
oxygen to nitrogen in vinylogous amides, such as the 4-
pyridones, was discussed in chapter 5. The rearrangement of
N-(4-pyridinoxymethyl)-4-pyridone at 200°C gave bis(N-4-
pyridonyl)methane. The rearrangement products from (i) N-
(4-pyridinoxymethyl)-4-pyridone, (ii) N-(3,5-dideutero-4-

154
pyridinoxymethyl)-2,6-dideutero-4-pyridone and (iii) a
mixture of N-(4-pyridinoxymethyl)-4-pyridone and N-(3,5-
didetue ro-4-pyridinoxymethyl)-2,6-didetuero-4-pyridone, were
analysed by mass spectrometry. The molecular ion peaks
(from m/z 202 to 208) of (i) and (ii) were used to calculate
the intensities of the molecular ion peaks for (iii) and
compared with the experimentally observed values. The
comparison showed a large increase at m/z 204, indicating
that the thermal rearrangement of alkyl groups from oxygen
to nitrogen in 4-alkoxypyridines was intermolecular.

BIBLIOGRAPHY
The system adopted for references is the one designated
by Katritzky and Rees in their book Comprehensive
Heterocyclic Chemistry, Pergamon Press, New York, 1984, Vol.
4, p. 1085. References are designated by a number-letter
code of which the first two digits (or the first four digits
for references before 1900) denote the year of publication,
the next one or two letters the journal, and the final
digits the page number. Books and all other sources are
coded MI (miscellaneous) and listed under the relevant year
of publication.
Letter Codes for Journal Titles
Code
Full Title
A
Ann. Chim.
ACR
Acc. Chem. Res.
AG ( E )
Angew. Chem. Int. Ed.
AHC
Adv. Heterocycl. Chem.
AJC
Aust. J. Chem.
BCSJ
Bull. Chem. Soc. Jm"-»
BP
Biopolymers
155

156
CB
Chem. Ber.
CC
J. Chem. Soc. Chem.
Commun.
Cl
Chem. Ind.
CJC
Can. J. Chem.
CR
Chem. Rev.
GCI
Gazz. Chim. Ital.
HCA
Helv. Chim. Acta.
JAM
J. Am. Chem. Soc.
JCP
J. Chem. Phys.
JCS
J. Chem. Soc.
JCS(B)
J. Chem. Soc. (B)
JCS(PI)
J. Chem. Soc. Perkin
Trans. 1
JCS(P2)
J. Chem. Soc. Perkin
Trans . 2
JHC
J. Heterocycl. Chem.
JMR
J. Mag. Reson.
JOC
J. Org. chem.
JOM
J. Organomet. Chem.
JPC
J. Phys. Chem.
M
Monatsh. Chem.
MI
Miscellaneous [book/journal]
MM
Macromoleucles
OMR
Org. Mag. Reson.
OR
Org. React.
RC
Rocz. Chim.
S
Synthesis
T
Tetrahedron
TL
Tetrahedron Lett.

157
31CB1049
E. Koenigs and H. Greiner, Chem. Ber., 1931,
64, 1049.
50JOC337
K. W. Campbell, J. F. Ackerman and B. K.
Campbell, J. Org. Chem., 1950, 15, 337.
53JOC534
E. Ochiai, J. Org. Chem., 1953, 18, 534.
55JCP1363
W. D. Phillips, J. Chem. Phys., 1955, 23,
1363 .
57JAM3160
K. B. Wiberg, T. M. Shryne and R. R. Kintner,
J. Am. Chem. Soc., 1957, 79, 3160.
59JCS2844
J. I. G. Cadogan, J. Chem. Soc., 1959, 2844.
60A1409
M. B. Bournazel, Ann. Chim. (Paris), 1960, 5,
1409 .
60JCS1286
F. M. Elkobaisi and W. J. Hickinbottom, J.
Chem. Soc., 1960, 1286.
61CR179
R. Roger and D. G. Neilson, Chem. Rev., 1961,
61, 179.
61JAM3688
D. J. Cram, C. A. Kingsbury and B. Rickborn,
J. Am. Chem. Soc., 1961, 83, 3688.
62JPC540
M. T. Rogers and J. C. Woodbrey, J. Physical
Chem., 1962, 66, 540.
63AHC311
A. R. Katritzky and J. M. Lagowski, Adv. Het.
Chem., 1963, 1, 311.
63JAM3728
L. A. La Planche and M. T. Rogers, J. Am.
Chem. Soc., 1963, 85, 3728.
6 3JAM3 8 9 0
D. J. Cram and L. Gosser, J. Am. Chem. Soc.,
1963, 85, 3890.
63JOC2885
R. B. Moffett, J. Org. Chem., 1963, 28, 2885.
63MI1
B. Pullman and A. Pullman, "Quantum
Biochemistry", Interscience, New York, 1963.
64AHC2
G. F.Duffin, Adv. Het. Chem., 1964, 3, 2.

158
6 4JAM3 3 7
L. A. La Planche and M. T. Rogers, J. Am.
Chem. Soc., 1964, 86, 337.
64JOC892
F. J. Dinan, and H. Tieckelmann, J. Org.
Chem., 1964,29, 892.
64MI1
L. A. Cohen and B. Witkop, in "Molecular
Rearrangements", P. de Mayo, ed., vol.2,
Interscience, New York, 1964.
64RTC186
P. J. V. Haak and Th. J. De Boer, Rec. Trav.
Chim., 1964, 83, 186.
64TL3083
P. Beak and J.Bonham, Tetrahedron Lett., 1964,
3083 .
65AG(E)1075
E. J. Corey and D. Seebach, Ang. Chem. Int.
Edn. Engl., 1965, 4, 1075.
65AG(E)1077
E. J. Corey and D. Seebach, Ang. Chem. Int.
Edn. Engl., 1965, 4, 1077.
65JAM3186
T. M. Harris, S. Boatman and C. R. Hauser,
J. Am. Chem. Soc., 1965, 87, 3186.
6 5JAM3 36 5
P. Beak and J. Bonham, J. Am. Chem. Soc.,
1965, 87, 3365.
65JCP3320
A. G. Wittaker and S. Siegel, J. Chem. Phys.,
1965, 42, 3320.
65JCS4911
D. J. Brown and R. V. Foster, J. Chem. Soc.,
1965, 4911.
6 5JOC1986
Y. Makisumi, J. Org. Chem., 1965, 30, 1986.
650R1
J. W. Schulenberg and S. Archer, Org. Reac.,
1965, 14, 1.
65T1681
A. R. Katritzky, B. Willis, R. T. C. Brownlee
and R. D. Topsom, Tetrahedron, 1965, 21,
1681.
65T2257
H. Pracejus, M. Kehlen, H. Kehlen and H.
Matschiner, Tetrahedron, 1965, 21, 2257.
66CC631
P. Beak and J. Bonham, J. Chem. Soc. Chem.
Comm., 1966, 631.

159
66JAM4766
J. A. Zoltewicz and C. L. Smith, J. Am. Chem.
Soc., 1966, 88, 4766.
66JOC248
G. A. Russel and S. A. Weiner, J. Org. Chem.,
1966, 31, 248.
66JOC3007
R. M. Moriarty, and J. M. Kleigman, J. Org.
Chem., 1966, 31, 3007.
66TL4593
H. A. Staab and D. Lauer, Tetrahedron Lett.,
1966, 4593.
67AJC1643
R. F. Evans, Aust. J. Chem., 1967, 20, 1643.
67CB3397
H. Paulsen and K. Todt, Chem. Ber., 1967, 100
3397 .
67CC122
D. Thacker and T. L. V. Ulbricht, J. Chem.
Soc. Chem. Comm., 1967, 122.
67CC1047
P. Bellingham, C. D. Johnson and A. R.
Katritzky, J. Chem. Soc. Chem. Comm., 1967,
1047 .
67HCA725
C. A. Grob and H. J. Wilkens, Hel. Chim.
Acta, 1967, 725.
67JCS(B)1226
P. Bellingham, C. D. Johnson and A. R.
Katritzky, J. Chem. Soc. (B), 1967, 1226.
67JAM3358
J. A. Zoltewicz and C. L. Smith, J. Am. Chem.
Soc., 1967, 89, 3358.
67JAM4300
H. S. Gutowsky, J. Jonas and T. H. Siddall,
III, J. Am. Chem. Soc., 1967, 89, 4300.
68CJC2821
Y. L. Chow, C. J. Colon and J. N. S. Tam, Can
J. Chem., 1968, 46, 2821.
68CPB715
Y. Kauazoe and Y. Yoshioka, Chem. Pharm. Bull
(Tokyo), 1968, 16, 715.
6 8JAMl56 9
P. Beak, J. Bonham and J. T. Lee Jr., J. Am.
Chem. Soc., 1968, 90, 1569.
68JAM4679
I. I. Schuster, A. K. Colter and R. J.
Kurland, J. Am. Chem. Soc., 1968, 90, 4679.

160
68JCS(B ) 866
P. Bellingham, C. D. Johnson and A. R.
Katritzky, J. Chem. Soc. (B), 1968, 866.
68MI1
"Topics in Stereochemistry" Vol. 3, ed., E.
L. Eliel and N. L. Allinger, Interscience, New
York, 1968.
68RSO601
I. F. Tupitsyn, N. N. Zatsepina, A. V. Kirora
and Yu. M. Kapustin, Reakts. Sposoknost Org.
Soedin, 1968, 5, 601.
69BCSJ1357
N. Sugiyama, M. Yamamoto and C. Kashima, Bull.
Chem. Soc. Japan, 1969, 42, 1357.
69BCSJ2389
C. Kashima, H. Yamamoto, S. Kobayashi and N.
Sugiyama, Bull. Chem. Soc. Japan, 1969, 42,
2389 .
69JAM5501
J. A. Zoltewicz, G. Grahe and C. L. Smith,
J. Am. Chem. Soc., 1969, 91, 5501.
69JOC589
P. Beak, E. M. Monroe, J. Org. Chem., 1969,
34, 589.
69M132
E. Ziegler, I. Herbst and Th. Kappe, Monatsh.
Chem., 1969, 100, 132.
69MM154
Y. Miron, B. R. McGarvey and H. Morawetz,
Macromoleucles, 1969, 2, 154.
69RC1687
L. Stefaniak, T. Urbanski, M. Witanowski and
H. Januszewski, Rocz. Chem., 1969, 43, 1687.
70CR517
W. E. Stewart and T. H. Siddal III, Chem.
Rev., 1970, 70, 517.
70JOC3462
J. A. Zoltewicz and A. A. Sale, J. Org. Chem.,
1970, 35, 3462.
70MI1
"The Chemistry of Amides", ed., J. Zabicky,
Interscience, London, 1970.
71AG(E)570
G. Binsch, E. L. Eliel and H. Kessler, Angew.
Chem. Int. Ed., 1971, 10, 570.
71JAM2225
J. N. Roitman and D. J. Cram, J. Am. Chem.
Soc., 1971, 93, 2225.

161
71JAM2231
J. N. Roitman and D. J. Cram, J. Am. Chem.
Soc., 1971, 93, 2231.
72CC303
B. C. Challis and A. D. Frenkel, J. Chem. Soc.
Chem. Comm., 1972, 303.
72CC788
W. A. Thomas and M. K. Williams, J. Chem.
Soc. Chem. Comm., 1972, 788.
72JCS(P2)755
L. Lunazzi, G. F. Pedulli, M. Tiecco and C. A.
Veracini, J. Chem. Soc. Perkin Trans. 2, 1972,
755.
72JOC3434
G. Montando and P. Finocchiaro, J.Org. Chem.,
1972, 37, 3434.
72MM197
G. Montando, P. Finocchiaro, P. Maravigna and
C. G. Overberger, Macromoleucles, 1972, 5,
197.
73AHC137
G. E. Calf and J. L. Garnett, Adv. Het. Chem.,
1973, 15, 137.
73JHC439
J. B. Kang, G. Sen and B.S. Thyagarajan, J.
Het. Chem., 1973, 10, 439.
74AHC1
J. A. Elvidge, J. R. Jones, C. O'Brien, E. A.
Evans and H. C. Sheppard, Adv. Het. Chem.,
1974, 16, 1.
74BCSJ631
M. Kitano and K. Kuchitsu, Bull. Chem. Soc.
Japan, 1974, 47, 631.
7 4JAM1807
E. L. Eliel, A. A. Hartmann and A. G.
Abatjoglou, J. Am. Chem. Soc., 1974, 96, 1807.
74JAM2260
C. H. Yoder, J. A. Sandberg and W. S. Moore,
J. Am. Chem. Soc., 1974, 96, 2260.
74JCS(P2)1363
J. A. Zoltewicz and R. E. Cross, J. Chem. Soc.
Perkin Trans. 2, 1974, 1363.
74MI1
"The Chemistry of Heterocyclic Compounds" ed.,
A. Weissberger and E. C. Taylor, v. 14,
supplement part 3, Interscience, New York,
1974 .

162
75BCSJ553
H. Nishihara, K. Nishihara, T. Uefuji and N.
Sakota, Bull. Chem. Soc. Japan, 1975, 48, 553.
75CJC1682
P. Deslongchamps, U. D. Cheriyan and D. R.
Patterson, Can. J. Chem., 1975, 53, 1682.
75GCI569
P. Finocchiaro and S. Caccamese, Gazz. Chim.
Italiana, 1975, 105, 569.
75JOC231
D. Seebach and E. J. Corey, J. Org. Chem.,
1975, 40, 231.
750R1
S. J. Rhoads and R. Raulins, Org. Reac., 1975,
22, 1.
76ACR26
K. Mislow, Acc. Chem. Res., 1976, 9, 26.
76RC2167
B. Boduszek and J. S. Wieczorek, Rocz. Chem.,
1976, 50, 2167.
76S467
D. J. Tracy, Synthesis, 1976, 467.
77BP1465
H. N. Cheng and F. A. Bovey, Biopolymers,
1977, 16, 1465.
77CI127
R. Louw and P. W. Franken, Chem. Ind., 1977,
127 .
77JAM8262
A. G. Abatjoglou, E. L. Eliel and L. F.
Kuyper, J. Am. Chem. Soc., 1977, 99, 8262.
77JOC3094
C. T. Goralski and G. A. Burk, J. Org. Chem.,
1977, 42, 3094.
77S589
G. B. Bennett, Synthesis, 1977, 589.
77TL1839
P. Beak, B. G. McKinnie and D. B. Reitz,
Tetrahedron Lett., 1977, 22, 1839.
78CR275
P. Beak and D. B. Reitz, Chem. Rev., 1978, 78,
275.
78JCS(P2)1157
J. S. Davies and W. A. Thomas, J. Chem. Soc.
Perkin Trans. 2, 1978, 1157.
78JMR131
D. Hofner, D. S. Stephenson and G. Binsch, J.
Mag. Res., 1978 , 32, 131.

163
78MI1
"Sadtler Standard Carbon-13 NMR Spectra”,
1978. Spectrum numbers 408, 95 and 3162.
7 9AG(E)2 3 9
D. Seebach, Ang. Chem. Int. Ed., 1979, 18,
239 .
79MI1
B. C. Challis and J. A. Challis in
"Comprehensive Organic Chemistry", Pergamon,
Oxford, 1979. Volume 2, chapter 9.9.
80CC87
M. R. Winkle, J. M. Lansinger and R. C.
Ronald, J. Chem. Soc. Chem. Comm., 1980, 87.
81JOC4108
N.G. Rondan, K. N. Houk, P. Beak, W. J.
Zajdel, J. Chandrasekhar and P. V. R.
Schleyer, J. Org. Chem., 1981, 46, 4108.
81JOC4316
D. B. Reitz, P. Beak and A. Tse, J. Org.
Chem., 1981, 46, 4316.
82T539
J. C. Gramain, N. Simonet, G. Vermeersch, N.
F. -Garot, S. Caplain and A. L. -Combier,
Tetrahedron, 1982, 38, 539.
83CJC2572
A. Rauk, D. F. Tavares, M. A. Khan, A. J.
Borkent and J. F. Olson, Can. J. Chem., 1983,
61, 2572.
8 3JAM6622
L. E. Overman, M. Kakimoto, M. E. Okazaki
and G. P. Meier, J. Am. Chem. Soc., 1983, 105,
6622 .
83JAM6629
L. E. Overman, L. T. Mendelson and E. J.
Jacobsen, J. Am. Chem. Soc., 1983, 105, 6629.
83T4133
A. R. Katritzky, A. E. Rahman, D. E. Leahy and
0. A. Schwarz, Tetrahedron, 1983, 39, 4133.
84CR471
P. Beak, W. J. Zajdel and D. B. Reitz, Chem.
Rev., 1984, 84, 471.
84JCS(P2)1089
G. Cirrincione, W. Hinz and R. A. Jones, J.
Chem. Soc. Perkin Trans. 2, 1984, 1089.
84JCS(Pi)1949
F. Babudri, S. Florio, A. Reho and G. Trapani,
J. Chem. Soc. Perkin Trans. 1, 1984, 1949.
84TL1223
A. R. Katritzky, G. R. Khan, and 0. A.
Schwarz, Tetrahedron Lett., 1984, 25, 1223.
84TL4787
U. Norinder and q wennerctrom, Tetrahedron
Lett.. 1984, 15 1787-
8 5 M11
Jerry March, "Advanced Organic Chemistry",
third edition, Wiley-Interscience, New York,
1985 .

BIOGRAPHICAL SKETCH
Ramiah Murugan was born on July 30, 1956 at Madurai, a
city in Tamil Nadu state in India. He received his Bachelor
of Science (special) degree in chemistry from American
College (affiliated to Madurai University) in April 1975.
Then he received his Master of Science degree in chemistry
(with specialization in organic chemistry) from the School
of Chemistry of Madurai University in April 1977. He was
awarded a gold medal for securing the first rank in the
University. From November 1977 to May 1978 he received a
CSIR Junior Research Fellowship from the Government of
India. From June 1978 to December 1981 he served as Junior
Scientist at University Service and Instrumentation Centre
of Madurai University, during which time he was in charge of
the Analytical Division and was also teaching organic
spectroscopy to Master of Science students. He entered the
graduate programme in chemistry at the University of Florida
in January 1982 to work towards his Ph. D.
He has an elder sister, two younger sisters and four
younger brothers. He is married to Sutharchana Devi and has
one daughter Meenasarani Linde.
164

I certify that I have read this study and that in my
opinion it confirms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality, as
a dissertation for the degree of Doctor of Philosophy.
V
Alan R. Katritzky, Chairman
Professor of Chemistry
I certify that I have read this study and that in my
opinion it confirms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality, as
a dissertation for the degree of Doctor of Philosophy.
William R. Dolbie r, Jr.
Professor of Chemist'ry
I certify that I have read this study and that in my
opinion it confirms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality, as
a dissertation for the degree of Doctor of Philosophy.
\
William M. Jorres
Professor of Chemisiry
I certify that I have read this study and that in my
opinion it confirms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality, as
a dissertation for the degree of Doctor of Philosophy.
Merle A. Bat tiste
Professor of Chemistry

I certify that I have read this study and that in my
opinion it confirms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality, as
a dissertation for the degree of Doctor of Philosophy.
Nicholas S.Bodor
Professor of Medicinal Chemistry
This dissertation was submitted to the Graduate Faculty
of the Department of Chemistry in the College of Liberal
Arts and Sciences and to the Graduate School and was
accepted as partial fulfillment of the requirements for the
degree of Doctor of Philosophy.
May, 1987
Dean, Graduate School

UNIVERSITY OF FLORIDA
3 1262 08554 1646

H0026

H0026
££* *'b 3-43 3-?3-i\ -Üa
44 44 metallationconfoOOmuru



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 EEXX2NJAI_FP1VR4 INGEST_TIME 2011-11-03T17:15:19Z PACKAGE AA00004844_00001
AGREEMENT_INFO ACCOUNT UF PROJECT UFDC
FILES



PAGE 2

0(7$//$7,21 &21)250$7,21$/ $1$/<6,6 +<'52*(1 (;&+$1*( $1' 5($55$1*(0(17 ,1 $0,'(6 %< 5$0,$+ 0858*$1 $ ',66(57$7,21 35(6(17(' 72 7+( *5$'8$7( 6&+22/ 2) 7+( 81,9(56,7< 2) )/25,'$ ,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

7R P\ ZLIH 6XWKDUFKDQD 'HYL

PAGE 4

$&.12:/('*0(176 ZRXOG OLNH WR VLQFHUHO\ WKDQN P\ UHVHDUFK GLUHFWRU 3URIHVVRU $ 5 .DWULW]N\ IRU KLV DGYLFH JXLGDQFH SDWLHQFH DQG VXSSRUW WKURXJK RXW WKH ODVW ILYH \HDUV ZRXOG DOVR OLNH WR WKDQN 3URIHVVRU : 0 -RQHV IRU KLV DGYLFH VXSSRUW DQG EOHVVLQJV GXULQJ WKH FUXFLDO PRPHQWV RI OLIHf§P\ PDUULDJH ZRXOG OLNH WR WKDQN 3URIHVVRU : 6 %UH\ 3URIHVVRU $ =ROWHZLF] DQG 'U 5 : .LQJ IRU WKHLU KHOSIXO GLVFXVVLRQV GXULQJ WKH FRXUVH RI WKLV ZRUN ZRXOG DOVR OLNH WR WKDQN YHU\ PXFK DOO WKH PHPEHUV RI RXU UHVHDUFK JURXS SDVW DQG SUHVHQW RI WKH ODVW ILYH \HDUV IRU WKHLU IULHQGVKLS VXSSRUW DQG ZRQGHUIXO GLVFXVVLRQV 6SHFLDO WKDQNV DUH GXH WR 0U -DPVKHG 1 /DP 0U 6WHYH &DWR DQG 'U *RUGRQ 5HZFDVWOH IRU WKHLU VXJJHVWLRQV DIWHU UHDGLQJ WKURXJK WKH PDQXVFULSW ZRXOG DOVR OLNH WR WKDQN DOO WKH IDFXOW\ DQG VWDII RI WKH &KHPLVWU\ 'HSDUWPHQW IRU WKHLU XQGHUVWDQGLQJ DQG IULHQGVKLS /DVW EXW QRW OHDVW ZRXOG OLNH WR WKDQN P\ IDPLO\ HVSHFLDOO\ P\ GDXJKWHU IRU SXWWLQJ XS ZLWK PH GXULQJ WKH SURFHVV RI ZULWLQJ DQG W\SLQJ rKLV GLVVHUWDWLRQ LQ

PAGE 5

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

PAGE 6

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

PAGE 7

$LP RI WKH :RUN 5HVXOWV DQG 'LVFXVVLRQ +\GURJHQ 'HXWHULXP ([FKDQJH LQ 1 3\ULGLQR[\PHWK\O fS\ULGRQH +\GURJHQ 'HXWHULXP ([FKDQJH LQ 1 3KHQR[\PHWK\OfS\ULGRQH DQG 1$U\OWKLRPHWK\OfS\ULGRQHV +\GURJHQ 'HXWHULXP ([FKDQJH LQ 'LPHWK\ODONR[\S\ULGLQH 0RGHO &RPSRXQGV +\GURJHQ 'HXWHULXP ([FKDQJH LQ $ONR[\S\ULGLQH 0RGHO FRPSRXQGV &RQFOXVLRQV ([SHULPHQWDO 0HWKRGV DQG 5HDJHQWV 3UHSDUDWLRQ RI 1S\ULGLQR[\PHWK\Of S\ULGRQH 3UHSDUDWLRQ RI 13KHQR[\PHWK\Of S\ULGRQH DQG 1$U\OWKLRPHWK\f S\U LGRQH 3UHSDUDWLRQ RI 13\ULG\OHWK\Of S\ULGRQH 3UHSDUDWLRQ RI 'LPHWK\O DONR[\S\UL GLQHV 3UHSDUDWLRQ RI $ONR[\S\ULGLQH 0RGHO &RPSRXQGV 5($55$1*(0(17 ,1 $0,'(6 2;<*(1 72 1,752*(1 0,*5$7,21 2) $/.
PAGE 8

/,67 2) 7$%/(6 7DEOH SDJH )RUPDWLRQ RI D/LWKLR 6SHFLHV RI $PLGHV DQG WKHLU 5HDFWLRQ ZLWK (OHFWURSKLOHV 105 &KHPLFDO 6KLIWV SSPf 9DOXHV +]f DQG 5HODWLYH 3RSXODWLRQ bf RI 'LDF\OLPLGD]ROLGLQHV f DQG f 105 &KHPLFDO 6KLIWV SSPf DQG 5HODWLYH 3RSXODWLRQ bf RI 'LDF\OKH[DK\GURS\ULPLGLQHV f DQG f ‘n+ 105 &KHPLFDO 6KLIWV SSPf DQG 5HODWLYH 3RSXODWLRQ bf RI 7ULDF\OKH[DK\GURV\P WULD]LQHV f DQG f A & 105 &KHPLFDO 6KLIWV SSPf RI 'LDF\O LPLGD]RO LGLQHV f DQG f A& 105 &KHPLFDO 6KLIWV SSPf RI 'LDF\OKH[DK\GURS\ULPLGLQHV f DQG f OA& 105 &KHPLFDO 6KLIWV SSPf RI 7ULDF\OKH[DK\GURV\PWULD]LQHV f DQG f 5HODWLYH $*r NFDO PROH Af IRU 'LIIHUHQW &RQIRUPHUV RI $PLGHV f &RDOHVFHQFH 7HPSHUDWXUHV DQG WKH )UHH (QHUJLHV RI $FWLYDWLRQ RI $PLGHV f 0DVV 6SHFWUDO 'DWD RI WKH 0ROHFXODU ,RQV IRU WKH 5HDUUDQJHG 3URGXFWV IURP f f DQG D 0L[WXUH RI f DQG f &DOFXODWHG 0DVV 6SHFWUDO 3HDN ,QWHQVLWLHV DQG WKH 'LIIHUHQFH %HWZHHQ WKH &DOFXODWHG DQG ([SHULPHQWDO 0DVV 6SHFWUDO 3HDN ,QWHQVLWLHV YL L

PAGE 9

/,67 2) ),*85(6 )LJXUH SDJH 0DMRU 5HVRQDQFH )RUPV IRU $PLGHV 6KRZLQJ 3UHGLFWHG %RQG /HQJWKV $f DQG %RQG $QJOHV 0HDQ 9DOXHV RI %RQG /HQJWKV $f DQG $QJOHV LQ &U\VWDOOLQH $PLGHV 0+] A+ 105 6SHFWUXP RI 'LEHQ]R\OLPLGD]ROLGLQH LQ &'&OAf DW r& 0+] + 105 6SHFWUXP RI 'LEHQ]R\OLPLGD]ROLGLQH LQ &'&OAf DW r& 0+] A+ 105 6SHFWUXP RI 'LS L YD OR\O LPL GD]R L G L QH LQ &'&O A f DW r& 0+] A+ 105 6SHFWUXP RI 'LSLYDOR\OLPLGD]ROLGLQH LQ &'&OAf DW r& 0+] A+ 105 6SHFWUXP RI 'LEHQ]R\OKH[DK\GURS\ULPLGLQH LQ &'&OAf DW r& 0+] A+ 105 6SHFWUXP RI 'LEHQ]R\OKH[DK\GURS\ULPLGLQH LQ &'&Of DW r& 0+] A+ 105 6SHFWUXP RI 'LSLYDOR\OKH[DK\GURS\ULPLGLQH LQ &'&Of DW & 0+] A+ 105 6SHFWUXP RI 'LSLYDOR\OKH[DK\GURS\ULPLGLQH LQ &'&Of DW & 0+] A+ 105 6SHFWUXP RI 7ULEHQ]R\OKH[DK\GURV\PWULD]LQH LQ &'&Of DW & 0+] A+ 105 6SHFWUXP RI f§ 7ULEHQ]R\OKH[DK\GURV\PWULD]LQH LQ &'&Of DW & 0+] ‘nn+ 105 6SHFWUXP RI 7ULSLYDOR\OKH[DK\GURV\PWULD]LQH LQ &'&Of DW & Y L L L

PAGE 10

0+] & 105 6SHFWUXP RI 'LEHQ]R\OLPLGD]ROLGLQH LQ &'&OAf DW r& 0+] A& 105 6SHFWUXP RI 'LEHQ]R\OLPLGD]ROLGLQH LQ &'&OAf DW r& 0+] & 105 6SHFWUXP RI 'LSLYDOR\OLPLGD]ROLGLQH LQ &'&OAf DW r& 0+] & 105 6SHFWUXP RI 'LSLYDOR\OLPLGD]ROLGLQH LQ &'&OAf DW r& 0+] A& 105 6SHFWUXP RI 'LEHQ]R\OKH[DK\GURS\ULPLGLQH LQ &'&OAf DW r& 0+] A& 105 6SHFWUXP RI 'LEHQ]R\OKH[DK\GURS\U LPLGLQH LQ &'&O f DW & I 0+] & 105 6SHFWUXP RI 'LSLYDOR\OKH[DK\GURS\ULPLGLQH LQ &'&Of DW & 0+] & 105 6SHFWUXP RI 'LSLYDOR\OKH[DK\GURS\ULPLGLQH LQ &'&Of DW r& 7 0+] & 105 6SHFWUXP RI 7ULEHQ]R\OKH[DK\GURV\PWULD]LQH LQ &'&Of DW & 7 0+] ‘n& 105 6SHFWUXP RI 7ULEHQ]R\OKH[DK\GURV\PWULD]LQH LQ &'&Of DW & 7 0+] & 105 6SHFWUXP RI 7ULSLYDOR\OKH[DK\GURV\PWULD]LQH LQ &'&Of DW & 0+] + 105 6SHFWUXP RI 1 3\ULGLQR[\PHWK\OfS\ULGRQH LQ '062GJf 0+] + 105 6SHFWUXP RI 1 3\ULGLQR[\PHWK\OfS\ULGRQH LQ 1D2''062GILf $IWHU ([FKDQJH DW r& 0+] A+ 105 6SHFWUXP RI 1 3\ULGLQR[\PHWK\OfS\ULGRQH LQ 1D2''062GAf $IWHU ([FKDQJH DW r& ,;

PAGE 11

0+] + 105 6SHFWUXP RI 3\ULGLQR[\ f HWKDQRO LQ '062GJf 0+] + 105 6SHFWUXP RI f§f§ 3\ULGLQR[\f HWKDQRO LQ &'21D&'2''062Gf DW r& 0+] + 105 6SHFWUXP RI f§ 3\ULGLQR[\fHWKDQRO LQ &'21D&'2''062GIL f $IWHU ([FKDQJH DW r& ,OO 0+] + 105 6SHFWUXP RI $PLQRSKHQR[\fS\ULGLQH LQ &'A21D'062GJf 0+= + 105 6SHFWUXP RI f§ $PLQRSKHQR[\fS\ULGLQH LQ &'21D'062Gf $IWHU ([FKDQJH DW r& %DVH FDWDO\]HG +\GURJHQ 'HXWHULXP ([FKDQJH LQ 'LIIHUHQW 1 DQG 2VXEVWLWXWHG 3\ULGRQHV 0DVV 6SHFWUXP RI Df 13\ULGLQR[\PHWK\Of S\ULGRQH Ef 13\ULGLQR[\PHWK\Of GLGHXWHURS\ULGRQH DQG Ff 1'LGHXWHUR S\ULGLQR[\PHWK\OfGLGHXWHURS\ULGRQH 0+] A+ 105 6SHFWUXP RI 1 3\ULGLQR[\PHWK\OfS\ULGRQH LQ '062GJf 0+] A+ 105 6SHFWUXP RI WKH 0DMRU 3URGXFW RI 5HDUUDQJPHQW %LV1S\ULGRQ\OfPHWKDQH LQ '062GJ f 0+] A+ 105 6SHFWUXP RI WKH 0LQRU 3URGXFW 2EWDLQHG 13\ULG\OfS\ULGRQH LQ '062GJf 0DVV 6SHFWUXP RI WKH 5HDUUDQJHG 3URGXFW 2EWDLQHG IURP 1 3\U LGLQR[\PHWK\OfS\U LGRQH 0DVV 6SHFWUXP RI WKH 5HDUUDQJHG 3URGXFW 2EWDLQHG IURP 1'LGHXWHURS\ULGLQR[\PHWK\Of GLGHXWH URS\U LGRQH 0DVV 6SHFWUXP RI WKH 5HDUUDQJHG 3URGXFW 2EWDLQHG IURP D 0L[WXUH RI 13\ULGLQR[\PHWK\Of S\ULGRQH DQG 1'LGHXWHUR S\ULGLQR[\PHKW\OfGLGHXWHURS\ULGRQH [

PAGE 12

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

PAGE 13

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fS\ULGRQH ZKLFK H[FKDQJHV WKH S\ULGRQH SURWRQV LQ DGGLWLRQ WR WKH S\ULGLQH SURWRQV DW WHPSHUDWXUHV EHWZHHQ r& 6WXGLHV RI PRGHO FRPSRXQGV VXFK DV f§f§ S\ULGLQR[\PHWK\OfHWKDQRO FRQILUP WKLV H[SODQDWLRQ 7KH PHFKDQLVP IRU WKH WKHUPDO UHDUUDQJHPHQW RI DON\O JURXSV IURP R[\JHQ WR QLWURJHQ LQ S\ULGRQHV KDG EHHQ SURSRVHG EXW QRW SURYHG $ PHFKDQLVWLF VWXG\ RI WKH WKHUPDO UHDUUDQJHPHQW XVLQJ WKH ODEHOOHG FRPSRXQG 1GLGHXWHUR S\ULGLQR[\PHWK\OfGLGHXWHURS\ULGRQH DQG LWV XQODEHOOHG DQDORJXH ZDV LQYHVWLJDWHG %DVHG RQ WKH SURGXFW UDWLRV REWDLQHG E\ PDVV VSHFWURPHWU\ WKH UHDUUDQJHPHQW ZDV IRXQG WR EH LQWHUPROHFXODU ;,

PAGE 14

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

PAGE 15

6WUXFWXUH RI WKH $PLGH *URXS 7KH SK\VLFDO VWUXFWXUH RI WKH DPLGH JURXS KDV EHHQ WKH VXEMHFW RI PXFK UHFHQW ZRUN 5HYLHZV RQ WKH PROHFXODU DQG HOHFWURQLF VWUXFWXUH >0,@ DQG QXFOHDU PDJQHWLF UHVRQDQFH 105f SURSHUWLHV >&5@ VXPPDUL]H PXFK RI WKH QHZ GHYHORSPHQWV LQFOXGLQJ WKH VKDSH DQG VWHUHRFKHPLVWU\ RI WKH DPLGH JURXS DQG VSHFWURVFRSLF SURSHUWLHV f *HRPHWU\ 7KH PROHFXODU VWUXFWXUH RI WKH DPLGH JURXS LQ ERWK WKH FRQGHQVHG DQG JDVHRXV SKDVHV LV IDLUO\ ZHOO HVWDEOLVKHG +RZHYHU VHYHUDO FRPSOLFDWLQJ IHDWXUHV QHHG WR EH WDNHQ LQWR FRQVLGHUDWLRQ ZKHQ LQWHUSUHWLQJ SK\VLFDO PHDVXUHPHQWV RQ WKHVH FRPSRXQGV 2QH RI WKHVH IHDWXUHV LV WKH SDUWLDO GRXEOH ERQG FKDUDFWHU RI WKH &f1 ERQG UHVXOWLQJ IURP GHORFDOL]DWLRQ RI WKH QLWURJHQ ORQH SDLU HOHFWURQV LQWR WKH QV\VWHP RI WKH FDUERQ\O ERQG 7KHUH DUH WZR H[WUHPH YDOHQFH ERQG IRUPV ]HUR FRQMXJDWLRQ Df DQG FRPSOHWH FRQMXJDWLRQ Ef DV VKRZQ LQ )LJXUH

PAGE 16

Ef )LJ 0DMRU 5HVRQDQFH )RUPV IRU $PLGHV 6KRZLQJ 3UHGLFWHG %RQG /HQJWKV ƒf DQG %RQG $QJOHV >0,@ ;UD\ GLIIUDFWLRQ VWXGLHV RI FU\VWDOOLQH DPLGHV >0,@ VKRZ D IDLUO\ FRQVWDQW JHRPHWU\ IRU WKH DPLGH JURXS $OO WKH KHDY\ DWRPV RI WKH DPLGH IXQFWLRQDOLW\ DUH HVVHQWLDOO\ LQ D SODQH 7KH PHDQ YDOXHV RI WKH ERQG OHQJWKV DQG WKH ERQG DQJOHV DUH JLYHQ LQ f )LJXUH f )LJ R 0HDQ 9DOXHV RI %RQG /HQJWKV $f DQG $QJOHV LQ &U\VWDOOLQH $PLGHV >0,@ 7KH JDV SKDVH PLFURZDYH DQG HOHFWURQ GLIIUDFWLRQ VWXGLHV >0@ >%&6-@ FRPSDUHG WR ;UD\ GLIIUDFWLRQ

PAGE 17

VWXGLHV RI FU\VWDOOLQH DPLGHV VKRZ WKDW WKH ERQG DQJOHV UHPDLQ HVVHQWLDOLW\ WKH VDPH EXW WKH & ERQG OHQJWK LV UHGXFHG WR ƒ ZLWK FRQFRPLWDQW OHQJWKHQLQJ RI WKH &1 ERQG WR ƒ 7KLV LPSOLHV WKDW WKHUH LV D JUHDWHU FRQWULEXWLRQ IURP VWUXFWXUH Df LQ WKH JDV SKDVH WKDQ LQ WKH VROLG SKDVH 5RWDWLRQDO %DUULHU 2QH RI WKH PRVW IXQGDPHQWDO FRQFHSWV LQ DOO LQYHVWLJDWLRQV RI VWUXFWXUH LV FRQIRUPDWLRQDO DQDO\VLV ,Q DPLGHV WKH FRQVHTXHQFH RI SDUWLDO GRXEOHERQG FKDUDFWHU LV WKH H[LVWHQFH RI FRQIRUPDWLRQDO LVRPHUV f DQG f DULVLQJ IURP WKH ODFN RI IUHH URWDWLRQ DERXW WKH &f1 ERQG 7KH H[LVWHQFH RI WKHVH LVRPHUV KDV EHHQ HVWDEOLVKHG E\ GLSROH PRPHQW PHDVXUHPHQW >-$0@ LQIUDUHG DQG 5DPDQ VSHFWURVFRSLF VWXGLHV >0,@ DQG E\ QXFOHDU PDJQHWLF UHVRQDQFH 105f FLV (f WUDQV =f f f

PAGE 18

$PLGHV KDYH EHHQ LQWHQVLYHO\ VWXGLHG E\ 105 >&5@ 7KRXJK PRVW RI WKHVH VWXGLHV KDYH GHDOW ZLWK URWDWLRQDO LVRPHUL]DWLRQ DERXW WKH &f1 ERQG FRQVLGHUDEOH DWWHQWLRQ KDV DOVR EHHQ JLYHQ WR FKHPLFDO VKLIWV FRXSOLQJV SURWRQ H[FKDQJH DQG DVVRFLDWLRQ RI WKH DPLGHV 7KH HIIHFW RI VROYHQW DQG FRQFHQWUDWLRQ RQ WKH IUHH HQHUJ\ RI DFWLYDWLRQ EDUULHUf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

PAGE 19

$F\FOLF DQG &\FOLF $PLGHV 7KH PRVW FRPPRQ V\QWKHWLF SDWKZD\ IRU DPLGHV WKHPVHOYHV LV WKDW RI ERQG IRUPDWLRQ EHWZHHQ D FDUERQ\OFDUERQ DWRP DQG DQ DPLQRQLWURJHQ DWRP DQG WKLV LV DFKLHYHG E\ WUHDWPHQW RI HLWKHU DPPRQLD RU D SULPDU\ RU D VHFRQGDU\ DPLQH ZLWK DQ DF\ODWLQJ DJHQW 7KLV \LHOGV D SULPDU\ VHFRQGDU\ RU WHUWLDU\ DPLGH UHVSHFWLYHO\ 7KH RWKHU FRPPRQ SDWKZD\ IRU DPLGH IRUPDWLRQ LV WKH LQWURGXFWLRQ RI D FDUERQ\O JURXS LQWR DQ XQVDWXUDWHG DPLQR FRPSRXQG IRU H[DPSOH SDUWLDO K\GUDWLRQ RI HLWKHU D QLWULOH RU DQ LPLGR\O GHULYDWLYH SURGXFLQJ WKH SULPDU\ RU VHFRQGDU\ DPLGH UHVSHFWLYHO\ 7KH LPLGR\O GHULYDWLYH LWVHOI FDQ LQ SULQFLSOH EH REWDLQHG E\ DON\ODWLRQ RI WKH QLWULOH 0HWKRGV RI 1DON\O RU 1DU\O ERQG IRUPDWLRQ RWKHU WKDQ GLUHFW UHSODFHPHQW RI WKH DPLGR +f SULQFLSDOO\ UHTXLUH UHDUUDQJHPHQWV VXFK DV LQ WKH 6FKPLGW RU %HFNPDQQ UHDFWLRQV 6\QWKHVLV RI DPLGHV E\ IRUPDWLRQ RI WKH ERQG EHWZHHQ DQ DON\O RU DU\O JURXS DQG WKH FDUERQ\O FDUERQ DWRP LV WKH PRVW GLIILFXOW PHWKRG WR DFKLHYH DQG UHTXLUHV PRUH VSHFLILF UHDJHQWV VXFK DV NHWHQHV LVRF\DQDWHV DQG LVRF\DQLGHV 1HLWKHU GLUHFW R[LGDWLRQ QRU UHGXFWLRQ RI VXLWDEOH SUHFXUVRUV KDV ZLGH DSSOLFDELOLW\ LQ DPLGH V\QWKHVLV 7KH V\QWKHVLV RI ODFWDPV F\FOLF DPLGHVf JHQHUDOO\ IROORZV WKH VDPH SURFHGXUHV DV IRU DF\FOLF DPLGHV H[FHSW

PAGE 20

ZKHUH VSHFLDO IDFWRUV VXFK DV ULQJ VL]H DQG HDVH RI UHDFWLRQ DUH FRQFHUQHG )XUWKHU PRGLILFDWLRQ RI WKH SDUHQW ODFWDP FDQ EH DFKLHYHG E\ DON\ODWLRQ RI WKH QLWURJHQ DWRP DQG VRPHWLPHV RI WKH FDUERQ D WR WKH FDUERQ\O JURXS XVLQJ FRQGLWLRQV VLPLODU WR WKRVH IRU DF\FOLF DPLGH DON\ODWLRQ 7KH QHZ PHWKRG DYDLODEOH IRU DPHWDOODWLRQ RI DPLGHV D WR QLWURJHQf IROORZHG E\ HOHFWURSKLOLF DGGLWLRQ JLYLQJ F[ HOHFWURSKLOH VXEVWLWXWHG DPLGHV >&5@ 7KLV ZDV RQH RI WKH PHWKRGV XVHG IRU SUHSDULQJ DPHWDOORDPLQH V\QWKHWLF HTXLYDOHQWV IRU IXUWKHU GHWDLOV VHH &KDSWHU f 9LQ\ORJRXV $PLGHV 3\ULGRQHV FDQ EH SUHSDUHG LQ WZR EDVLF ZD\V E\ ULQJ FORVXUH UHDFWLRQV DQG E\ WKH WUDQVIRUPDWLRQ RI RWKHU ULQJ FRPSRXQGV )RU H[DPSOH LQ WKH ODWWHU FDVH S\URQHV FDQ EH WUDQVIRUPHG LQWR S\ULGRQHV MXVW E\ WUHDWLQJ WKH FRUUHVSRQGLQJ S\URQHV ZLWK WKH UHTXLUHG DPLQHV +RZHYHU WKH ULQJ FORVXUH UHDFWLRQV \LHOGLQJ S\ULGRQHV KDYH PDQ\ PRUH SRVVLEOLWLHV XVLQJ Lf D WULNHWRQH RU D NHWRDOGHK\GH DQG DPPRQLD >-$0@ LLf GLNHWRQHV DQG DURPDWLF 6FKLII EDVHV >%&6-O @ LLLf GLNHWRQHV DQG EHQ]RQLWULOH >%&6-@ LYf GLOSURS\Q\O NHWRQH DQG SULPDU\ DPLQHV $DQG Yf SULPDU\ DQG VHFRQGDU\ HQDPLQHV SUHSDUHG IURP HWK\O DFHWRDFHWDWH RU GLNHWRQHV ZLWK GLNHWHQH >0@

PAGE 21

5HDFWLYLW\ RI $PLGHV 6LQFH DOO WKUHH DWRPV LQ WKH 2&1 FKDLQ DUH SRWHQWLDOO\ UHDFWLYH DPLGHV EHFRPH YHUVDWLOH RUJDQLF FRPSRXQGV 7KLV LV SULPDULO\ GXH WR WKH GHORFDOL]DWLRQ RI WKH Q HOHFWURQV DORQJ WKH 2&1 FKDLQ +HQFH WKH JURXQG VWDWH VWUXFWXUH RI DPLGH LV D K\EULG RI WKH WZR UHVRQDQFH IRUPV Df DQG Ef $OWKRXJK YHUVDWLOLW\ RIWHQ PHDQV FRPSOH[LW\ VLPSOLILFDWLRQ KHUH FDQ EH DFKLHYHG E\ UHFRJQL]LQJ WKDW WKH PDMRULW\ RI UHDFWLRQV RI DPLGHV IDOO LQWR WZR FODVVHV 7KH ILUVW LQYROYHV QXFOHRSKLOLF DWWDFN E\ WKH R[\JHQ DWRP RU RFFDVLRQDOO\ E\ WKH QLWURJHQ DWRP RQ HLWKHU SRVLWLYHO\ FKDUJHG RU QHXWUDO HOHFWURSKLOLF UHDJHQWV +HUH WKH UHVRQDQFH IRUP Ef LV XVXDOO\ WKH PRUH DSSURSULDWH UHDFWLYH VSHFLHV 7KH VHFRQG DQG OHVV FRPPRQ SURFHVV LQYROYHV QXFOHRSKLOLF DGGLWLRQ WR WKH DPLGH FDUERQ\O JURXS RI Df 0RVW RWKHU UHDFWLRQV RI DPLGHV VXFK DV GHK\GUDWLRQ HOLPLQDWLRQ GHDPLQDWLRQ HWF DUH VHTXHQWLDO WR WKHVH WZR SURFHVVHV Df Ef

PAGE 22

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f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

PAGE 23

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f WR LQYHVWLJDWH WKH V\QHUJLVWLF HIIHFW RI DPLGH IXQFWLRQDOLW\ RQ WKH DPHWDOODWLRQ RI DPLGHV LLf WR VWXG\ WKH FRQIRUPDWLRQDO EHKDYLRU HTXLOLEULD DQG NLQHWLFVf RI ELVn DQG WULVDPLGHV XVLQJ 105 VSHFWURVFRS\ LLLf WR HOXFLGDWH WKH PHFKDQLVP RI WKH UHDUUDQJHPHQW RI DQ LPLGDWH WR DQ DPLGH LQ D YLQ\ORJRXV DPLGH DQG LYf WR VWXG\ WKH EDVH FDWDO\]HG K\GURJHQ GHXWHULXP H[FKDQJH EHKDYLRU RI GLIIHUHQW DQG 1 VXEVWLWXWHG YLQ\ORJRXV DPLGHV

PAGE 24

&+$37(5 0(7$//$7,21 2) $0,'(6 ,QWURGXFWLRQ 7KH PDLQ DLP RI WKH PHWDOODWLRQ VWXGLHV RQ DPLGHV ZDV IRU WKH WUDQVIRUPDWLRQ RI DPLQHV LQWR DVXEVWLWXWHG DPLQHV 7KHUHIRUH EHIRUH GLVFXVVLQJ WKH REMHFWLYH RI WKLV ZRUN D EULHI GLVFXVVLRQ LV JLYHQ RQ WKH GLIIHUHQW PHWKRGV DYDLODEOH IRU DPLQH WUDQVIRUPDWLRQ 7KH FODVVLFDO PHWKRGV IRU WKH SUHSDUDWLRQ DQG WUDQVIRUPDWLRQ RI DPLQHV HPSOR\ Lf QXFOHRSKLOLF VXEVWLWXWLRQ E\ QLWURJHQ LLf QXFOHRSKLOLF DGGLWLRQ WR D FDUERQ QLWURJHQ GRXEOH ERQG DQG LLLf UDGLFDO VXEVWLWXWLRQ DW FDUERQ DGMDFHQW WR QLWURJHQ VFKHPH f 1 < 1 ( 1 , 1 f§ 6FKHPH 5HFHQW PHWKRGV KRZHYHU LQYROYH LQWURGXFLQJ DQ DFWLYDWLQJ JURXS RQ WKH QLWURJHQ DWRP DQG WKHQ UHPRYLQJ WKH SURWRQ IURP WKH FDUERQ DGMDFHQW WR WKH QLWURJHQ XVLQJ PHWDO

PAGE 25

DON\OV WR JHQHUDWH DPHWDOOR DPLQH V\QWKHWLF HTXLYDOHQWV 7KHQ DGGLWLRQ RI DQ HOHFWURSKLOH IROORZHG E\ WKH UHPRYDO RI DFWLYDWLQJ JURXS JLYHV WKH DHOHFWURSKLOH VXEVWLWXWHG DPLQH VFKHPH f + 1f§+ 6FKHPH = W f $ QXPEHU RI VSHFLHV KDYH EHHQ XVHG DV DFWLYDWLQJ JURXSV ,Q D UHFHQW UHYLHZ >&3@ WKH GLIIHUHQW JURXSV XVHG IRU WKLV WUDQVIRUPDWLRQ KDYH EHHQ GLVFXVVHG LW DOVR FRPSDUHV WKH DGYDQWDJHV DQG GLVDGYDQWDJHV RI WKH GLIIHUHQW JURXSV ZKLFK DULVH HLWKHU IURP WKH LQLWLDO LQWURGXFWLRQ RI WKH JURXS RU UHPRYDO DIWHU WKH WUDQVIRUPDWLRQ ,Q DOO WKH JURXSV GLVFXVVHG WKH PDLQ LGHD EHKLQG WKH DFWLYDWLRQ ZDV WKHLU DELOLW\ WR VWDELOL]H DQ f§FDUEDQLRQ E\ GLSROH VWDELOL]DWLRQ

PAGE 26

'LSROH 6WDELOL]HG &DUEDQLRQV $ FDUEDQLRQ LV FRQVLGHUHG WR EH GLSROH VWDELOL]HG ZKHQ LW LV DGMDFHQW WR D KHWHURDWRP ZKLFK LV WKH SRVLWLYH HQG RI D GLSROH 6FKHPH f 7KH JURXS = FDQ SURYLGH VWDELOL]DWLRQ LQ WKH WUDQVLWLRQ VWDWH OHDGLQJ WR f E\ FRPSOH[DWLRQ ZLWK WKH PHWDO RI WKH EDVH E\ GLSROH VWDELOL]DWLRQ DQGRU E\ UHVRQDQFH GHORFDOL]DWLRQ >&5@ 0HFKDQLVP RI PHWDODWLRQ KDV EHHQ UHYLHZHG >&5@ ,Q DGGLWLRQ WR GLSROH VWDELOL]DWLRQ LQ WKH OLWKLDWLRQ RI DPLGHV E\ ,5 REVHUYDWLRQ LQ D VWRSSHGIORZ VSHFWURPHWHU DQG V\Q VXEVWLWXWLRQ LQGLFDWH FRPSOH[DWLRQ SOD\V D PDMRU UROH LQ WKH UHDFWLRQ VHH f RI 6FKHPH f &DUER[DPLGR *URXS 6WDELOL]HG &DUEDQLRQV 7KH REVHUYDWLRQ WKDW GLSROH VWDELOL]HG FDUEDQLRQV f FDQ EH IRUPHG IURP DPLGHV DQG XQGHUJR HOHFWURSKLOLF VXEVWLWXWLRQ DV VKRZQ LQ VFKHPH OHG WR LQYHVWLJDWLRQV RI D QXPEHU RI V\VWHPV LQ ZKLFK WKH DFWLYDWLQJ IXQFWLRQ = FRQWDLQV D FDUERQ\O JURXS >&5 $*(f -2&@ 7KH FDUERQ\O JURXS VKRXOG EH HIILFLHQWO\ DGGHG WR DQG FOHDYHG IURP WKH DPLQH DV ZHOO DV EHLQJ UHVLVWDQW WR QXFOHRSKLOLF DGGLWLRQ E\ WKH DON\O OLWKLXP EDVH ZKLFK LV UHTXLUHG WR IRUP WKH FDUEDQLRQLF LQWHUPHGLDWH f

PAGE 27

2 5 + VHF%X/L r‘ &+5 R &+5 FKU 6FKHPH 2 /L , UFA6AKU &+5 f 9DULRXV VXEVWLWXHQWV DGMDFHQW WR WKH FDUERQ\O KDYH EHHQ LQYHVWLJDWHG LQ GLIIHUHQW DPLGHV DQG WKH GLHWK\OSURS\O JURXS ZDV IRXQG WR EH WKH EHVW RI DOO WKRVH FRQVLGHUHG >-2&@ $OKRXJK D JUHDW QXPEHU RI DF\O JURXSV KDYH EHHQ XVHG LQ WKH WUDQVIRUPDWLRQ RI DPLQHV LQWR DVXEVWLWXWHG DPLQHV WKHUH KDV EHHQ QR LQYHVWLJDWLRQ RI ZKHWKHU WKHUH LV V\QHUJLVWLF HIIHFW ZLWK WZR RU PRUH DPLGH IXQFWLRQDOLWLHV RQ WKH VWDELOL]DWLRQ RI D FDUEDQLRQ

PAGE 28

6\QHUJLVWLF (IIHFWV LQ 6WDELOL]DWLRQ 'LSROH VWDELOL]HG DQLRQV RI W\SH 55n& 15; < DUH NQRZQ IRU D ZLGH YDULHW\ RI JURXSV ; < >7/&5 @ +RZHYHU OLWWOH LV NQRZQ DERXW WKH V\QHUJLVWLF HIIHFW RI VXFK VWDELOL]DWLRQ LQ GHULYDWLYHV RI W\SH 5& 15n; 7@ WKDW OLWKLDWLRQ RI PHWK\OHQHELVS\UD]OHV WR JLYH PHWDOODWHG GHULYDWLYHV RI W\SH f LV LQGHHG VRPHZKDW HDVLHU WKDQ WKH IRUPDWLRQ RI WKH FRUUHVSRQGLQJ PRQRF\FOLF DQDORJXHV f &+/L &+/L 7 f &+/L f Df Ef 7KH FODVVLF H[DPSOH RI WKH V\QHUJLVWLF HIIHFW KDV EHHQ WKH ZRUN RQ F\FORKH[DQHGLWKLDQH ZKLFK KDV EHHQ JUHDWO\ H[SORLWHG LQ RUJDQLF V\QWKHVLV >-$0 -$0 $*(f $*(f -2&-

PAGE 29

$LP RI WKH :RUN 7KH DLP ZDV WR VWXG\ WKH DPHWDOODWLRQ EHKDYLRU RI D VHULHV RI FRPSRXQGV FRQWDLQLQJ WKH VWUXFWXUDO IHDWXUH &+15&25nf 5HVXOWV DQG 'LVFXVVLRQ &\FOLF GLDPLQHV DQG WULDPLQHV ZHUH FKRVHQ DV WKH VWDUWLQJ FRPSRXQGV DQG WKH DF\O GHULYDWLYHV RI WKHVH FRPSRXQGV ZHUH SUHSDUHG IRU WKH VWXG\ 7KH DF\O XQLW ZDV HLWKHU D EHQ]R\O RU D SLYDOR\O JURXS 7KH FRPSRXQGV SUHSDUHG IRU WKH VWXG\ ZHUH GLEHQ]R\OLPLGD]ROLGLQH f GLSLYDOR\OLPLGD]ROLGLQH f GLEHQ]R\OKH[DK\GURS\ULPLGLQH f GLSLYDOR\OKH[DK\GURS\ULPLGLQH f WULEHQ]R\OKH[DK\GURV\PWULD]LQH f DQG WULSLYDOR\OKH[DK\GURV\PWULD]LQH f 1&25 &2 5 f 5 &+ f 5 &&+f AA1&25 &2 5 f 5 &+ f 5 &&+f &2 5 f5 &+ f5 &&+f

PAGE 30

3UHSDUDWLRQ RI $PLGHV &RPSRXQGV f DQG f ZHUH SUHSDUHG IURP HWK\OHQH GLDPLQH IRUPDOLQ DQG EHQ]R\O FKORULGH RU SLYDOR\O FKORULGH UHVSHFWLYHO\ VFKHPH f &RPSRXQGV f DQG f ZHUH SUHSDUHG IURP SURSDQHGLDPLQH IRUPDOLQ DQG EHQ]R\O FKORULGH RU SLYDOR\O FKORULGH UHVSHFWLYHO\ VFKHPH f +RZHYHU FRPSRXQGV f DQG f ZHUH SUHSDUHG IURP V\PWULR[DQH DQG EHQ]RQLWULOH RU SLYDORQLWULOH UHVSHFWLYHO\ VFKHPH f +1&+f 1+ +&+2  = Q = 1D2+ 5&2& f 5 &+ Q f 5 &&+f &0 ,, F 6FKHPH f 5 &+ Q f 5 &&+f Q 5&1 KRr &2 5 f 5 &t+ f 5 &&+f 6FKHPH

PAGE 31

/LWKLDWLRQ RI 'LDF\OLPLGD]ROLGLQHV /LWKLDWLRQ RI f ZLWK OLWKLXP GLLVRSURS\ODPLGH /'$f LQ WHWUDK\GURIXUDQ 7+)f DW r& JDYH D GDUN EURZQ VROXWLRQ RI D FDUEDQLRQ 8QGHU PRVW FRQGLWLRQV WKH YHU\ UHDFWLYH FDUEDQLRQ UHDFWHG ZLWK PRUH RI f DFWLQJ DV DQ HOHFWURSKLOH WR JLYH WKH VHOI FRQGHQVDWLRQ SURGXFW f )RUPDWLRQ RI f ZDV DOVR FRQILUPHG E\ WKH DSSHDUDQFH RI D NHWRQH FDUERQ\O VLJQDO LQ WKH 105 $GGLWLRQ RI /'$ WR D PL[WXUH RI f DQG DQ HOHFWURSKLOH LQ 7+) VWLOO JDYH f 8VH RI EHQ]DOGHK\GH RU SDUDWROXDOGHK\GH DV WKH HOHFWURSKLOH JDYH WKH FRUUHVSRQGLQJ EHQ]\O DOFRKRO DORQJ ZLWK VWDUWLQJ PDWHULDO DV REVHUYHG IURP A+ DQG & 105 VSHFWUD DQG GLPHUV RI FRPSRXQG f DV REVHUYHG IURP PDVV VSHFWURPHWU\ 7KH XVH RI DPLGH f ZDV DQ DWWHPSW WR DYRLG VHOI FRQGHQVDWLRQ E\ WKH LQWURGXFWLRQ RI VWHULF FURZGLQJ DURXQG WKH FDUERQ\O JURXS +RZHYHU WKLV PHWKRG IDLOHG DV f GLG QRW UHDFW ZLWK /'$ HYHQ DW r& (YLGHQWO\ WKH WHUW EXW\O JURXS LQFUHDVHG WKH VWHULF FURZGLQJ QRW RQO\ DURXQG WKH FDUERQ\O EXW DOVR DURXQG WKH & FDUERQ WKXV KLQGHULQJ WKH DSSURDFK RI WKH EDVH /'$ WR WKH & K\GURJHQ 6LPLODU H[SODQDWLRQV KDYH DOVR EHHQ JLYHQ IRU GLEHQ]R\O GLPHWK\OTXLQR[DOLQHV QRW UHDFWLQJ ZLWK /'$ >-&63L f @

PAGE 32

8VH RI OHVV QXFOHRSKLOLF WHUWEXW\OLWKLXP IRU GHSURWRQDWLRQ LQVWHDG RI /'$ JDYH WKH H[SHFWHG SURGXFW DIWHU WUHDWPHQW ZLWK DQ HOHFWURSKLOH %\ WKLV SURFHGXUH WKH & PHWK\ODWHG FRPSRXQG f ZDV REWDLQHG IURP FRPSRXQG f XVLQJ PHWK\O LRGLGH DV WKH HOHFWURSKLOH +RZHYHU WKH H[SHFWHG SURGXFW ZDV QRW LVRODWHG ZLWK FRPSRXQG f DQG PHWK\O LRGLGH f ( &2&+ f ( &+ QFRFK &2 /LWKLDWLRQ RI 'LDF\OKH[DK\GURS\ULPLGLQHV /LWKLDWLRQ RI f ZLWK /'$ DOVR DIIRUGHG D GDUN FRORUHG VROXWLRQ LQGLFDWLQJ WKH IRUPDWLRQ RI WKH FDUEDQLRQ EXW DJDLQ RQ ZRUNXS RQO\ WKH VHOI FRQGHQVDWLRQ SURGXFW f ZDV REWDLQHG 7KH VDPH SURGXFW f ZDV DOVR REWDLQHG RQ DGGLQJ /'$ WR D VROXWLRQ RI f DQG DQ HOHFWURSKLOH LQ 7+) :KHQ EHQ]DOGHK\GH RU SDUDWROXDOGHK\GH ZDV XVHG DV WKH HOHFWURSKLOH WKH FRUUHVSRQGLQJ EHQ]\O DOFRKRO ZDV IRUPHG DV HYLGHQFHG E\ DQG 105 8VH RI WHUWEXW\OLWKLXP DV WKH EDVH ZLWK FRPSRXQG f JDYH WKH H[SHFWHG FDUEDQLRQ ZKLFK ZDV WUDSSHG ZLWK WR JLYH f

PAGE 33

$ PRUH VWDEOH FDUEDQLRQ ZDV REWDLQHG IURP f LQ 7+) DW r& ZLWK /'$ DQG WKLV ZDV WUDSSHG ZLWK 'A2 WR JLYH f DQG ZLWK PHWK\O LRGLGH WR JLYH f 7KH A+ 105 VSHFWUXP RI f VKRZHG IRXU VLJQDOV ZLWK FKHPLFDO VKLIWV LGHQWLFDO WR WKH VWDUWLQJ PDWHULDO f KRZHYHU WKH LQWHQVLW\ RI WKH VLJQDO IRU WKH & SURWRQ ZDV RQH IRXUWK RI WKH VLJQDO IRU WKH & DQG & SURWRQV f 5 &+ M ( &2&+ M AA1&25 f 5 &+ ( AWUA( f 5 &&+f ( &2 f 5 &&+f ( FK 5 0HWDOODWLRQ RI 7ULDF\OKH[DK\GURV\PWULD]LQHV /RZ VROXELOLW\ RI f LQ 7+) DQG '0( EHORZ r& SUHYHQWHG WKH XVXDO SURFHGXUH ZLWK /'$ DV EDVH +RZHYHU /'$ DGGLWLRQ DW r& JDYH WKH FDUEDQLRQ ZKLFK ZDV WUDSSHG ZLWK '2 WR JLYH f 0HWDOODWLRQ XQGHU SRODU FRQGLWLRQV ZDV DWWHPSWHG EXW WUHDWPHQW RI f ZLWK GLPV\O VRGLXP IROORZHG E\ DQ HOHFWURSKLOH JDYH RQO\ VWDUWLQJ PDWHULDO EDFN

PAGE 34

/LWKLDWLRQ RI f LQ 7+) DW r& ZLWK /'$ JDYH WKH FDUEDQLRQ ZKLFK ZDV WUDSSHG ZLWK '2 WR JLYH f f 5 &+ ( f 5 &&+f ( &RQFOXVLRQV /LWKLDWLRQ VWXGLHV ZLWK GLDF\OLPLGD]ROLGLQHV GLDF\OKH[DK\GURS\ULPLGLQHV DQG WULDF\OKH[DK\GURV\P WULD]LQHV 7DEOH f LQGLFDWH WKDW QR VXEVWDQWLDO DGGLWLRQDO LQFUHDVH LQ FDUEDQLRQ VWDELOLW\ RFFXUV DV D UHVXOW RI WKH LQWURGXFWLRQ RI WKH VHFRQG GLSRODU VWDELOL]LQJ JURXS 7KLV PLJKW EH GXH WR WKH IDFW WKDW WKH FRQIRUPHU IDYRULQJ WKH GRXEOH VWDELOL]DWLRQ ZDV QRW WKH SUHGRPLQDQW FRQIRUPHU GLVFXVVHG LQ FKDSWHU f :LWKLQ WKH DPLGHV VWXGLHG WKH FDUEDQLRQV GHULYHG IURP WKH EHQ]R\O GHULYDWLYHV f f DQG f ZHUH IRXQG WR EH OHVV VWDEOH ZLWK f EHLQJ WKH OHDVW +RZHYHU FDUEDQLRQV GHULYHG IURP SLYDOR\O GHULYDWLYHV f DQG f ZHUH IRXQG WR EH PRUH VWDEOH ZLWK f EHLQJ WKH PRVW 7KLV PLJKW KDYH EHHQ GXH WR WKH LQFUHDVH LQ VWHULF FURZGLQJ DURXQG WKH DPLGH & ERQGV PDNLQJ WKHP OHVV VXVFHSWLEOH IRU QXFOHRSKLOLF

PAGE 35

7DEOH )RUPDWLRQ RI D/LWKLR 6SHFLHV RI $PLGHV DQG WKHLU 5HDFWLRQ ZLWK (OHFWURSKLOHV $PLGH 3URFHGXUH (OHFWURSKLOH 3URGXFW
PAGE 36

DGGLWLRQ UHDFWLRQV ,Q DGGLWLRQ ULQJ VL]H ZDV DOVR IRXQG WR EH D IDFWRU )LYHPHPEHUHG ULQJ ZDV IRXQG WR EH PRUH LQIOXHQFHG E\ WKH VWHULF QDWXUH RI WKH DF\O XQLW WKDQ WKH VL[PHPEHUHG ([SHULPHQWDO 0HOWLQJ SRLQWV ZHUH UHFRUGHG RQ D %ULVWROLQH KRWVWDJH PLFURVFRSH DQG ZHUH XQFRUUHFWHG 3URWRQ 105 VSHFWUD ZHUH UHFRUGHG RQ D 9DULDQ (0 / VSHFWURPHWHU XVLQJ LQWHUQDO 0HA6L DV WKH UHIHUHQFH ,5 VSHFWUD ZHUH REWDLQHG RQ D 3HUNLQ(OPHU % VSHFWURSKRWRPHWHU 5HDJHQWV 7HWUDK\GURIXUDQ 7+)f ZDV UHIOX[HG RYHU DQG GLVWLOOHG IURP VRGLXP EHQ]RSKHQRQH NHW\O Q%X/L 0 LQ KH[DQHf DQG W%X/L 0 LQ SHQWDQHf ZHUH VWDQGDUGLVHG E\ WLWUDWLRQ >&&@ 'LLVRSURS\ODPLQH ZDV UHIOX[HG RYHU DQG GLVWLOOHG IURP &D+A 3UHSDUDWLRQ RI $F\O 'HULYDWLYHV RI ,PLGD]ROLGLQHV +H[DK\GURS\ULPLGLQHV DQG +H[DK\GURV\PWULD]LQHV 3UHSDUDWLRQ RI GLEHQ]R\OLPLGD]ROLGLQH f (WK\OHQHGLDPLQH J 0f DQG IRUPDOGHK\GH J b VROXWLRQf DW r& ZHUH VWLUUHG IRU K 7KH YLVFRXV

PAGE 37

FRORUOHVV OLTXLG ZDV WKHQ NHSW DW r& %HQ]R\O FKORULGH J 0f ZDV DGGHG GURSZLVH RYHU PLQ ZKLOH PDLQWDLQLQJ D S+ RI ZLWK b 1D2+ VROXWLRQ P/f 7KH PL[WXUH ZDV WKHQ VWLUUHG IRU K DW r& 7KH GLEHQ]R\OLPLGD]ROLGLQH VHSDUDWHG RXW DQG ZDV UHFU\VWDOOL]HG IURP DFHWRQH J bf DV SODWHV PS r& OLW > -+& @ PS r&f ?! &+% U f FP PD[ M &'&f + Vf + Vf DQG + Vf 3UHSDUDWLRQ RI GLSLYDOR\OLPLGD]ROLGLQH f (WK\OHQHGLDPLQH J 0f IRUPDOGHK\GH J b VROXWLRQf DQG ZDWHU P/f ZHUH VWLUUHG DW r& IRU K 7R WKH YLVFRXV FRORUOHVV OLTXLG DTXHRXV VRGLXP K\GUR[LGH J 0 LQ P/ RI ZDWHUf ZDV DGGHG 7KH PL[WXUH ZDV FRROHG WR EHWZHHQ DQG r& DQG WULPHWK\ODFHW\O FKORULGH J 0f DGGHG GURSZLVH $IWHU IXUWKHU VWLUULQJ IRU K GLSLYDOR\OLPLGD]ROLGLQH J bf VHSDUDWHG 7KH FUXGH VROLG ZDV ZDVKHG ZLWK ZDWHU DQG UHFU\VWDOOL]HG IURP FKORURIRUP WR JLYH SULVPV PS r& )RXQG & + 1 AL+1A UHFXnUHV & + 1 bf Y &+%Uf FP &'&Of + Vf PD [ M M + Vf DQG + Vf 3UHSDUDWLRQ RI GLEHQ]R\OKH[DK\GURS\ULPLGLQH f 3URSDQHGLDPLQH J 0f ZDWHU P/f DQG IRUPDOGHK\GH B P/ f ‘ U cU O F f H G H& IRU K 6RGLXP K\GUR[LGH 0 P/f ZDV DGGHG DW r& DQG WKHQ

PAGE 38

EHQ]R\O FKORULGH J 0f GURSZLVH $IWHU VWLUULQJ IRU DQRWKHU K GLEHQ]R\OKH[DK\GURS\ULPLGLQH J bf VHSDUDWHG &U\VWDOOL]DWLRQ IURP HWKHUFKORURIRUP JDYH SODWHV PS r& OLW>$-&@ PS r&f Y OXF ; &+%Uf FP &'&f + Pf + W +]f + Vf DQG + Vf 3UHSDUDWLRQ RI GLSLYDOR\OKH[DK\GURS\ULPLGLQH f 3URSDQHGLDPLQH J 0f IRUPDOGHK\GH b P/f DQG ZDWHU P/f ZHUH VWLUUHG DW r& IRU K 6RGLXP K\GUR[LGH 0 P/f ZDV DGGHG DW r& DQG WKHQ SLYDOR\O FKORULGH J 0f ZDV DGGHG GURSZLVH $IWHU VWLUULQJ WKH PL[WXUH DW r& IRU K FROXPQ FKURPWRJUDSK\ DOXPLQD DQG HWKHUf JDYH GLSLYDOR\OKH[DK\GURS\ULPLGLQH J bf ZKLFK FU\VWDOOL]HG DV SODWHV IURP HWKHUf PS r& )RXQG & + 1 &@B+1r UHTXLUHV & + 1 bf Y &+%Uf FPr &'&Of + Vf ,XD ; M M + Pf + W +]f DQG + Vf 3UHSDUDWLRQ RI WULEHQ]R\OKH[DK\GURV\PWULD]LQH f &RPSRXQG f ZDV SUHSDUHG DV UHSRUWHG HDUOLHU >6@ LW IRUPHG SULVPV IURP HWKHUFKORURIRUP PS r& OLW >6@ PS r&f ?! &+%Uf FP PD[ &'&f + Vf + Vf

PAGE 39

3UHSDUDWLRQ RI WULSLYDOR\OKH[DK\GURV\PWULD]LQH f &RPSRXQG f ZDV SUHSDUHG IROORZLQJ WKH OLWHUDWXUH PHWKRG > 6 @ IRU f LQ b \LHOG DV QHHGOHV IURP HWKHUFKORURIRUP PS r& )RXQG & + 1 FL+1r UHTXLUHV & + 1 bf Y &+%Uf FP &'&f + Vf DQG ,OOD ; M M! + 6f /LWKLDWLRQ RI WKH $F\O 'HULYDWLYHV RI ,PLGD]ROLGLQHV +H[DK\GURS\ULPLGLQHV DQG +H[DK\GURV\PWULD]LQHV *HQHUDO SURFHGXUH $ /'$ PPROf ZDV SUHSDUHG E\ DGGLQJ GURSZLVH GLn LVRSURS\ODPLQH P/ PPROf WR QEXW\OOLWKLXP LQ KH[DQH PPROf DW r& XQGHU QLWURJHQ 6WLUULQJ ZDV FRQWLQXHG XQWLO LW EHFDPH FORXG\ Kf DQG WKHQ GU\ 7+) P/f ZDV DGGHG 7KH PL[WXUH ZDV WKHQ FRROHG WR r& DQG WKH DPLGH PPROf LQ GU\ 7+) P/f ZDV DGGHG 6WLUULQJ ZDV FRQWLQXHG IRU K DW r& DQG IRU K PRUH DW r& :DWHU P/f ZDV DGGHG DQG VROYHQWV UHPRYHG DW r& PP+J 7KH UHVLGXH LQ PHWK\OHQH FKORULGH P/f ZDV ZDVKHG ZLWK VDWXUDWHG DTXHRXV 1D&O P/f DQG ZDWHU P/f DQG WKHQ GULHG VRGLXP VXOSKDWHf DQG HYDSRUDWHG DW r& PP+J 3URGXFWV ZHUH VHSDUDWHG E\ FROXPQ FKURPDWRJUDSK\

PAGE 40

*HQHUDO SURFHGXUH % 6LPLODU WR SURFHGXUH $ H[FHSW WKDW WEXW\OLWKLXP ZDV XVHG LQVWHDG RI /'$ /LWKLDWLRQ RI 'LEHQ]R\OLPLGD]ROLGLQH 'LEHQ]R\OPHWK\OLPLGD]ROLGLQH f )ROORZLQJ SURFHGXUH % XVLQJ GLEHQ]R\OLPLGD]ROLGLQH f ZLWK PHWK\O LRGLGH DV WKH HOHFWURSKLOH JDYH GLEHQ]R\OPHWK\OLPLGD]ROLGLQH f bf DV QHHGOHV IURP &+&O PS & )RXQG & + 1 &+1r UHFXLLnHV &n + 1 bf YPD[&+%Uf FP &'&f + Pf + T +]f + Pf DQG + G +]f 7ULEHQ]R\OLPLGD]ROLGLQH f 'LEHQ]R\OLPLGD]ROLGLQH f IROORZLQJ SURFHGXUH $ VHOI FRQGHQVHG WR JLYH WULEHQ]R\OLPLGD]ROLGLQH f bf DV QHHGOHV IURP &+& PS r& )RXQG & + 1 A+1A UHFXLUHV & + 1 bf ?! Y &+%UFP &'&Of + Pf PD[ M M + Vf DQG & SURWRQ QRW REVHUYHG

PAGE 41

/LWKLDWLRQ RI 'LEHQ]R\OKH[DK\GURS\ULPLGLQH 'HXWHULROGLEHQ]R\OKH[DK\GURS\ULPLGLQH f 'LEHQ]R\OKH[DK\GURS\ULPLGLQH f IROORZLQJ SURFHGXUH % ZLWK '2 DV WKH HOHFWURSKLOH JDYH GHXWHULR GLEHQ]R\OKH[DK\GURS\ULPLGLQH f bf DV QHHGOHV IURP HWKHU PS r& )RXQG & + 1 A+'1r UHFXAUHV Fn + 1 f A!PD[ &+%UfA FP 6 &'&Of + Vf + Vf + W +]f DQG + Pf 7ULEHQ]R\OKH[DK\GURS\ULPLGLQH f 'LEHQ]R\OKH[DK\GURS\ULPLGLQH f IROORZLQJ SURFHGXUH $ ZLWKRXW DQ\ HOHFWURSKLOH JDYH WULEHQ]R\OKH[DK\GURS\ULPLGLQH f bf DV QHHGOHV IURP &+&O PS r& )RXQG & + 1 &+1r UH^-XLUHV &n + 1 bf A!PD[ &+%UAf FP 6 &'&f + Pf + Pf + Pf DQG & SURWRQ QRW REVHUYHG /LWKLDWLRQ RI 'LSLYDOR\OKH[DK\GURS\ULPLGLQH 'HXWHULROGLSLYDOR\OKH[DK\GURS\ULPLGLQH f 'LSLYDOR\OKH[DK\GURS\ULPLGLQH f IROORZLQJ SURFHGXUH $ ZLWK 'a DV HOHFWURSKLOH JDYH GHXWHULR GLSLYDOR\OKH[DK\GURS\ U LPLGLQH f ‘ f DV SODWHV IURP

PAGE 42

&+& PS r& )RXQG & + 1 &+&'1&8 UHTXLUHV & + 1 bf Y ; = M = = ,FO; &+%Uf FP &'&f + Vf + W +]f + Pf DQG + Vf 'LSLYDOR\OPHWK\OKH[DK\GURS\ULPLGLQH f 'LSLYDOR\OKH[DK\GURS\ULPLGLQH f IROORZLQJ SURFHGXUH $ ZLWK PHWK\O LRGLGH DV WKH HOHFWURSKLOH JDYH GLSLYDOR\OPHWK\OKH[DK\GURS\ULPLGLQH f b EDVHG RQ UHFRYHU\ RI VWDUWLQJ PDWHULDOf DV QHHGOHV IURP &+&OA PS r& )RXQG & + 1 &@B+1r UHFXLUHV & + 1 bf &+% Uf FP ,7OD ; M &'&f + T +]f + Pf + Pf + Vf DQG + G +]f /LWKLDWLRQ RI 7ULEHQ]R\OKH[DK\GURV\PWULD]LQH 'HXWHULROWULEHQ]R\OKH[DK\GURV\PWULD]LQH f 7ULEHQ]R\OKH[DK\GURV\PWULD]LQH f IROORZLQJ SURFHGXUH $ EXW ZLWK DGGLWLRQ RI /'$ WR f LQ 7+) DW r& ZLWK DV WKH HOHFWURSKLOH JDYH GHXWHULRO WULEHQ]R\OKH[DK\GURV\PWULD]LQH f bf DV SODWHV IURP &+&O PS r& )RXQG & + 1 &n!+'1r UHXLUHV &n + 1 bf Y &+%UFP &'&Of + Vf DQG P X [ M + 6f

PAGE 43

/LWKLDWLRQ RI 7ULSLYDOR\OKH[DK\GURV\P WULD]LQH 'HXWHULROWULSLYDOR\OKH[DK\GURV\PWULD]LQH f 7ULSLYDOR\OKH[DK\GURV\PWULD]LQH f IROORZLQJ SURFHGXUH $ ZLWK '2 DV WKH HOHFWURSKLOH JDYH GHXWHULRWULSLYDOR\OKH[DK\GURV\PWULD]LQH f bf DV SODWHV IURP &+&OA PS r& )RXQG & + 1 A+'1r UHWXLUHV & + 1 bf YPRA&+%UMf FPnrn &'&Of + Vf DQG ,8D ; M M + V f

PAGE 44

&+$37(5 &21)250$7,21$/ $1$/<6,6 2) $0,'(6 ,QWURGXFWLRQ 'XULQJ WKH ODVW WZR GHFDGHV 105 VSHFWURVFRS\ KDV GHYHORSHG LQWR RQH RI WKH PRVW YDOXDEOH WHFKQLTXHV IRU LQYHVWLJDWLQJ PROHFXODU VWUXFWXUH DQG VWHUHRFKHPLVWU\ 1RW RQO\ FDQ 105 JLYH WKH H[WHQW RI HTXLOLEULXP EHWZHHQ GLIIHUHQW FRQIRUPHUV EXW FDQ DOVR \LHOG LQIRUPDWLRQ DERXW WKH G\QDPLF EHKDYLRU RI WKH GLIIHUHQW FRQIRUPHUV DW YDULRXV WHPSHUDWXUHV 7KLV LV UHIHUUHG WR DV G\QDPLF QXFOHDU PDJQHWLF UHVRQDQFH '105f 7KH EDUULHU KHLJKWV RU WKH IUHH HQHUJ\ RI DFWLYDWLRQ RI G\QDPLF SURFHVVHV DPHQDEOH WR WKLV WHFKQLTXH FRQYHQLHQWO\ H[WHQG MXVW IURP WKH ERUGHU OLQH RI NFDO PROH A EHORZ ZKLFK FRPSRXQGV EHFRPH WRR XQVWDEOH WR EH LVRODWHG WR DERXW NFDO PROH A 5HVWULFWHG URWDWLRQ DERXW WKH &f1 ERQG LQ DPLGHV LV WKH FODVVLFDO H[DPSOH RI D UDWH SURFHVV WKDW FDQ EH VWXGLHG E\ '105 $FWLYDWLRQ SDUDPHWHUV FDQ EH REWDLQHG WR D JUHDWHU DFFXUDF\ XVLQJ WRWDO OLQH VKDSH DQDO\VLV +RZHYHU D JUHDW QXPEHU RI UHIHUHQFHV DUH DYDLODEOH LQGLFDWLQJ WKDW WKH

PAGE 45

FRDOHVFHQFH WHPSHUDWXUH KDV EHHQ XVHG WR REWDLQ WKH IUHH HQHUJ\ RI DFWLYDWLRQ &RQIRUPDWLRQDO $QDO\VLV 8VLQJ '105 7KRXJK '105 KDV EHHQ XVHG WR VWXG\ DOO W\SHV RI FRPSRXQGV OLNH VXEVWLWXWHG HWKDQHV DPLGHV FDUEDPDWHV WKLRDPLGHV QLWURVRDPLQHV QLWULOHV DOGHK\GHV DQG NHWRQHV RQO\ DPLGHV ZLOO EH GLVFXVVHG KHUH 5HVRQDQFH WKHRU\ GHVFULEHV WKH HOHFWURQLF VWUXFWXUH RI DPLGHV DV D K\EULG RI Df DQG Ef VXJJHVWLQJ D FHUWDLQ DPRXQW RI GRXEOHERQG FKDUDFWHU IRU WKH &f1 ERQG DQG WKXV WKHUH LV D FRQFRPLWDQW LQFUHDVH RI WKH URWDWLRQDO EDUULHU RYHU WKDW LQ SXUH VLQJOH ERQGV 7KHUH LV D FKDQFH W 0 WR REVHUYH WKH UDWH SURFHVV E\ '105 EHFDXVH 5 DQG 5 UHVLGH W LQ GLIIHUHQW PDJQHWLF HQYLURQPHQWV 5 EHLQJ PRUH VKLHOGHG WKDQ 5 f >-$0@ LQ WKH IL[HG VWUXFWXUH f EXW DUH WLPHDYHUDJHG RQ UDSLG URWDWLRQ 7KLV SUHGLFWLRQ ZDV ILUVW FRQILUPHG IRU GLPHWK\OIRUPDPLGH DQG GLPHWK\ODFHWDPLGH >-&3@ 5 5 Df Ef

PAGE 46

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f VROYHQW DQG FRQFHQWUDWLRQ RQ WKH EDUULHU ,Q FHUWDLQ FDVHV VWDEOH DPLGH FRQIRUPHUV KDYH EHHQ LVRODWHG LQ SXUH IRUP >7/@ VXFK DV LQ WKH FDVH RI f ZKHUH D VHYHUH VWHULF LQWHUDFWLRQ UDLVHV WKH EDUULHU E\ DQ DGGLWLRQDO DPRXQW NFDO PROHf &&+! &&+! Df Ef

PAGE 47

'105 6WXGLHV RQ 3RO\DPLGHV 5HVWULFWLRQ RI URWDWLRQ DERXW WKH &f1 ERQG RI DPLGHV KDV EHHQ WKH VXEMHFW RI LQWHQVLYH VWXG\ DQG WKH VWUXFWXUDO LQIOXHQFHV RQ WKH HTXLOLEULD DQG NLQHWLFV RI WKH V\QDQWL LQWHUFRQYHUVLRQ DUH ZHOO XQGHUVWRRG IRU PRQRDPLGHV VFKHPH f >0,@ +RZHYHU WKH VDPH ZHDOWK RI LQIRUPDWLRQ LV QRW DYDLODEOH IRU SRO\DPLGHV &RQIRUPDWLRQDO SURSHUWLHV RI SRO\DPLGHV KDYH EHHQ REWDLQHG IURP 105 VWXGLHV RI WKH FRQIRUPDWLRQ RI PRGHO GLDPLGHV GHULYHG IURP WUDQV F\FORKH[DQH FDUER[\OLF DFLG DQG GLIIHUHQW DOLSKDWLF DPLQHV >00@ DQG SLSHUD]LQH RU 11nGLPHWK\OHWK\OHQHGLDPLQH DQG DOLSKDWLF RU DURPDWLF FDUER[\OLF DFLGV >00@ 6LJQDOV IRU WKH GLIIHUHQW FRQIRUPDWLRQDO LVRPHUV LQ GLDPLGHV KDYH EHHQ DVVLJQHG XVLQJ SDUDPDJQHWLF VKLIWV LQGXFHG E\ (XIRGfA FRPSOH[HV >-2&@ 6FKHPH

PAGE 48

,QGHHG WKH LQYHVWLJDWLRQ RI '105 VSHFWUD LQYROYLQJ PRUH WKDQ WZR GLIIHUHQW VSHFLHV KDV EHHQ UHODWLYHO\ OLPLWHG 105 LQYHVWLJDWLRQ RI WKLRSKHQHGLFDUER[DOGHK\GH KDV EHHQ GRQH LQ OLTXLG FU\VWDOV >-&63f@ 5RWDWLRQDO LVRPHULVP RI 11nGLPHWK\ODZELVEHQ]R\ODPLQRfDONDQHV >-&63f@ DQG WULQLWURVRKH[DK\GUROWULD]LQH >5&@ KDV EHHQ VWXGLHG XVLQJ YDULDEOH WHPSHUDWXUH 105 VSHFWURVFRS\ 6WHUHRLVRPHUL]DWLRQ RI 11nGLDFHW\O 11nGLPHWK\OK\GUD]LQH XVLQJ YDULDEOH WHPSHUDWXUH A+ 105 VSHFWURVFRS\ KDV DOVR EHHQ VWXGLHG DQG D GLVFXVVLRQ DERXW WKH PHFKDQLVP RI VWHUHRLVRPHULVDWLRQ ZDV JLYHQ >*&,@ $LPV RI WKH ZRUN 7KH JRDOV RI WKLV ZRUN ZHUH Lf WR HOXFLGDWH WKH HTXLOLEULD RQ VRPH F\FOLF PRGHO V\VWHPV RI ELV DQG WULV DPLGHV LLf WR FDOFXODWH WKH URWDWLRQDO EDUULHUV DQG LLLf WR GHGXFH WKH PHFKDQLVP RI URWDWLRQ EDVHG RQ WKH VSHFWUDO EHKDYLRU DW YDULRXV WHPSHUDWXUHV 5HVXOWV DQG 'LVFXVVLRQ 7KH PRGHO V\VWHPV FKRVHQ IRU WKH ELVDPLGH VWXGLHV ZHUH GLDF\OLPLGD]ROLGLQHV f DQG f DQG GLDF\OKH[DK\GURS\ULPLGLQHV f DQG f )RU WKH WULV DPLGH VWXGLHV LW ZDV Wf U ,KH[DK\GURV\PWULD]LQHV f DQG f

PAGE 49

f 5 &+F f 5 &&+f f 5 &+ f 5 &&+f 52&1 1&25 5 &2 f 5 &+ f 5 &&+f 52&1 1&25 &RQIRUPHUV RI 'LDPLGHV DQG 7ULDPLGHV $ VLQJOH DPLGH ERQG FDQ H[KLELW WZR FRQIRUPDWLRQV 6LPLODUO\ WZR DPLGH ERQGV WRJHWKHU FDQ H[KLELW IRXU FRQIRUPDWLRQV DQG WKUHH DPLGH ERQGV WRJHWKHU FDQ H[KLELW HLJKW FRQIRUPDWLRQV +RZHYHU RQ GHULYLQJ WKHVH DPLGHV E\ DF\ODWLQJ F\FOLF GL DQG WULDPLQHV NHHSLQJ WKH DF\O JURXSV WKH VDPHf VRPH RI WKH FRQIRUPHUV EHFRPH LQGLVWLQJXLVKDEOH )RU H[DPSOH LQ FRPSRXQGV f f f DQG f DOWKRXJK WKHUH DUH IRXU SRVVLEOH FRQIRUPHUV RQO\ WKUHH DUH GLVWLQJXLVKDEOH )XUWKHUPRUH IRU FRPSRXQGV f DQG f RI WKH HLJKW SRVVLEOH FRQIRUPHUV RQO\ WZR RI WKHP DUH GLVWLQJXLVKDEOH 7KH LQGLVWLQJXLVKDEOH FRQIRUPHUV DUH UHIHUUHG WR DV WRSRPHUV > *n U } a

PAGE 50

'LVWLQJXLVKLQJ WKH GLIIHUHQW FRQIRUUDHUV H[SHULPHQWDOO\ LQ WKLV FDVH XVLQJ 105f ZDV QRW DQ HDV\ WDVN 7R GLDJQRVH WKLV PRGHO FRPSRXQGV ZHUH GHYHORSHG WR DVVLJQ FKHPLFDO VKLIWV WR WKH GLIIHUHQW FRQIRUPDWLRQV RI WKH FRPSRXQGV f 0RGHO &RPSRXQGV IRU &RQIRUPDWLRQDO $QDO\VLV RI $F\O 'HULYDWLYHV RI &\FOLF 6HFRQGDU\ $PLQHV ,PLGD]ROLGLQH a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f VKRZHG WKH 1PHWK\O QHFHVVDULO\ V\Q WR WKH FDUERQ\Of DW GHOWD SSP

PAGE 51

>&-&@ %\ DQDORJ\ WKH V\QPHWK\O LQ 11 GLPHWK\OSLYDODPLGH f KDV EHHQ DVVLJQHG WR WKH VLJQDO DW SSP DQG WKH DQWLPHWK\O WR WKH VLJQDO DW SSP LQ WKH + 105 VSHFWUXP REWDLQHG DW r& f f ,9L f 5 &&+af M f 5 &+ +f&Ann1VYX &+ f 5 + f 5 &+ ,Q WKH SKHQ\O VHULHV WKH PRGHO FRPSRXQG 1PHWK\O WHWUDK\GURLVRTXLQRORQH f VKRZHG WKH QHFHVVDULO\ V\Qf 1&+A VLJQDO DW GHOWD SSP >7@ 11'LPHWK\OEHQ]DPLGH f DW r& LQ &%A%OA VKRZHG VLJQDOV DW GHOWD DQG SSP IRU WKH 1&+A SURWRQV >-3&@ DQG LQ FRPSDULVRQ ZLWK f WKH VLJQDO DW GHOWD SSP ZDV DVVLJQHG WR PHWK\O V\Q WR WKH FDUERQ\O

PAGE 52

)LJ +&2&1 M R 1&2&e+F E M 706 aL U 7 7 L 0+] A+ 105 6SHFWUXP RI 'LEHQ]R\OLPLGD]ROLGLQH LQ &'&OAf DW &

PAGE 53

L ‘ U )LJ 0+] + 105 6SHFWUXP RI 'LEHQ]R\OLPLGD]ROLGLQH LQ &'&OAf DW &

PAGE 54

, , 0+] + 105 6SHFWUXP RI 'LSLYDOR\OLPLGD]ROLGLQH LQ &'&OAf DW & )LJ

PAGE 55

H F )LJ 0+] + 105 6SHFWUXP RI 'LSLYDOR\OLPLGD]ROLGLQH LQ &'&OMf DW &

PAGE 56

,Q WKH FDVH RI VSHFWUD WKH VLJQDOV ZHUH DVVLJQHG WR GLIIHUHQW FRQIRUPHUV E\ UHIHUULQJ WR PRGHO FRPSRXQGV f f DQG SDUWLFXODUO\ f LQ ZKLFK WKH 1PHWK\O FDUERQV V\Q WR WKH FDUERQ\O JURXS KDG EHHQ DOZD\V VKLHOGHG SSP UHVSHFWLYHO\f FRPSDUHG WR WKH DQWL 1 PHWK\O FDUERQV SSP UHVSHFWLYHO\f >0,@ ,Q DGGLWLRQ WKH LQWHQVLW\ DQG WKH QXPEHU RI VLJQDOV ZHUH DOVR XVHG IRU WKH VLJQDO DVVLJQPHQWV $Q LQWHUHVWLQJ IHDWXUH RI WKHVH UHVXOWV IURP WKH PRGHO V\VWHPV FRQVLGHUHG ERWK IRU SURWRQ DQG FDUERQ LV WKDW JURXSV V\Q WR WKH FDUERQ\O R[\JHQ DUH DOZD\V VKLHOGHG RYHU WKH JURXSV DQWL WR LW 'LDF\OLPLGD]ROLGLQHV &RQIRUPDWLRQDO (TXLOLEULD IURP K 105 6SHFWUD $W r& IRU FRPSRXQG f ILJXUH f DQG IRU f ILJXUH f D + VLQJOHW IRU &+ DQG D + VLQJOHW IRU &+ ZHUH REVHUYHG ZKLFK GHPRQVWUDWHG UDSLG URWDWLRQ DERXW ERWK DPLGH OLQNV 7DEOH f $V WKH WHPSHUDWXUH ZDV ORZHUHG WKHVH SHDNV EURDGHQHG DQG VSOLW DQG EHORZ r& IRU f ILJXUH f DQG EHORZ r& IRU f ILJXUH f VHSDUDWH VLJQDOV ZHUH REVHUYHG IRU HDFK RI WKH WKUHH FRQIRUPHUV 7DEOH f ,Q DGGLWLRQ WR WKH DERYH f VKRZV VLJQDOV IRU WKH SKHQ\O SURWRQV DW SSP DV D EURDG VLQJOHW DQG f IRU WKH W%X DW SSP DV D VLQJOHW 2Q

PAGE 57

7DEOH A+ 105 &KHPLFDO 6KLIWV SSPf 'LDF\OLPLGD]ROLGLQHV f 9DOXHV DQG +]f DQG f 5HODWLYH 3RSXODWLRQ bf IRU 7HPS FRPSRXQG &+ O SRSQ FK SRSQ 5 r& FRQIRUPH Uf 6 bf 0 bf t 0 D f E 6 V & Df V P Ef W W Ff V f E V V n Df V G V H Ef W G V H W Ff V G V H 0 PXOWLSOLFLW\ W WULSOHW V VLQJOHW P PXOWLSOHW FRXSOLQJ FRQVWDQW +] f FL E LQWHQVLW\ / 0+] VSHFWUXP ,QWHQVLW\ UHIHUHQFH VWDQGDUG )RU ORZ WHPSHUDWXUH VSHFWUD WRWDO LQWHQVLW\ RI IRU WKHVH SHDNV WDNHQ DV VWDQGDUG F 0+] VSHFWUXP G H 7HQWDWLYH DVVLJQPHQW 7RWDO LQWHQVLW\ LQGLYLGXDO LQWHQVLWLHV QRW PHDVXUDEOH GXH WR RYHUODS

PAGE 58

FRROLQJ WKHVH SHDNV EURDGHQ DQG UHDSSHDU UHVSHFWLYHO\ DV D PXOWLSOHW QHDU SSP IRU f DQG DV WKUHH VLQJOHWV DW DQG SSP IRU f &RPSDULQJ WKH PRGHO FRPSRXQGV IRU FKHPLFDO VKLIW DVVLJQPHQW LQ FRQIRUPHUV Df Ef DQG Ff VFKHPH f RI f DQG f ZH H[SHFW WKH SURWRQV WR EH DW KLJKHVW ILHOG LQ Df ZKHUH WKH\ DUH V\Q WR ERWK FDUERQ\OV DQG DW ORZHVW ILHOG LQ Ff ZKHUH WKH\ DUH DQWL WR ERWK FDUERQ\OV &RQYHUVHO\ FRQIRUPHU Df VKRXOG VKRZ D VLQJOHW DW ORZHU ILHOG IRU WKH AA SURWRQV WKDQ WKH VLQJOHW IRU Ff ,Q WKH XQV\PPHWULFDO FRQIRUPHU Ef WKH AA SURWRQV VKRXOG GLVSOD\ DQ $$n;;n SDWWHUQ ZLWK WKH FKHPLFDO VKLIW IRU $ QHDUHU WR WKDW RI FRQIRUPHU Ff DQG RI ; QHDUHU WR FRQIRUPHU Df 7KH DVVLJQPHQWV LQ 7DEOH IROORZHG WKHVH FRQVLGHUDWLRQV 7KH UHODWLYH SURSRUWLRQV RI WKH WKUHH FRQIRUPHUV REWDLQHG IURP WKH UHODWLYH VLJQDO LQWHQVLWLHV DUH DOVR VKRZQ LQ 7DEOH 7KRVH IRU WKH &+ LQGLFDWH DfEfFf b IRU f DQG DfEfFf b IRU f 7KRVH IRU WKH &+ LQGLFDWH DfEfFf b IRU f DQG DfEfFf b IRU f 6LQFH WKH &+ VLJQDOV DUH VHSDUDWH VLQJOHWV

PAGE 59

IRU WKH GLIIHUHQW FRQIRUPHUV WKH\ DUH FRQVLGHUHG WR EH PRUH UHOLDEOH IRU LVRPHU SURSRUWLRQ GHGXFWLRQ WKDQ WKH &+ VLJQDOV IRU ZKLFK WKH VLQJOHW IRU WKH FRQIRUPHUV Df DQG Ff RYHUODSV ZLWK WKH $$n;;n GRXEOH WULSOHWV IURP FRQIRUPHU Ef 5DWLRQDOL]LQJ RXU UHVXOWV LW VHHPV WKDW LQ WKH HTXLOLEULXP IRU f DW r& FRQIRUPHU Ef ZDV IDYRUHG RYHU Df E\ NFDO PROH DQG RYHU Ff E\ NFDO PROH A +RZHYHU IRU f DW r& FRQIRUPHU Ef ZDV IDYRUHG RYHU Df E\ NFDO PROH DQG RYHU Ff E\ NFDO PROH 'LDF\OKH[DK\GURS\ULPLGLQHV &RQIRUPDWLRQDO (TXLOLEULD IURP K 105 6SHFWUD $W r& FRPSRXQGV f ILJXUH f DQG f ILJXUH f VKRZHG D K VLQJOHW IRU WKH &+ SURWRQV ZKLFK GHPRQVWUDWHV WKDW MXVW DV IRU f DQG f UDSLG URWDWLRQ RFFXUV DERXW ERWK DPLGH OLQNV 7DEOH f $W ORZ WHPSHUDWXUHV IRU f ILJXUH f WKH SHDNV EURDGHQ DQG VSOLW DQG DW r& VHSDUDWH VLJQDOV ZHUH REVHUYHG IRU HDFK RI WKH WKUHH FRQIRUPHUV +RZHYHU IRU f ILJXUH f DW r& VHSDUDWH VLJQDOV ZHUH VHHQ RQO\ IRU WZR FRQIRUPHUV

PAGE 60

6LJQDO DVVLJQPHQWV ZHUH EDVHG RQ PRGHO FRPSRXQGV GLVFXVVHG HDUOLHU 7KH SURWRQV JDYH DQ DGGLWLRQDO VLJQDO DURXQG SSP 7KH DVVLJQPHQWV RI 7DEOH IROORZ WKHVH FRQVLGHUDWLRQV )RU H[DPSOH WKH DVVLJQPHQWV IRU WKH &+ SURWRQV RI f DQG f DUH DV IROORZV DW r& f VKRZHG WKUHH VLJQDOV IRU WKH &+ SURWRQV 8VLQJ WKH UXOH GHULYHG IURP PRGHO FRPSRXQGV WKDW SURWRQV V\Q WR WKH FDUERQ\O R[\JHQ ZHUH VKLHOGHG WKH RQH WR WKH ORZHVW ILHOG ZDV DVVLJQHG WR Ff WKH RQH WR WKH KLJKHVW ILHOG WR Df DQG WKH PLGGOH RQH WR Ef VFKHPH f 2Q VLPLODU JURXQGV RI WKH WZR VLJQDOV REVHUYHG IRU FRPSRXQG f WKH PRVW LQWHQVH VLJQDO ZDV DVVLJQHG WR Ef DQG WKH UHPDLQLQJ RQH EHLQJ DW KLJKHU ILHOG WKDQ WKDW RI Ef ZDV DVVLJQHG WR Df $VVLJQPHQWV IRU WKH &A&J SURWRQV ZHUH PDGH VLPLODUO\ 7DEOH f 5HODWLYH VLJQDO LQWHQVLWLHV DQG WKH LVRPHU SURSRUWLRQV IURP WKH &+ VLJQDOV DUH VKRZQ LQ 7DEOH )RU f DfEfFf b DQG IRU f DfEfFf b )URP WKH &+ VLJQDOV LW ZDV QRW SRVVLEOH WR GHULYH FRQIRUPHU SURSRUWLRQV EHFDXVH RI DGGLWLRQDO FRXSOLQJ WR WKH &+ DQG RYHUODSSLQJ RI VLJQDOV

PAGE 61

G 706 KFRFQ[AQFRFK 7a f§Ua aL )LJ L f • 0+] A+ 105 6SHFWUXP RI 'LEHQ]R\OKH[DK\GURS\ULPLGLQH LQ & f DW &

PAGE 62

G )LJ 0+] A+ 105 6SHFWUXP RI 'LEHQ]R\OKH[DK\GURS\ULPLGLQH LQ &'&Of DW r&

PAGE 63

706 FK fARFQA QFRF FK f G FKFL G N U 7 7 )LJ 0+] O+ 105 6SHFWUXP RI 'LSLYDOR\OKH[DK\GURS\ULPLGLQH LQ &'&f

PAGE 64

DFHWRQH E G E n8A706 7 7 7 7 7 7 7 0+] + 105 6SHFWUXP RI 'LSLYDOR\OKH[DK\GURS\ULPLGLQH LQ &'&2&'f DW & )LJ

PAGE 65

7DEOH 105 &KHPLFDO 6KLIWV SSPf DQG 5HODWLYH 3RSXODWLRQ bf IRU 'LDF\O KH[DK\GURS\ULPLGLQHV f DQG f 7HPS FRPSRXQG &+ SRSQ f&+ &+ 5 r& FRQIRUPH Uf 60f bf 6 0 f 60f t0f D f V f E Wf& Pf Pf G Df Vf Pf H IPf H Pf H Ef Vf Pf I Pf Pf Pf Ff Vf Pf I Pf Pf D f Vf 1! 2 2 Wf& Pf V f Df Vf Pf H Pf H V f H EfJ Vf P f Pf Vf 0 P /WLSOLFLW\ W WULSOHW V VLQJOHW LQWHQVLW\ 0+] VSHFWUXP E ,QWHQVLW\ UHIHFHQFH VWDQGDUG DW ORZ WHPSHUDWXUH WRWDO LQWHQVLW\ IRU WKHVH SHDNV WDNHQ DV F %HLQJ DW ORZ ILHOG 0+]f WKLV VLJQDO LV VHHQ DV DQ DSSDUHQW WULSOHW ZLWK +] G I 0+] VSHFWUXP ,QGLYLGXDO LQWHQVLWLHV QRW PHDVXUDEOH GXH WR RYHUODS 7HQWDWLYH DVVLJQPHQW J 1R SHDNV IRU Ff REVHUYHG

PAGE 66

7KH HTXLOLEULXP DW r& IRU f IDYRUHG FRQIRUPHU Ef RYHU Df E\ NFDO PROHn DQG FRQIRUPHU Ef RYHU Ff E\ NFDO PROH A +RZHYHU IRU f WKH HTXLOLEULXP DW r& IDYRUHG FRQIRUPHU Ef RYHU Df E\ NFDO PROHnrn 7ULDF\OKH[DK\GURV\PWULD]LQHV &RQIRUPDWLRQDO (TXLOLEULD IURP + 105 6SHFWUD $W r& FRPSRXQGV f ILJXUH f DQG f ILJXUH f VKRZHG D + VLQJOHW IRU WKH WKUHH &+ SURWRQV GHPRQVWUDWLQJ UDSLG URWDWLRQ DERXW DOO WKUHH DPLGH OLQNV $V WKH WHPSHUDWXUH ZDV ORZHUHG WKH SHDNV EURDGHQHG DQG VSOLW DQG DW r& VHSDUDWH VLJQDOV ZHUH REVHUYHG IRU f ILJXUH f IRU HDFK RI WKH WZR FRQIRUPHUV +RZHYHU IRU f RQO\ RQH FRQIRUPHU [f ZDV REVHUYHG HYHQ IRU VSHFWUD UHFRUGHG DV ORZ DV r& XVLQJ DFHWRQHGJ DV WKH VROYHQW 7DEOH f VFKHPH f 6LJQDO DVVLJQPHQWV VKRZQ LQ 7DEOH IROORZ WKH VDPH UXOHV REVHUYHG IRU VLJQDO DVVLJQPHQW IRU LPLGD]ROLGLQHV f DQG f LH WKH SURWRQV V\Q WR WKH FDUERQ\O R[\JHQ ZHUH VKLHOGHG 7KH PHWK\OHQH SURWRQV IRU f DW r& VKRZHG IRXU VLQJOHWV RI ZKLFK WKUHH VLJQDOV ZHUH RI

PAGE 67

E D 706 7 f§, I 0+] /+ 105 6SHFWUXP RI 7ULEHQ]R\OKH[DK\GURV\PULD]LQH LQ &'& f DW r& )LJ

PAGE 68

)LJ 0+] + 105 6SHFWUXP RI 7ULEHQ]R\O KH[DK\GURV\PWULD]LQH LQ &'&OAf DW r&

PAGE 69

0+] A+ 105 6SHFWUXP RI 7ULSLYDOR\OKH[DK\GURV\PWULD]LQH LQ &'& f DW r& )LJ LL

PAGE 70

FU 7DEOH E+ 105 &KHPLFDO 6KLIWV SSPf DQG 5HODWLYH 3RSXODWLRQ bf IRU 7ULDF\OKH[DK\GURV\PWULD]LQHV f DQG f 7HPS FRPSRXQG FK SRSQ 1VXEVWLW r& FRQIRUPHUf 60f bf 00f D f Vf RV 2 2 FU V f X R P [f V f P f G \f Vf H Pf G Vf V f D f V f E Vf n [fI Vf V f PXOWLSOLFLW\ V VLQJOHW P PXOWLSOHW LQWHQVLW\ D 0+] VSHFWUXP & G VWDQGDUG UHIHUHQFH LQWHQVLW\ 0+] VSHFWUXP 7RWDO LQWHQVLW\ LQGLYLGXDO LQWHQVLWLHV QRW PHDVXUDEOH GXH WR RYHUODS H 7RWDO LQWHQVLWLHV RI WKH WKUHH VLJQDOV WRJHWKHU E 6LJQDOV IRU \f QRW REVHUYHG HYHQ DW r&

PAGE 71

HTXDO LQWHQVLW\ FRUUHVSRQGLQJ WR FRQIRUPHU \f 7KH RQH UHPDLQLQJ VLJQDO ZDV DVVLJQHG WR FRQIRUPHU [f LQ ZKLFK DOO PHWK\OHQH SURWRQV DUH LGHQWLFDO 5HODWLYH VLJQDO LQWHQVLWLHV DQG WKH LVRPHU SURSRUWLRQV IURP WKH &+ VLJQDOV DUH VKRZQ LQ 7DEOH )RU f [f\f b DQG IRU f [f\f b )RU WKH HTXLOLEULXP DW r& f IDYRUHG FRQIRUPHU \f RYHU [f E\ NFDO PROH A +RZHYHU f ZDV IRXQG WR H[LVW H[FOXVLYHO\ LQ WKH [f FRQIRUPHU 'LDF\OLPLGD]ROLGLQHV &RQIRUPDWLRQDO 6WXG\ IURP •& 105 6SHFWUD 7KH 0+] VSHFWUD RI f ILJXUH f DW r& ZHUH QHDU FRDOHVFHQFH DQG VKRZHG EURDGHQHG OLQHV IRU & & DQG & ZKLFK EHFDPH VKDUS VLQJOHWV DW r& f ILJXUH f VKRZHG VKDUS VLQJOHWV IRU WKHVH FDUERQV DW r& $W r& IRU f ILJXUH f DQG r& IRU f ILJXUH f VLJQDOV ZHUH VHHQ IRU WKH LQGLYLGXDO FRQIRUPHUV 7DEOH f 7KH VLJQDOV ZHUH DVVLJQHG WR GLIIHUHQW FRQIRUPHUV EDVHG RQ WKH PRGHO FRPSRXQGV GLVFXVVHG HDUOLHU VHH VHFWLRQ f

PAGE 72

D D f 0+] 105 6SHFWUXP RI 'LEHQ]R\OLPLGD]ROLGLQH LQ &'&OAf DW & )LJ M L

PAGE 73

105 6SHFWUXP RI 'LEHQ]R\OLPLGD]ROLGLQH LQ &'&OAf DW )LJ 0+] &

PAGE 74

D D E _ E D +&f&2&1YYA 1&2&&+f FU} f§L U Q f§ )LJ  0+] 105 6SHFWUXP RI 'LSLYDOR\OLPLGD]ROLGLQH LQ &'&f DW r& fr}

PAGE 75

)LJ L U / 0+] & 105 6SHFWUXP RI 'LSLYDOR\OLPLGD]ROLGLQH LQ &'&Of DW &

PAGE 76

7DEOH & 105 6KLIWV 6 SSPf IRU 'LDF\OLPLGD]ROLGLQHV f DQG f &RPS 7HPS &RQIRUn ,PLGD]ROLGLQH 5VXEVWLWXHQW R LL X QR r& PDWLRQ ULQJ & + RU FFKf & & & & &n&D F F D /n/ & f E E F F F G Df D D H Ef D D Ff H D ,D E G Df D D Ef D D Ff H H H D D H D 7HQWDWLYH DVVLJQPHQW E 0+] VSHFWUXP F RQH EURDG XQUHVROYHG SHDN G 0+] VSHFWUXP 1RW REVHUYHG

PAGE 77

)RU FRPSRXQG f FRQIRUPHUV Df Ef DQG Ff VKRZHG D WRWDO RI IRXU VLJQDOV GXH WR & DQG & FDUERQV 2I WKHVH WKH WZR LQWHUPHGLDWH FKHPLFDO VKLIWV ZHUH RI HTXDO LQWHQVLW\ DQG ZHUH XQDPELJXRXVO\ DVVLJQHG WR WKH FRQIRUPHU Ef )URP WKH UXOH VWDWHG DERYH WKDW WKH FDUERQ V\Q WR WKH FDUERQ\O R[\JHQ ZDV VKLHOGHG WKH PHGLXP LQWHQVLW\ SHDN DW SSP ZDV DVVLJQHG WR Df DQG WKH ORZ LQWHQVLW\ SHDN DW SSP WR Ff 7KHVH DVVLJQPHQWV DUH LQ IDLU DJUHHPHQW ZLWK WKH FRQIRUPHU SRSXODWLRQV GHGXFHG IURP WKH SURWRQ VSHFWUDf )RU WKH & RQO\ WZR VLJQDOV ZHUH REWDLQHG WKH SHDN RI KLJKHU LQWHQVLW\ ZDV DVVLJQHG WR Ef DQG WKH RWKHU RQH EHLQJ DW D KLJKHU ILHOG WKDQ WKDW IRU Ef ZDV DVVLJQHG WR Df 7KH H[SHFWHG SHDN IRU WKH OHDVW SRSXODWHG LVRPHU Ff ZDV QRW REVHUYHG &RPSRXQG f GLVSOD\HG RQO\ WKUHH SHDNV IRU WKH FDUERQ DWRPV WZR RI HTXDO DQG KLJK LQWHQVLW\ ZHUH XQDPELJXRXVO\ DVVLJQHG WR Ef WKH OHVV LQWHQVH SHDN DW ORZHU ILHOG ZDV DVVLJQHG WR Df DJDLQ EDVHG RQ WKH UXOH WKDW WKH FDUERQ V\Q WR WKH FDUERQ\O R[\JHQ ZDV VKLHOGHG :LWK FRQIRUPHU Ff EHLQJ WKH OHDVW SRSXODWHG FI SURWRQ VSHFWUDf LWV SHDNV ZHUH QRW REVHUYHG 6LPLODUO\ IRU WKH & FDUERQ SHDNV ZHUH IRXQG RQO\ IRU Df DQG Ef

PAGE 78

L 7KH & FKHPLFDO VKLIW DVVLJQPHQWV RI WKH SKHQ\O JURXS LQ f DQG WKH WEXW\O JURXS LQ f ZHUH EDVHG RQ WKH GLIIHUHQFH LQ LQWHQVLW\ RI WKH VLJQDOV WKH RIIUHVRQDQFH VSHFWUD DQG IRU 5 &J+A FRPSDULVRQ ZLWK WKH VSHFWUXP RI f ,Q FRPSRXQG f WKH & DQG & FDUERQV RI WKH SKHQ\O ULQJ VKRZHG UHODWLYHO\ LQWHQVH VLJQDOV GRXEOHWV LQ RIIUHVRQDQFH VSHFWUXPf DQG &O D ORZ LQWHQVLW\ VLJQDO VLQJOHW LQ RIIUHVRQDQFH VSHFWUXPf ,Q FRPSRXQG f WKH TXDWHUQDU\ FDUERQ RI &&+AfA VKRZHG D ORZ LQWHQVLW\ VLJQDO DW FD SSP DQG WKH PHWK\O JURXSV JDYH D YHU\ LQWHQVH VLJQDO DW KLJKHU ILHOG 7KH ORZHVW ILHOG VLJQDO LQ WKH VSHFWUD RI FRPSRXQGV f DQG f ZDV WKDW RI WKH FDUERQ\O FDUERQV 7KH ORZ WHPSHUDWXUH VSHFWUXP RI HDFK RI WKH FRPSRXQG VKRZHG WKUHH & VLJQDOV RI ZKLFK WKH WZR RI HTXDO LQWHQVLW\ ZHUH DVVLJQHG WR WKH WZR FDUERQ\O JURXSV LQ FRQIRUPHU Ef 7KH VLJQDO GXH WR WKH OHDVW SRSXODWHG FRQIRUPHU Df LQ f DQG Ff LQ f ZDV QRW REVHUYHG 'LDF\OKH[DK\GURS\ULPLGLQHV &RQIRUPDWLRQDO 6WXG\ IURP 105 6SHFWUD 7KH 0+] VSHFWUXP RI f ILJXUH f DW r& ZDV QHDU FRDOHVFHQFH DQG VKRZHG EURDGHQHG VLJQDOV IRU & & & DQG & ZKLFK EHFDPH VKDUS VLJQDOV DW r& f ILJXUH f VKRZV VKDUS VLJQDOV IRU WKH ULQJ FDUERQV DW

PAGE 79

D f§ f§ n U )LJ / 0+] 105 6SHFWUXP RI 'LEHQ]R\OKH[DK\GURS\ULPLGLQH LQ &'&OAf DW r&

PAGE 80

D HUA6H +&A_I1AI.@A&+ e +V: R F U \ +& &+ ,IWOX\: J fL R / 0+] 105 6SHFWUXP RI 'LEHQ]R\OKH[DK\GURS\ULPLGLQH LQ &'&OAf DW r& )LJ

PAGE 81

E KF f FRF 1&2& FK f I H I L L L U / 0+] & 105 6SHFWUXP RI 'LSLYDOR\OKH[DK\GURS\ULPLGLQH LQ &'& f DW r&

PAGE 82

)LJ / 0+] & 105 6SHFWUXP RI 'LSLYDOR\OKH[DK\GURS\ULPLGLQH LQ FGFRFGf DW r&

PAGE 83

r& $W r& VLJQDOV IRU WKH LQGLYLGXDO FRQIRUPHUV DSSHDUHG LQ WKH VSHFWUXP RI f ILJXUH f +RZHYHU IRU f DW r& VHSDUDWH VLJQDOV ZHUH VHHQ RQO\ IRU WZR FRQIRUPHUV DV ZDV GHVFULEHG DERYH IRU WKH VSHFWUXP ILJXUH f 6LJQDOV ZHUH DVVLJQHG E\ UHIHUHQFH WR PRGHO FRPSRXQGV DV GLVFXVVHG HDUOLHU 7KH & FDUERQ JDYH DQ DGGLWLRQDO VLJQDO DURXQG SSP 7KH DVVLJQPHQWV RI 7DEOH IROORZ WKHVH FRQVLGHUDWLRQV $Q LOOXVWUDWLRQ IRU WKH & FDUERQV RI f DQG f LV DV IROORZV DW r& f VKRZHG WKUHH VLJQDOV IRU WKH & FDUERQ 8VLQJ WKH UXOH WKDW WKH FDUERQ V\Q WR WKH FDUERQ\O ZDV WKH PRVW VKLHOGHG WKH PRVW GRZQILHOG VLJQDO ZDV DVVLJQHG WR Ff WKH PRVW XSILHOG VLJQDO WR Df DQG WKH UHPDLQLQJ RQH WR Ef %DVHG RQ VLPLODU FRQVLGHUDWLRQV RI WKH WZR VLJQDOV VHHQ IRU WKH & FDUERQ RI f WKH PRVW LQWHQVH ZDV DVVLJQHG WR Ef 6LQFH WKH UHPDLQLQJ RQH ZDV DW D KLJKHU ILHOG WKDQ Ef LW ZDV DVVLJQHG WR Df 7KHVH DVVLJQPHQWV DJUHH ZLWK FRQIRUPHU SRSXODWLRQV GHGXFHG IURP WKH SURWRQ VSHFWUD $VVLJQPHQWV IRU WKH && FDUERQV ZHUH PDGH VLPLODUO\

PAGE 84

7DEOH & 105 6KLIWV t SSPf IRU 'LDF\OKH[DK\GURS\ULPLGLQHV f DQG f 7HPS &RPS 3\ULPLGLQH 5LQJ 56XEVWLWXHQW R Q R r& FRQIR & & & & & + RU FFKf PDWLRQf & & n & &n& & D f M4 2 Df r & r r r Ef & r r r r Ff & r r r r G D f E Df r EfG r r D 0+] VSHFWUXP E 0+] VSHFWUXP F 7HQWDWLYH DVVLJQPHQW G &RQIRUPHU Ff QRW REVHUYHG

PAGE 85

i7ULDF\OKH[DK\GURV\PWULD]LQHV &RQIRUPDWLRQDO 6WXG\ IURP -& 105 6SHFWUD 7KH 0+] VSHFWUD RI f ILJXUH f DQG f ILJXUH f DW r& VKRZHG VLJQDOV IRU WKH WKUHH PHWK\OHQH FDUERQV DW DQG SSP UHVSHFWLYHO\ $W r& IRU f ILJXUH f VLJQDOV ZHUH VHHQ IRU WKH LQGLYLGXDO FRQIRUPHUV +RZHYHU IRU f RQO\ RQH FRQIRUPHU [f ZDV REVHUYHG HYHQ DW D WHPSHUDWXUH DV ORZ DV r& 7KLV ZDV WKH VDPH UHVXOW DV VHHQ LQ LWV A+ VSHFWUXP 7KH VLJQDO DVVLJQPHQWV IRU WKH WZR FRQIRUPHUV [f DQG \f RI FRPSRXQG f DQG RQH FRQIRUPHU [f RI FRPSRXQG f ZHUH DOVR EDVHG RQ WKH PRGHO FRPSRXQGV GLVFXVVHG HDUOLHU 7KH VLJQDO DVVLJQPHQWV DUH VKRZQ LQ 7DEOH .LQHWLF 3DUDPHWHUV 7KH NLQHWLF SDUDPHWHUV REWDLQHG ZHUH WKH IUHH HQHUJ\ GLIIHUHQFH EHWZHHQ FRQIRUPHUV DQG WKH IUHH HQHUJ\ RI DFWLYDWLRQ IRU WKH EDUULHU WR URWDWLRQ DURXQG WKH DPLGH &f1 ERQGV 7KH IUHH HQHUJ\ GLIIHUHQFHV $*rf ZHUH FDOFXODWHG IURP WKH SRSXODWLRQ UDWLRV RI WKHLU & PHWK\OHQH SURWRQV VLJQDOVf REWDLQHG IRU HDFK RI WKH DPLGHV IURP WKHLU A+ 105 VSHFWUD DQG DUH JLYHQ LQ WDEOH )UHH HQHUJLHV $*rf ZKLFK DUH FRPSHQVDWHG IRU WKH HQWURS\ IDFWRU IRU WKH WRSRPHUV RI XQV\PPHWULFDO LVRPHUVf DUH DOVR JLYHQ LQ WDEOH

PAGE 86

0+= F 105 6SHFWUXP RI 7ULEHQ]R\OKH[DK\GURV\P WQD]LQH &'&DW r& LQ )LJ

PAGE 87

W L L U E 0+] & 105 6SHFWUXP RI 7ULEHQ]R\OKH[DK\GURV\PWULD]LQH LQ &'&f DW r& )LJ

PAGE 88

D +R&fR&2& E G G D 1 1&2&&+ / E G&2 E&&+f )LJ 0+] & 105 6SHFWUXP RI 7ULSLYDOR\OKH[DK\GURV\PWUD]LQH LQ &'&Of DW &

PAGE 89

f 7HPS &RPS 7ULD]LQH r& FRQIRUn ULQJ PDWLRQ f &n&n& & D f E [f r \f r r r D f LRRK [f D B K BB U FL E 0+] VSHFWUXP 0+] VSHFWUXP QRW REVHUYHG HYHQ DW & 5 VXEVWLWXHQW R LL R &+ rU & f & FFKf & n & & r r r r r r r r r r r r 7HQWDWLYH DVVLJQPHQW A &RQIRUPHU f -?

PAGE 90

7DEOH 5HODWLYH $ *r NFDO PROH AfD IRU 'LIIHUHQW &RQIRUPHUV RI $PLGHV f +H[DK\GUR ,PLGD]ROLGLQHV +H[DK\GURS\ULPLGLQHV V\PWULD]LQHV FRQIRUPHU f f f f FRQIRUPHU f f Df [f f & f f f f f Ef \f E f f f f f F f E D f f f Q D &DO LODWHG XVLQJ WKH VWDQGDUG HTXDWLRQ $ *r 57 ,Q ZKHUH LV REWDLQHG IFf F IURP FXH REVHUYHG UHODWLYH SRSXODWLRQ UDWLRV 1RW REVHUYHG LQ 105 9DOXHV JLYHQ LQ SDUHQWKHVLV DUH REWDLQHG DIWHU FRPSHQVDWLQJ IRU WKH WZR GLVWLQJXLVKDEOH IRUPV RI WKH FRQIRUPHU Ef LQ f f f DQG f DQG WKUHH LQGLVWLQJXLVKDEOH IRUPV RI WKH XQV\PPHWULFDO FRQIRUPHU \f LQ f DQG f

PAGE 91

,Q LPLGD]ROLGLQHV f DQG f Ef ZDV WKH PRVW VWDEOH FRQIRUPHU ERWK EHIRUH DQG DIWHU FRPSHQVDWLQJ IRU HQWURS\ +RZHYHU WKH UHODWLYH VWDELOLW\ RI FRQIRUPHUV Df DQG Ff EHFDPH LQWHUFKDQJHG RQ JRLQJ IURP f WR f ,Q KH[DK\GURS\ULPLGLQHV f DQG f Ef ZDV WKH PRVW VWDEOH FRQIRUPHU +RZHYHU DIWHU WKH FRUUHFWLRQ IRU HQWURS\ LQ f Df EHFRPHV WKH PRVW VWDEOH FRQIRUPHU ,Q f FRQIRUPHU Ff LV QRW REVHUYHG DW DOO ,Q KH[DK\GURV\PWULD]LQH f \f ZDV WKH PRVW VWDEOH FRQIRUPHU EXW DIWHU FRPSHQVDWLQJ IRU HQWURS\ [f EHFDPH WKH PRVW VWDEOH FRQIRUPHU ,Q f FRQIRUPHU \f ZDV QRW REVHUYHG DW DOO ,Q FRQFOXVLRQ WKH FRQIRUPHU LQ ZKLFK WKH WZR WHUW EXW\O JURXSV ZHUH RQ WKH VDPH VLGH EHFDPH HLWKHU WKH OHDVW VWDEOH FRQIRUPHU RU ZDV QRW REVHUYHG DW DOO 7KH IUHH HQHUJ\ RI DFWLYDWLRQ $*Af IRU WKH EDUULHU WR URWDWLRQ DURXQG WKH DPLGH &f1 ERQGV ZDV FDOFXODWHG IURP WKH FRDOHVFHQFH WHPSHUDWXUH REVHUYHG LQ WKH + 105 VSHFWUD IRU WKH PHWK\OHQH SURWRQV 1&+1f WDEOH f $OO WKH DPLGHV VKRZHG RQO\ RQH FRDOHVFHQFH WHPSHUDWXUH H[FHSW IRU FRPSRXQG f ZKLFK VKRZHG RQO\ RQH FRQIRUPHU HYHQ DW YHU\ ORZ WHPSHUDWXUH r&f

PAGE 92

7DEOH &RDOHVFHQFH 7HPSHUDWXUHV DQG )UHH (QHUJLHV RI $FWLYDWLRQ RI $PLGHV f $PLGH $ Y &RDOHVFHQFH $ *r REVHUYHG WHPSHUDWXUH NFDO PROH H[FKDQJH LQ 1&+ 1f 7Ff 5RWDWLRQDO %DUULHUG f DfEf EfFf f DfEf EfFf f DfEf EfFf f F DfEf EfFf f [f\f fG D 2QO\ RQH FRDOHVFHQFH WHPSHUDWXUH ZDV REVHUYHG E &DOFXODWHG XVLQJ WKH HTXDWLRQ $ *57F ORJH7F$ Yf F 2QO\ WZR FRQIRUPHUV Df DQG Ef ZHUH REVHUYHG G 2QO\ RQH FRQIRUPHU [f ZDV REVHUYHG

PAGE 93

6LQFH LPLGD]ROLGLQHV DQG KH[DK\GURS\ULPLGLQHV KDYH WKUHH FRQIRUPHUV WZR $Y YDOXHV ZHUH REWDLQHG RQH EHWZHHQ FRQIRUPHUV Df DQG Ef DQG WKH RWKHU EHWZHHQ Ef DQG Fff DQG KHQFH WZR IUHH HQHUJLHV RI DFWLYDWLRQ ZHUH REWDLQHG IRU HDFK RI WKH DPLGHV %RWK YDOXHV GLIIHUHG E\ NFDO PROH )RU KH[DK\GURV\PWULD]LQH f IRXU VLJQDOV ZHUH VHHQ IRU WKH WZR FRQIRUPHUV 7KH WKUHH HTXDO LQWHQVLW\ VLJQDOV DW DQG SSP ZHUH DVVLJQHG WR FRQIRUPHU \f DQG WKH UHPDLQLQJ VLJQDO DW SSP ZDV DVVLJQHG WR FRQIRUPHU [f VHH 7DEOH f 7KH VLJQDO DW DQG SSP ZHUH DOPRVW WKH VDPH KHQFH IRU WKH FRQYHUVLRQ RI [f WR \f WZR $Y YDOXHV ZHUH REWDLQHG RQH EHWZHHQ DQG SSP DQG WKH RWKHU EHWZHHQ DQG SSPf 7KH WZR FDOFXODWHG IUHH HQHUJLHV RI DFWLYDWLRQ GLIIHUHG E\ NFDO PROHnrn 7KH EHQ]DPLGHV KDG KLJKHU IUmHH HQHUJLHV RI DFWLYDWLRQ WKDQ WKH FRUUHVSRQGLQJ SLYDODPLGHV 7KH IUHH HQHUJ\ RI DFWLYDWLRQ IRU WULEHQ]R\OKH[DK\GURV\PWULD]LQH f ZDV ORZHU E\ NFDO PROH Af WKDQ WKDW IRU WKH EHQ]R\O GHULYDWLYHV RI LPLGD]ROLGLQH f DQG KH[DK\GURS\ULPLGLQH f 7KLV GHFUHDVH LQ DFWLYDWLRQ EDUULHU PLJKW SRVVLEO\ EH GXH WR OHVV HQHUJHWLF URWDWLRQ SURFHVVHV GLVFXVVHG LQ VHFWLRQ f

PAGE 94

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f RI URWDWLRQ DERXW WKH GLIIHUHQW DPLGH &f1 ERQGV DOVR EHFRPHV DQ LPSRUWDQW IDFWRU &RPSRXQGV OLNH 1DF\OVXEVWLWXWHG VDWXUDWHG KHWHURF\FOLF DPLQHV >&& -&63f &% %&6%3 &-&@ DQG WULQLWURVRV\P WULD]LQH >-05@ KDYH EHHQ LQYHVWLJDWHG E\ '105 +RZHYHU WKHUH KDV EHHQ QR PHQWLRQ RI WKH FORFNZLVH RU DQWLFORFNZLVH URWDWLRQ RI WKH DPLGH &f1 DQG WKH QLWURVR 11 ERQGV UHVSHFWLYHO\ )URP EDQG VKDSH DQDO\VLV RI WKH H[FKDQJH EURDGHQHG VSHFWUD RI GLQLWURVRSLSHUD]LQH FLVGLPHWK\OO GLQLWURVRSLSHUD]LQH WUDQVGLPHWK\ GLQLWURVRSLSHUD]LQH DQG WULQLWURVRKH[DK\GURV\P WULD]LQH WKH SRVVLELOLW\ RI FRUUHODWHG WZR ERQG URWDWLRQV

PAGE 95

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f ZLWK PRUH WKDQ WZR FRQIRUPHUV WKH URWDWLRQV DURXQG WKH DPLGH &f1 ERQGV FRXOG HLWKHU EH $f LQGLYLGXDO VHTXHQWLDOf RU %f FRQFHUWHG FRUUHODWHGf >-05@ &RPSRXQGV f f f DQG f FDQ H[LVW LQ WKUHH GLVWLQFW FRQIRUPHUV Df Ef DQG Ff VFKHPH DQG f )RU HDFK RI WKHVH DPLGHV PHFKDQLVP $f JRLQJ DORQJ WKH VLGHV RI WKH VTXDUHf LQWHUFRQYHUWV FRQIRUPHUV Df DQG

PAGE 96

2 5 5 2 Ef 2 5 f 5 &+ f 5 &&+f 5 Ef 2 5 Ff 5 f 5 &+ f 5 &&+f

PAGE 97

Ef DQG FRQIRUPHUV Ef DQG Ff EXW QRW GLUHFWO\ Df WR Ff 2Q WKH FRQWUDU\ PHFKDQLVP %f JRLQJ DORQJ WKH GLDJRQDO RI WKH VTXDUHf GLUHFWO\ LQWHUFRQYHUWV Df DQG Ff ZKHUHDV Ef LQWHUFRQYHUWV RQO\ ZLWK LWV WRSRPHU >$*(f@ )RU WKH WULVDPLGHV f DQG f VFKHPH f PHFKDQLVP $f JRLQJ DORQJ WKH VLGHV RI WKH FXEHf LQWHUFRQYHUWV FRQIRUPHUV [f DQG \f DV ZHOO DV FKDQJLQJ FRQIRUPHU \f LQWR LWV WRSRPHUV 0HFKDQLVP %f KDV WZR SRVVLELOLWLHV )LUVWO\ ZKHQ WZR DPLGH ERQGV URWDWH DQG WKH WKLUG GRHV QRW JRLQJ DORQJ WKH GLDJRQDO RI WKH IDFHV RI WKH FXEHf 7KLV LQWHUFRQYHUWV FRQIRUPHUV [f DQG \f DV ZHOO DV FKDQJLQJ FRQIRUPHU \f LQWR LWV WRSRPHUV 6HFRQGO\ ZKHQ DOO WKUHH DPLGH ERQGV URWDWH JRLQJ DORQJ WKH GLDJRQDO RI WKH FXEHf ,Q WKLV FDVH ERWK [f DQG \f PHUHO\ FKDQJH LQWR WKHLU FRUUHVSRQGLQJ WRSRPHUV >O$*(f@ VFKHPH f $W KLJKHU WHPSHUDWXUHV IDVW URWDWLRQ DURXQG WKH DPLGH &1 ERQGV VKRXOG OHDG WR D VLQJOHW LQ WKH 105 VSHFWUXP IRU HDFK PHWK\OHQH EHWZHHQ WZR KHWHUR DWRPV LQ WKH ULQJ LUUHJDUGOHVV RI ZKHWKHU PHFKDQLVP $f RU %f LV RSHUDWLQJ +LJKHU WHPSHUDWXUH VSHFWUD LQGHHG VKRZHG VLQJOHWV IRU WKH & PHWK\OHQH SURWRQV RI f f f DQG f 6LPLODUO\ WKH & & DQG & PHWK\OHQH SURWRQV JDYH RQH VLQJOHW IRU f DQG IRU f

PAGE 98

5 2 f 5 &+ f 5 &&+f 6FKHPH

PAGE 99

$V WKH WHPSHUDWXUH ZDV ORZHUHG WKHVH VLJQDOV IRU f EURDGHQHG FRDOHVFHG DQG VHSDUDWHG DV H[SHFWHG LQWR WZR RU PRUH SHDNV 6XUSULVLQJO\ WKH VLJQDO IRU FRPSRXQG f UHPDLQHG DV D VLQJOHW HYHQ DW r& 7KXV LW FDQ EH DVVXPHG WKDW LQ FRPSRXQG f WKH URWDWLRQV DURXQG WKH DPLGH &f1 ERQGV FRXOG EH FRUUHODWHG WKDW LV DOO WKUHH DPLGH ERQGV URWDWH VLPXOWDQHRXVO\ +RZHYHU WKH SRVVLEOLW\ RI WKUHH VHTXHQWLDO URWDWLRQV ZLWK FRQIRUPHU \f DV D VKRUW OLYHG LQWHUPHGLDWH LQ WKH WUDQVLWRU\ VWDWH FDQ QRW EH UXOHG RXW 7KH WZR ULQJ IOLS PHFKDQLVP >$&5@ DV VHHQ LQ 5A= FRPSRXQGV ZKHUH = UHSUHVHQWV HLWKHU % &+ RU 1 DQG 5 UHSUHVHQWV DU\O JURXSV FDQ EH H[WHQGHG WR FRPSRXQG f ZKHUH 5 UHSUHVHQWV WKH SLYDOR\O JURXS DQG = UHSUHVHQWV WKH KH[DK\GURV\PWULD]LQH JURXS 6LQFH '105 VSHFWURVFRS\ GHDOV H[FOXVLYHO\ ZLWK WKH SKHQRPHQRQ RI VLWH H[FKDQJH DPRQJ QXFOHL DQG LV XQLQIRUPDWLYH ZLWK UHVSHFW WR LQWHUPHGLDWH VWDWHV WKH LQIRUPDWLRQ DERXW WUDQVLWRU\ VWDWHV FDQ QRW EH REWDLQHG +RZHYHU IRU WKH SUHVHQW V\VWHP LW FDQ EH H[WUDSRODWHG IURP UHVXOWV WKDW KDYH EHHQ REWDLQHG RQ WULDU\O ERUDQHV XVLQJ PROHFXODU PHFKDQLFV >$&5@ DQG VLPSOH W\SH LQWHUDFWLRQV >&-&@

PAGE 100

&RQVLGHULQJ RQO\ VLPXOWDQHRXV FRUUHODWHGf URWDWLRQV IRU FRPSRXQGV f ff DQG f WKH URWDWLRQV DURXQG WKH DPLGH &f1 ERQGV FRXOG EH HLWKHU LQ WKH VDPH GLUHFWLRQ RU LQ RSSRVLWH GLUHFWLRQV )RU FRQIRUPHUV Df DQG Ff LI WKH URWDWLRQ LV LQ WKH VDPH GLUHFWLRQ WKHQ LQ WKH WUDQVLWLRQ VWDWH WKH 5 JURXSV SRLQW LQ WKH RSSRVLWH GLUHFWLRQ +RZHYHU LI WKH URWDWLRQ LV LQ RSSRVLWH GLUHFWLRQV WKHQ LQ WKH WUDQVLWRU\ VWDWH WKH 5 JURXSV SRLQW LQ WKH VDPH GLUHFWLRQ 7KXV IURP VLPSOH W\SH LQWHUDFWLRQV >&-&@ VDPH VLGH URWDWLRQV ZRXOG EH IDYRUHG )RU FRQIRUPHU Ef WKH FRQYHUVH LV WUXH WKDW LV RSSRVLWH VLGH URWDWLRQV DUH IDYRUHG 2Q H[WHQGLQJ VLPLODU DUJXPHQWV IRU WKH GLIIHUHQW FRQIRUPHUV RI FRPSRXQG f DQG f LW LV REYLRXV WKDW WKHUH DUH WKUHH SRVVLEOH ZD\V IRU WKH VLPXOWDQHRXV URWDWLRQV Lf RQH DPLGH ERQG LQ RQH GLUHFWLRQ DQG WKH RWKHU WZR LQ WKH RSSRVLWH GLUHFWLRQ LLf WZR DPLGH ERQGV LQ RQH GLUHFWLRQ DQG WKH WKLUG LQ WKH RSSRVLWH GLUHFWLRQ DQG LLLf DOO WKH WKUHH DPLGH ERQGV LQ RQH GLUHFWLRQ RI ZKLFK Lf DQG LLf DUH HVVHQWLDOO\ WKH VDPH &RQIRUPHU [f ZKLFK LV VLPLODU WR FRQIRUPHU Ef FDQ QRW URWDWH LQ WKH VDPH GLUHFWLRQ VLQFH DOO WKH 5 JURXSV ZLOO SRLQW LQ WKH VDPH GLUHFWLRQ LQ WKH WUDQVLWRU\ VWDWH ZKLFK LV QRW D IDYRUDEOH SURFHVV +HQFH LW KDV WR JR WKURXJK HLWKHU

PAGE 101

Lf RU LLf ZKLFK DUH WKH VDPH )RU FRQIRUPHU \f KRZHYHU HLWKHU RI WKH PHFKDQLVPV Lf RU LLff RU LLLf ZRXOG SURGXFH WKH VDPH WUDQVLWRU\ VWDWH 6R FRQIRUPHU \f FDQ URWDWH E\ HLWKHU RI WKH WZR SRVVLEOH PHFKDQLVPV &RQFOXVLRQV /RZ WHPSHUDWXUH DQG 105 VSHFWUD ZHUH UHSRUWHG IRU GLDF\OLPLGD]ROLGLQHV GLDF\OKH[DK\GURS\ULPLGLQHV DQG WULDF\OKH[DK\GURV\P WULD]LQHV 3HDNV IRU WKH LQGLYLGXDO FRQIRUPHUV IRXQG ZHUH DVVLJQHG E\ XVLQJ PRGHO FRPSRXQGV IURP UHODWLYH LQWHQVLWLHV DQG E\ LQWHUQDO FRQVLVWHQFLHV &RQIRUPHU SRSXODWLRQV WKH HQHUJ\ GLIIHUHQFH DQG WKH HQHUJ\ EDUULHU IRU WKHLU LQWHUFRQYHUVLRQ EHWZHHQ WKHP ZHUH GHGXFHG 7DEOH DQG 7DEOH f $ PHFKDQLVP IRU WKHLU LQWHUFRQYHUVLRQ ZDV SURSRVHG &RQIRUPHU SRSXODWLRQV DQG WKH HQHUJ\ GLIIHUHQFH EHWZHHQ WKH FRQIRUPHUV LQGLFDWH WKDW WKH FRQIRUPHU LQ ZKLFK WKH WZR WHUWEXW\O JURXSV SRLQW WRZDUGV HDFK RWKHU LV WKH OHDVW SRSXODWHG DQG KHQFH WKH OHDVW VWDEOH 7KLV ZDV PRVW SURQRXQFHG LQ FRPSRXQGV f DQG f ZKHUH VXFK D FRQIRUPHU ZDV QRW REVHUYHG DW DOO

PAGE 102

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r& >IRU f DQG f@ ZHUH XVHG ,Q WKHVH FDVHV &'A&2&'A ZDV XVHG DV WKH VROYHQW 7HWUDPHWK\OVLODQH ZDV XVHG DV WKH LQWHUQDO UHIHUHQFH 7KH VROYHQWV XVHG IRU WKH PRGHO V\VWHPV WDNHQ IURP WKH OLWHUDWXUH ZHUH HLWKHU &&OA >IRU f DQG f@ &'& >IRU f f DQG f@ RU &+%U >IRU f@

PAGE 103

5RRP WHPSHUDWXUH 105 VSHFWUD ZHUH UHFRUGHG RQ D 9DUDQ (0 / VSHFWURPHWHU DQG URRP WHPSHUDWXUH DQG KLJK WHPSHUDWXUH 105 VSHFWUD ZHUH UHFRUGHG RQ D -HRO ); VSHFWURPHWHU /RZ WHPSHUDWXUH n+ DQG VSHFWUD ZHUH UHFRUGHG RQ D 1LFROHW 17 VSHFWURPHWHU 3UHSDUDWLRQ RI $PLGHV 7KH V\QWKHVLV RI VDWXUDWHG KHWHURF\FOLF DPLGHV f f f f f DQG f ZDV GLVFXVVHG LQ WKH H[SHULPHQWDO SDUW RI FKDSWHU

PAGE 104

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

PAGE 105

+\GURJHQ 'HXWHULXP ([FKDQJH LQ 3\ULGRQHV +\GURJHQGHXWHULXP +'f H[FKDQJH FDQ EH FDWDO\]HG ERWK E\ DFLGV DV ZHOO DV EDVHV :LWK 1 DQG VXEVWLWXWHG S\ULGRQHV ERWK DFLG >-&6 %f 57& && -&6%f &3%@ DV ZHOO DV EDVH FDWDO\]HG >-$0 7/ -2&@ H[FKDQJHV KDYH EHHQ UHSRUWHG *HQHUDOO\ DFLG FDWDO\]HG H[FKDQJH UHTXLUHV PXFK KDUVKHU FRQGLWLRQV WKDQ WKH EDVH FDWDO\]HG UHDFWLRQ $FLG FDWDO\VLV RI K\GURJHQ H[FKDQJH LQ S\ULGRQHV $FLG FDWDO\]HG K\GURJHQGHXWHULXP H[FKDQJH RFFXUV DW WKH DQG SRVLWLRQV RI S\ULGRQHV f DW r& $ONR[\S\ULGLQH f EHKDYH VLPLODUO\ +RZHYHU PHWKR[\S\ULGLQH f GRHV QRW H[FKDQJH XQGHU WKHVH FRQGLWLRQV EXW XQGHUJRHV D UHDUUDQJHPHQW RI WKH PHWK\O JURXS IURP R[\JHQ WR QLWURJHQ >-&6%f@ f f f f

PAGE 106

2&+ &+ 2&+ KFAb QAFK f V n1 f %)n + f %DVH FDWDO\VLV RI K\GURJHQ H[FKDQJH LQ S\ULGRQHV %DVH FDWDO\]HG K\GURJHQGHXWHULXP H[FKDQJH RQ WKH RWKHU KDQG WDNHV SODFH DW WKH DQG SRVLWLRQV RI 1 DON\OS\ULGRQHV f DQG f DW r& DQG DW WKH VDPH SRVLWLRQV RI PHWKR[\OPHWK\OS\ULGLQLXP WHWUDIOXRURERUDWH f > -$0 7/ -2&@ DW r& )RU FRPSDULVRQ WKH K\GURJHQGHXWHULXP H[FKDQJH RI WKH SDUHQW V\VWHP S\ULGLQH Lf LQ &++&+ VROXWLRQ DW & >-$0 @ RU LLf LQ ''B DW r& >-$0@ RU LLLf LQ 1'a1D1' DW r& >562@ GLVSOD\V WKH UHDFWLYLW\ RUGHU f f 7KH OHDVW UHDFWLYLW\ RI WKH SURWRQ DGMDFHQW WR QLWURJHQ KDV EHHQ DVFULEHG WR GHFUHDVH LQ VFKDUDFWHU RI WKH &+ ERQG DQG WR HOHFWURVWDWLF UHSXOVLRQ EHWZHHQ WKH FRSODQDU QLWURJHQ DQG WKH HOHFWURQ SDLU RI WKH DGMDFHQW DQLRQ EHLQJ IRUPHG >-$0@ 7KH HIIHFWV RI KDORJHQ VXEVWLWXHQWV LQ WKH S\ULGLQH ULQJ RQ WKH UDWHV RI +' H[FKDQJH KDYH EHHQ VWXGLHG >-$0@ $ KDORJHQ DW WKH SRVLWLRQ DFFHOHUDWHV H[FKDQJH DW WKH SRVLWLRQ nKL KDORJHQ DW WKH SRVLWLRQ DFFHOHUDWHV H[FKDQJH DW WKH fSRVLWLRQV >$+&@

PAGE 107

$ONR[\S\ULGLQHV DUH VXVFHSWLEOH WR DON\OR[\JHQ FOHDYDJH RI WKH DONR[\ JURXS E\ DQ 61 PHFKDQLVP >-2&@ DQG FDQ DOVR XQGHUJR LVRPHUL]DWLRQ DW HOHYDWHG WHPSHUDWXUHV WR WKH WKHUPRG\QDPLFDOO\ PRUH VWDEOH 1DON\OS\ULGRQHV >&&@ 0HFKDQLVWLF VWXGLHV RI WKH FOHDYDJH RI DON\O S\ULG\O HWKHUV UHYHDOHG WKDW PHWKR[\S\ULGLQH f ZLWK &'A2'&'A2 DW r& VKRZHG H[FKDQJH DW WKH SRVLWLRQV RI WKH S\ULGLQH ULQJ LQ DGGLWLRQ WR WKH H[SHFWHG HWKHU FOHDYDJH >-2&@ $LP RI WKH :RUN )XUWKHU WR WKH LQYHVWLJDWLRQ RI WKH V\QHUJLVWLF HIIHFW RI DPLGH JURXSV GHVFULEHG LQ FKDSWHU FRPSRXQGV ZLWK DPLGH IXQFWLRQV LQ D ULQJ ZHUH DOVR FRQVLGHUHG %LV1 S\ULGRQ\OfPH WKDQH f DQG ELV1S\ULGRQ\OfPH WKDQH f ZHUH FKRVHQ IRU WKLV VWXG\ &RPSRXQG f ZDV SUHSDUHG IURP S\ULGRQH DQG PHWK\OHQH FKORULGH XQGHU SKDVH WUDQVIHU FRQGLWLRQV +RZHYHU VLPLODU UHDFWLRQ ZLWK S\ULGRQH JDYH 1S\ULGLQR[\PHWK\OfS\ULGRQH f 6FKHPH f LQVWHDG RI f EXW FRPSRXQG f RQ KHDWLQJ DW r& UHDUUDQJHG WR f $ GHWDLOHG LQYHVWLJDWLRQ RI WKH PHFKDQLVP RI WKLV UHDUUDQJHPHQW LV GLVFXVVHG LQ FKDSWHU

PAGE 108

%DVH FDWDO\]HG K\GURJHQ GHXWHULXP H[FKDQJH RQ WKHVH FRPSRXQGV f ZDV LQYHVWLJDWHG XQGHU DTXHRXV FRQGLWLRQV VLQFH WKH S\ULGRQHV ZHUH NQRZQ WR EH VWDEOH WR DTXHRXV EDVLF FRQGLWLRQV >0@ 7KH H[FKDQJHV ZHUH GRQH LQ '062GJ VROYHQW DQG ZLWK 1D2' DV WKH EDVH DQG ZHUH IROORZHG E\ A+ 105 &RPSRXQG f VKRZHG H[FKDQJH RQO\ DW WKH SRVLWLRQ RI WKH S\ULGRQH ULQJV VLPLODUO\ f VKRZHG H[FKDQJH RQO\ DW WKH SRVLWLRQV RI WKH S\ULGRQH ULQJV ,QWHUHVWLQJO\ FRPSRXQG f VKRZHG H[FKDQJH DW S\ULGLQH SRVLWLRQV LQ DGGLWLRQ WR WKH H[SHFWHG H[FKDQJH DW WKH S\ULGRQH SRVLWLRQV DW DPELHQW WHPSHUDWXUH +RZHYHU QRQH RI WKHVH FRPSRXQGV f VKRZHG DQ\ H[FKDQJH DW WKH 1&+1 LQ f DQG f RU DW WKH 1&+ LQ f SRVLWLRQV

PAGE 109

+ FKFL 6FKHPH f $OWKRXJK WKH RULJLQDO REMHFWLYHV ZHUH WKHUHIRUH QRW DWWDLQHG LQ WKDW WKH 1&IA1 JURXSV UHPDLQHG LQHUW WKH REVHUYDWLRQ RI DPELHQW WHPSHUDWXUH H[FKDQJH DW S\ULGLQH SRVLWLRQV RI FRPSRXQG f OHDG WR WKH LQYHVWLJDWLRQ RI WKH K\GURJHQGHXWHULXP H[FKDQJH RI YDULRXV 1VXEVWLWXWHG S\ULGRQHV DQG 2VXEVWLWXWHG R[\S\ULGLQHV XVLQJ 105 ,Q DGGLWLRQ WKHUH ZDV LQWHUHVW LQ GHXWHULXP ODEHOOHG VXEVWLWXWHG S\ULGLQHV 7KH PDLQ DLP RI WKLV ZRUN ZDV WR ILQG RXW WKH PHFKDQLVP RI WKLV IDFLOH H[FKDQJH LQ FRPSRXQG f 5HVXOWV DQG 'LVFXVVLRQ +\GURJHQ'HXWHULXP ([FKDQJH LQ 1 3\ULGLQR[\PHWK\OfS\ULGRQH 7KH EDVH FDWDO\]HG +' H ‘fKLQJH ZLWK 1D2' IRU FRPSRXQG fZDV SHUIRUPHG LQ '062GA 7KH VSHFWUXP RI WKH VWDUWLQJ FRPSRXQG f LV VKRZQ LQ )LJXUH VLJQDO

PAGE 110

DVVLJQPHQWV IROORZHG IURP VLPSOH PRGHO FRPSRXQGV PXOWLSOLFLW\ DQG FRXSOLQJ FRQVWDQW YDOXHV 2I WKH IRXU GRXEOHWV DQG D VLQJOHW VHHQ WKH VLQJOHW ZDV DVVLJQHG WR WKH 1&IA2 SURWRQV 7KH GRXEOHWV DW DQG SSP ZHUH DVVLJQHG WR WKH S\ULGRQH DQG SURWRQV UHVSHFWLYHO\ DQG WKH GRXEOHWV DW DQG SSP ZHUH DVVLJQHG WR WKH S\ULGLQH DQG SURWRQV UHVSHFWLYHO\ 7KH GLVDSSHDUDQFH RI WKH VLJQDO DW SSP DW r& VKRZHG WKH H[SHFWHG H[FKDQJH DW WKH SRVLWLRQV RI WKH S\ULGRQH )LJXUH f )RU 1PHWK\OS\ULGRQH VLPLODU H[FKDQJH DW S\ULGRQH SRVLWLRQV KDV EHHQ UHSRUWHG DW r& >-$0@ 2Q ZDUPLQJ XS WR r& WKH VLJQDO DW SSP EHJDQ WR GHFUHDVH LQ LQWHQVLW\ LQGLFDWLQJ DQ H[FKDQJH DW WKH DQG SRVLWLRQV RI WKH S\ULGLQH ULQJ )LJXUH f )RU PHWKR[\S\ULGLQH VLPLODU H[FKDQJH DW S\ULGLQH SRVLWLRQV KDV EHHQ UHSRUWHG DW r& >-2&@ 1R IXUWKHU H[FKDQJH ZDV REVHUYHG HLWKHU RQ FRQWLQXLQJ DW WKLV WHPSHUDWXUH RU RQ IXUWKHU LQFUHDVH LQ WKH WHPSHUDWXUH 7KH IDFW WKDW PHWKR[\S\ULGLQH GRHV QRW VKRZ H[FKDQJH RI WKH SRVLWLRQV DW DPELHQW WHPSHUDWXUH >-2&@ VXJJHVWV WKDW WKH H[FKDQJH PLJKW EH SURFHHGLQJ HLWKHU E\ DQ LQWHU RU LQWUDPROHFXODU DEVWUDFWLRQ RI WKH SURWRQ E\ WKH DQLRQ IRUPHG DW WKH S\ULGRQH f SRVLWLRQ

PAGE 111

R ) L 2 0+] A+ 105 6SHFWUXP RI 13\ULGLQR[\PHWK\fS\ULGRQH LQ '062Gf E

PAGE 112

+2' 2 E2 0+] A+ 105 6SHFWUXP RI 13\ULGLQR[\PHWK\fS\ULGRQH LQ 1D2' '062GJf $IWHU ([FKDQJH DW rF

PAGE 113

0+] + 105 6SHFWUXP RI 13\ULGLQR[\PHWK\fS\ULGRQH LQ 1D2' '062GU f $IWHU ([FKDQJH DW r& E R

PAGE 114

6R LW ZDV EHOLHYHG WKDW WKH EDVH FDWDO\VHG +' H[FKDQJH RI FRPSRXQG f FRXOG KDYH KDSSHQHG WKURXJK HLWKHU Lf DQ LQWUDPROHFXODU VHYHQPHPEHUHG LQWHUPHGLDWH f RU LLf DQ LQWUDPROHFXODU ILYHPHPEHUHG LQWHUPHGLDWH f RU LLLf D GLUHFW DEVWUDFWLRQ RI SURWRQ E\ VLPSOH LQGXFWLYH HIIHFW VLPLODU WR WKDW REVHUYHG IRU FKORURS\ULGLQHV >-$0@ DQG PHWKR[\S\ULGLQH >-2&@ ,Q FDVH LLLf WKH GLUHFW DEVWUDFWLRQ RI SURWRQ PD\ EH FDXVHG HLWKHU ZLWK DQ LQFUHDVHG LQGXFWLYH HOHFWURQ ZLWKGUDZLQJ RU D GHFUHDVH LQ PHVRPHULF HOHFWURQ GRQDWLRQ E\ R[\JHQ f + f 7KH ILYHPHPEHUHG LQWHUPHGLDWH f ZDV UXOHG RXW RQ WKH EDVLV WKDW QR H[FKDQJH ZDV REVHUYHG DW WKH 1&+Q PHWK\OHQH SURWRQV RI f 7KH VDPH ZDV IRXQG WR EH WUXH IRU WKH +' H[FKDQJH EHKDYLRU RQ GLIIHUHQW PRGHO V\VWHPV WR WHVW LLf DV GLVFXVVHG ORWH cKLV FKDSWHU

PAGE 115

7KH VHYHQPHPEHUHG F\FOLF LQWHUPHGLDWH RI Lf VHHPHG XQOLNHO\ EHFDXVH ZLWK IRXU VS K\EULGL]HG DWRPV WKHUH ZLOO EH D VHYHUH VWUDLQ LQ WKH ULQJ DOVR HQWURS\ GRHV QRW IDYRU WKLV LQWHUPHGLDWH f +RZHYHU PRGHO FRPSRXQGV ZHUH SUHSDUHG WR WHVW DOO WKH WKUHH SRVVLEOH PHFKDQLVPV Lf LLf DQG LLLf +\GURJHQ'HXWHULXP ([FKDQJH LQ 13KHQR[\PHWK\Of S\ULGRQH DQG “$U\OWKLRPHWK\OfS\ULGRQHV 7R WHVW PHFKDQLVPV Lf DQG LLf 1SKHQR[\PHWK\Of S\ULGRQH f DQG 1PHWK\OWKLRSKHQ\OPHWK\OfS\ULGRQH f ZHUH SUHSDUHG IURP S\ULGRQH DQG FKORURPHWK\OSKHQ\O HWKHU DQG S\ULGRQH DQG FKORURPHWK\OPHWK\OSKHQ\Of VXOILGH UHVSHFWLYHO\ VFKHPH f $U f $U &+ ; 6FKHPH f $U &+T&+ ; 6 f $U 12f&+ ; 6

PAGE 116

+\GURJHQGHXWHULXP H[FKDQJH VWXGLHV RQ f IROORZHG E\ + 105 VKRZHG DV H[SHFWHG H[FKDQJH DW WKH K\GURJHQV RI WKH S\ULGRQH ULQJ DW r& 2Q LQFUHDVLQJ WKH WHPSHUDWXUH WR r& RU PRUH QR H[FKDQJH LQ WKH SKHQ\O ULQJ K\GURJHQV ZDV REVHUYHG 6LPLODUO\ K\GURJHQGHXWHULXP H[FKDQJH RI f RFFXUUHG DV H[SHFWHG DW WKH PHWK\OHQH K\GURJHQV DW r& DQG RQ ZDUPLQJ XS WR r& WKH K\GURJHQV RI WKH S\ULGRQH ULQJ DOVR H[FKDQJHG 3URORQJHG KHDWLQJ DW WKLV WHPSHUDWXUH RU LQFUHDVLQJ WKH WHPSHUDWXUH GLG QRW VKRZ DQ\ H[FKDQJH LQ WKH PHWK\OSKHQ\O ULQJ K\GURJHQV 7KLV OHDG WR WKH EHOLHI WKDW WKH DU\O ULQJ KDV WR EH D S\ULGLQH ULQJ LQ RUGHU IRU DQ H[FKDQJH WR RFFXU 7KXV D VWXG\ RI WKH K\GURJHQGHXWHULXP H[FKDQJH EHKDYLRU RI 1 QLWURSKHQ\OWKLRPHWK\OfS\ULGRQH f ZDV DWWHPSWHG LQ ZKLFK ZH H[SHFW WKH QLWURSKHQ\O ULQJ WR EHKDYH OLNH WKH S\ULG\O ULQJ &RPSRXQG f ZDV SUHSDUHG IURP S\ULGRQH DQG FKORURPHWK\O QLWURSKHQ\Of VXOILGH VFKHPH f +RZHYHU FRPSRXQG f RQ +' H[FKDQJH LQ '062GJ DQG 1D2' DQG IROORZHG E\ A+ 105 VKRZHG VLJQDO EURDGHQLQJ 7KLV ZDV GXH WR WKH UDGLFDO DQLRQ IRUPHG E\ DQ DURPDWLF QLWUR FRPSRXQG LQ WKH SUHVHQFH RI D FDUEDQLRQ DV KDV EHHQ UHSRUWHG LQ WKH OLWHUDWXUH >-2&@ 7KH IRUPDWLRQ RI D GDUN UHG FRORU WRJHWKHU ZLWK WKH GLVDSSHDUDQFH RI WKH PHWK\OHQH

PAGE 117

VLQJOHW DQG WKH UHGXFWLRQ LQ WKH LQWHQVLW\ RI WKH S\ULGRQH SURWRQ VLJQDO LQGLFDWHG H[FKDQJH DW WKHVH VLWHV 7KH QLWURSKHQ\OWKLR JURXS EHLQJ D EHWWHU OHDYLQJ JURXS RQ FRQWLQXLQJ WKH H[FKDQJH WKH FRPSRXQG XQGHUZHQW 61 GLVSODFHPHQW DQG QLWURSKHQ\O WKLRO ZDV LVRODWHG IURP WKH UHDFWLRQ PL[WXUH +HQFH 1S\ULG\OHWK\OfS\ULGRQH f ZDV SUHSDUHG IURP S\ULGRQH DQG YLQ\OS\ULGLQH VFKHPH f LQ RUGHU WR WHVW PHFKDQLVP Lf +RZHYHU FRPSRXQG f LQ '062GA RQ WUHDWPHQW ZLWK 1D2' DQG IROORZHG E\ A+ 105 VKRZHG WKH DOLSKDWLF &+&+ VLJQDOV WR GLVDSSHDU DQG YLQ\OLF VLJQDOV EHJDQ WR DSSHDU DQG WKH\ LQFUHDVHG LQ LQWHQVLW\ ZLWK WLPH 7KLV LQGLFDWHG WKDW WKH VWDUWLQJ PDWHULDOV ZHUH IRUPHG DV KDV EHHQ REVHUYHG IRU VLPLODU 1SURWHFWHG FRPSRXQGV >7/@ f

PAGE 118

+\GURJHQ'HXWHULXP ([FKDQJH LQ 'LPHWK\O DONR[\S\ULGLQH 0RGHO &RPSRXQGV ,Q RUGHU WR WHVW PHFKDQLVP LLLf DQG LLf EHQ]R\OPHWKR[\GLPHWK\OS\ULGRQH f DQG ELV GLPHWK\OS\ULGLQR[\fPHWKDQH f ZHUH SUHSDUHG &RPSRXQG f ZDV SUHSDUHG IURP DEURPRDFHWRSKHQRQH DQG GLPHWK\OS\ULGRQH DQG FRPSRXQG f IURP GLPHWK\OS\ULGRQH DQG PHWK\OHQH FKORULGH XQGHU SKDVH WUDQVIHU FRQGLWLRQV VFKHPH f UFKFL r KFAQAFK KFAQAFK + f 5 &+&2 R 6FKHPH f 5 'Ln PH WK\OS\ULGLQR[\f &RPSRXQG f LQ '062GJ DQG 1D2' DQG IROORZHG E\ 105 VKRZHG H[FKDQJH RQO\ DW WKH PHWK\OHQH SURWRQV DQG FRQWLQXLQJ WKH H[FKDQJH OHG WR WKH 61 GLVSODFHPHQW RI WKH GLPHWK\OS\ULGRQH &RPSRXQG f ZDV IRXQG WR EH VWDEOH XQGHU WKHVH FRQGLWLRQV +RZHYHU QR H[FKDQJH DW WKH S\ULGLQH SRVLWLRQV ZDV REVHUYHG RQ SURORQJLQJ WKH FRQGLWLRQV IRU D ORQJ WLPH WKH PHWK\O JURXSV EHJDQ WR VKRZ DQ H[FKDQJH

PAGE 119

$ GUDZEDFN LQ WKHVH PRGHO V\VWHPV ZDV WKDW WKRXJK WKH S\ULGLQH ULQJ ZDV SUHVHQW WKH PHWK\O JURXSV SUHVHQW DW WKH SRVLWLRQV PD\ UHWDUG WKH H[FKDQJH DV KDV EHHQ REVHUYHG LQ H[FKDQJH VWXGLHV ZLWK VXEVWLWXWHG S\ULGLQHV >-&63f @ $V D UHVXOW PRGHO V\VWHPV ZLWKRXW PHWK\O JURXSV LQ WKH S\ULGLQH ULQJ ZHUH FRQVLGHUHG +\GURJHQ'HXWHULXP ([FKDQJH LQ $ONR[\S\ULGLQH 0RGHO &RPSRXQGV ,Q RUGHU WR WHVW PHFKDQLVP LLLf ZLWK DQ LQFUHDVH LQ WKH LQGXFWLYH HOHFWURQ ZLWKGUDZDO RU D GHFUHDVH LQ WKH PHVRPHULF HOHFWURQ GRQDWLRQ E\ R[\JHQ WKH IROORZLQJ PRGHO FRPSRXQGV ZHUH SUHSDUHG 3\ULG\O EHQ]RDWH f DQG SKHQR[\S\ULGLQH f PDLQO\ ZLWK DQ LQFUHDVH LQ WKH HOHFWURQ ZLWKGUDZDO E\ R[\JHQ GXH WR WKH UHVRQDQFH HIIHFW KDSSHQLQJ LQ WKH RSSRVLWH GLUHFWLRQ ZLWK WKH FDUERQ\O DQG D SKHQ\O JURXS UHVSHFWLYHO\ $QG S\ULGLQR[\fHWKDQRO f DQG DPLQRSKHQR[\fS\ULGLQH f PDLQO\ ZLWK D GHFUHDVH LQ WKH PHVRPHULF HOHFWURQ GRQDWLRQ E\ R[\JHQ GXH WR DQ LQWUDPROHFXODU K\GURJHQ ERQGLQJ EHWZHHQ WKH 2+ DQG R[\JHQ DQG 1+ DQG R[\JHQ UHVSHFWLYHO\ &RPSRXQG f ZDV SUHSDUHG IURP S\ULGRQH DQG EHQ]R\O FKORULGH VFKHPH f DQG FRPSRXQG f IURP FKORURS\ULGLQH K\GURFKORULGH DQG SKHQRO VFKHPH f

PAGE 120

3\ULG\O EHQ]RDWH f LQ '062GA DQG 1D2' DQG IROORZHG E\ 105 VKRZHG K\GURO\VLV ZKLOH SKHQR[\S\ULGLQH f GLG QRW VKRZ DQ\ H[FKDQJH FRFK + 6FKHPH f f f f 5 R 5 &+F E M 5 &+&+2+ 5 1+&+ 6FKHPH &RPSRXQG f ZDV SUHSDUHG IURP FKORURS\ULGLQH K\GURFKORULGH DQG HWK\OHQH JO\FRO DQG FRPSRXQG f ZDV SUHSDUHG VLPLODUO\ IURP FKORURS\ULGLQH K\GURFKORULGH DQG DPLQRSKHQRO VFKHPH n"

PAGE 121

7KH A+ 105 VSHFWUXP RI S\ULGLQR[\fHWKDQRO f LQ '062GJ VKRZHG D PXOWLSOHW EHWZHHQ SSP IRU WKH &+&+ SURWRQV DQG D EURDG VLJQDO DW SSP IRU 2+ 7KH GRXEOHW DW SSP DQG D EURDG VLQJOHW DW SSP ZHUH DVVLJQHG WR WKH S\ULGLQH DQG SURWRQV UHVSHFWLYHO\ )LJXUH f 2Q DGGLQJ &'A21D WKH PXOWLSOHW EHWZHHQ SSP QDUURZHG WKH VLJQDO DW SSP EHFDPH D GRXEOHW LQGLFDWLQJ WKDW LQ QHXWUDO VROXWLRQ IRU f WKH DFLGLF 2+ SURWRQ LV HTXLOLEUDWLQJ EHWZHHQ WKH K\GUR[\O R[\JHQ DQG WKH QLWURJHQf DQG DV H[SHFWHG WKH EURDG VLQJOHW DW SSP GLVDSSHDUHG )LJXUH f 2Q LQFUHDVLQJ WKH WHPSHUDWXUH WKH DOLSKDWLF PXOWLSOHW EHJDQ WR GLVDSSHDU DQG D QHZ DOLSKDWLF VLQJOHW SHDN EHJDQ WR DSSHDU LQGLFDWLQJ WKH HWKHU FOHDYDJH RI f DQG IRUPDWLRQ RI HWK\OHQH JO\FRO +RZHYHU DW r& WKH GRXEOHW DW SSP EHJDQ WR GHFUHDVH LQ LQWHQVLW\ ZLWK DQ LQFUHDVH LQ LQWHQVLW\ RI WKH VLJQDO DW SSP LQGLFDWLQJ WKH H[FKDQJH DW S\ULGLQH SRVLWLRQV )LJXUH f $PLQRSKHQR[\fS\ULGLQH f )LJXUH f LQ &'A21D&'A2''062GJ DQG IROORZHG E\ A+ 105 VKRZHG D GHFUHDVH LQ LQWHQVLW\ RI WKH S\ULGLQH SURWRQV VLJQDO ZLWK DQ LQFUHDVH LQ WKH VLJQDO LQWHQVLW\ RI WKH S\ULGLQH SURWRQV )LJXUH f 7KLV LQGLFDWHG DQ H[FKDQJH DW WKH S\ULGLQH SRVLWLRQV 7KH H[SHFWHG HWKHU FOHDYDJH

PAGE 122

f§? U )LJ 0+] + 105 6SHFWUXP RI 3\ULGLQR[\fHWKDQRO LQ '062GJf R

PAGE 123

0+] /+ 105 6SHFWUXP '062Gf DW r& E )LJ RI 3\ULGLQR[\fHWKDQRO LQ &'A21D&'A2'

PAGE 124

)LJ 0+R + 105 6SHFWUXP RI 3\ U LGLQR[\ f H WKDQRO LQ &'21D&'21D '062GJf $IWHU ([FKDQJH DW r& A

PAGE 125

D D )LJ 0+= + 105 6SHFWUXP RI $PLQRSKHQR[\fS\ULGLQH LQ &'21D '062GJf

PAGE 127

UHDFWLRQ ZDV DOVR REVHUYHG KHUH 7KLV REVHUYDWLRQ RI H[FKDQJH DW S\ULGLQH SRVLWLRQV ZLWK FRPSRXQGV f DQG f ZDV VLPLODU WR WKDW REVHUYHG IRU FRPSRXQG f DW r&f EXW DW D KLJKHU WHPSHUDWXUH r&f 7KLV REVHUYDWLRQ OHG WR WKH FRQFOXVLRQ WKDW LQ FRPSRXQG f WKH H[FKDQJH DW WKH S\ULGLQH SRVLWLRQV ZDV SURFHHGLQJ E\ PHFKDQLVP Lf 7KH IDFW WKDW PHWKR[\S\ULGLQH GLG QRW VKRZ DQ\ H[FKDQJH VLPLODU WR f f DQG f VKRZHG WKDW WKHUH ZDV DQ LQWHUDFWLRQ EHWZHHQ WKH ORQH SDLU RQ R[\JHQ DWWDFKHG WR WKH S\ULGLQH ULQJ DQG WKH HDVLO\ H[FKDQJHDEOH SURWRQ DW WKH \SRVLWLRQ RI WKH 2VXEVWLWXHQW ([SHULPHQWDO HYLGHQFH IRU WKH DVVLVWDQFH E\ WKH R[\JHQ IRU WKH SURWRQ UHPRYDO ZDV REWDLQHG E\ FRPSDULQJ WKH K\GURJHQGHXWHULXP H[FKDQJH EHKDYLRU RI FRPSRXQG f DQG 1PHWK\OS\ULGRQH f >-$0@ XQGHU LGHQWLFDO FRQGLWLRQV &RPSRXQG f ZDV IRXQG WR H[FKDQJH LQ '062 GJ DQG 1D2' ILYH WLPHV IDVWHU WKDQ f +HQFH LQ WKH H[FKDQJH RI FRPSRXQG f WKH HIIHFW KDV WR EH DQ HQKDQFHG LQGXFWLYH HOHFWURQ ZLWKGUDZDO E\ R[\JHQ DQG WKH WUDQVLWLRQ VWDWH LQYROYHG PD\ EH DV VKRZQ LQ f

PAGE 128

2 N fW % f &RQFOXVLRQV )URP WKH UHVXOWV REWDLQHG IRU WKH EDVH FDWDO\]HG K\GURJHQ GHXWHULXP H[FKDQJH EHKDYLRU RI 1VXEVWLWXWHG S\ULGRQHV DQG 2VXEVWLWXWHG R[\S\ULGLQHV )LJXUH f WKH IROORZLQJ SRLQWV FDQ EH VDLG f $ KHWHURDWRP DW WKH _SRVLWLRQ RI WKH 1DON\O VXEVWLWXWLRQ HQKDQFHV WKH +' H[FKDQJH UDWH IRU WKH SRVLWLRQV LQ 1DON\OS\ULGRQHV f $ KHWHURDWRP DW WKH \SRVLWLRQ RI WKH 2DON\O VXEVWLWXWLRQ ZLWK H[FKDQJHDEOH K\GURJHQ RU D \DFLGLF &+ HQKDQFHV WKH K\GURJHQ H[FKDQJH UDWH IRU WKH SRVLWLRQV LQ DONR[\S\ULGLQHV f ,Q JHQHUDO E\ PDQLSXODWLQJ WKH VXEVWLWXHQWV RQ QLWURJHQ LQ 1DON\OS\ULGRQHV DQG R[\JHQ LQ R[\S\ULGLQHV EDVH FDWDO\]HG K\GURJHQ H[FKDQJH FDQ EH DFKLHYHG HLWKHU DW WKH SRVLWLRQV RU DW WKH SRVLWLRQV DW DPELHQW WHPSHUDWXUHV

PAGE 129

)LJXUH %DVH &DWDO\]HG +\GURJHQ'HXWHULXP ([FKDQJH LQ 'LIIHUHQW 1 DQG 26XEVWLWXWHG 3\ULGRQHV WKH H[FKDQJLQJ SRVLWLRQV DUH LQGLFDWHG E\ r PDUNf f f f f

PAGE 130

([SHULPHQWDO 0HOWLQJ SRLQWV ZHUH UHFRUGHG RQ D %ULVWROLQH KRWVWDJH PLFURVFRSH DQG DUH XQFRUUHFWHG 7KH 105 VSHFWUD ZHUH UHFRUGHG RQ D 9DULDQ / VSHFWURPHWHU XVLQJ 706 DV WKH LQWHUQDO UHIHUHQFH DQG 105 VSHFWUD ZHUH UHFRUGHG RQ D -(2/ ); VSHFWURPHWHU DQG 9DULDQ ;/ VSHFWURPHWHU XVLQJ WKH VROYHQW '062GJf SHDN DV WKH UHIHUHQFH 7KH ,5 VSHFWUD ZHUH REWDLQHG RQ D 3HUNLQ(OPHU % VSHFWURSKRWRPHWHU 0HWKRG DQG 5HDJHQWV $OO K\GURJHQGHXWHULXP H[FKDQJHV KDYH EHHQ GRQH ZLWK H[FHVV 1D2' 0f LQ GLPHWK\OVXOIR[LGHGJ DV VROYHQW XQOHVV LQGLFDWHG $OO H[FKDQJHV ZHUH IROORZHG XVLQJ WKH GHFUHDVH LQ WKH SHDN LQWHQVLW\ RI WKH H[FKDQJLQJ SURWRQ FRXSOHG ZLWK WKH GLVDSSHDUDQFH RI WKH FRXSOLQJ RI WKH H[FKDQJLQJ SURWRQ ZLWK WKH YLFLQDO SURWRQ A+ 105f DQG ZHUH FRQILUPHG ZLWK 105 ZKLFK VKRZHG D GHFUHDVH LQ VLJQDO LQWHQVLW\ RI WKH FDUERQ WR ZKLFK WKH H[FKDQJLQJ SURWRQ LV DWWDFKHG *HQHUDO SURFHGXUH IRU K\GURJHQGHXWHULXP H[FKDQJH 7KH S\ULGRQH PJf ZDV WDNHQ LQ D PP 105 WXEH DQG ZDV GLVVROYHG LQ P/ RI '062G 7R WKLV 1D2' RU &'2'

PAGE 131

P/ 0f ZDV DGGHG DQG WKH A+ 105 VSHFWUD ZHUH UHFRUGHG SHULRGLFDOO\ )RU KLJKHU WHPSHUDWXUH H[FKDQJH WKH 105 WXEHV ZHUH KHDWHG LQ DQ RLO EDWK PDLQWDLQHG DW WKH UHTXLUHG WHPSHUDWXUH &KORURPHWK\O SKHQ\O HWKHU ES r& PPf OLW >&, @ ES r& PPff FKORURPHWK\O SKHQ\O VXOILGH ES r& PPf OLW>-2&f ES r& PPff GLPHWK\OS\ULGRQH PS r& OLW>-2&@ PS r&f 1PHWK\OS\ULGRQH f PS r& OLW>-$0@ PS r&f DQG S\ULG\OEHQ]RDWH f PS r& LW>-&6@ PS r&f ZHUH SUHSDUHG E\ OLWHUDWXUH PHWKRGV 0HWKR[\S\ULGLQH f ES r& PPf OLW>-$0@ ES r& PPff ZDV SUHSDUHG IURP PHWKR[\S\ULGLQH1R[LGH IROORZLQJ DQ DQDORJRXV SURFHGXUH >-2&@ 3\ULGRQH f DQG PHWKR[\S\ULGLQH1R[LGH ZHUH REWDLQHG IURP $OGULFK 3UHSDUDWLRQ RI 13\ULGLQR[\PHWK\OfS\ULGRQH 3\ULGRQH J PROHf EHQ]\OWULHWK\ODPPRQLXP FKORULGH J PROHf SRWDVVLXP FDUERQDWH J PROHf DQG SRWDVVLXP K\GUR[LGH b Jf ZHUH YLJRURXVO\ VWLUUHG DQG UHIOX[HG LQ PHWK\OHQH FKORULGH P/f $IWHU K WKH &+& ZDV ILOWHUHG RII WKH UHVLGXH H[WUDFWHG ZLWK KRW &WA&O DQG FRPELQHG ZLWK WKH ILOWUDWH

PAGE 132

,W ZDV GULHG ZLWK DQK\GURXV 0J62A ILOWHUHG DQG WKH VROYHQW HYDSRUDWHG WR JLYH J bf RI f PS r& ,5 &+%UAf FP + 105 '062GJf V +f G + +]f G + +]f G + +]f G + +]f $QDO FDOHG IRU &MA + T1 + & + 1 )RXQG & + 1 3UHSDUDWLRQ RI 13KHQR[\PHWK\OfS\ULGRQH DQG 1 $U\OWKLRPHWK\OfS\ULGRQHV 3UHSDUDWLRQ RI 1SKHQR[\PHWK\OfS\ULGRQH f 3\ULGRQH J PROHf EHQ]\OWULHWK\ODPPRQLXP FKORULGH J PROHf SRWDVVLXP K\GUR[LGH J bf DQG FKORURPHWK\O SKHQ\O HWKHU >7/@ J PROHf ZHUH YLJRURXVO\ VWLUUHG DQG UHIOX[HG LQ PHWK\OHQH FKORULGH P/f $IWHU K ZDV ILOWHUHG RII DQG WKH UHVXGH H[WUDFWHG ZLWK KRW &+&, FRPELQHG ZLWK WKH ILOWUDWH DQG GULHG ZLWK DQK\GURXV 0J62A 7KLV ZDV WKHQ ILOWHUHG DQG VROYHQW HYDSRUDWHG WR JLYH J bf RI f PS r& ,5 &+%UAf FP + 105 '062 GJf V +f G + +=f P +f G + +]f $QDO FDOHG IRU &@BA+@B @B12R & + 1 )RXQG & + 1

PAGE 133

3UHSDUDWLRQ RI 1PHWK\SKHQ\OWKLRfS\ULGRQH f 7R D VROXWLRQ RI S\ULGRQH J PROHf GLVVROYHG LQ DEVROXWH HWKDQRO P/f ZDV DGGHG VRGLXP J PROHf $IWHU WKH PHWDO KDG GLVVROYHG PHWK\OSKHQ\O FKORURPHWK\O VXOILGH >-2&@ J PROHf ZDV DGGHG DQG WKH PL[WXUH UHIOX[HG IRU K $IWHU FRROLQJ WR r& LW ZDV SRXUHG LQWR ZDWHU DQG H[WUDFWHG ZLWK FKORURIRUP [ P/f 7KH &+&OA H[WUDFW ZDV GULHG ZLWK DQK\GURXV 0J62A ILOWHUHG DQG UHPRYDO RI WKH VROYHQW JDYH J bf RI f PS r& ,5&+%Uf FP + 105 &'&f 6 V +f V +f G + +]f P +f $QDO FDOHG IRU &A+A126 & + 1 )RXQG & + 1 3UHSDUDWLRQ RI 1QLWURSKHQ\OWKLRfS\ULGRQHf 3UHSDUHG IROORZLQJ WKH VDPH SURFHGXUH DV GHVFULEHG IRU f EXW XVLQJ QLWURSKHQ\O FKORURPHWK\O VXOILGH >-2&@ JDYH J bf RI f PS r& ,5&+% U f FP + 105 '062GJf V +f G + +]f P +f G + +]f $QDO FDOHG IRU FL+1r6 & + 1 )RXQG & + 1

PAGE 134

3UHSDUDWLRQ RI 13\ULG\OHWK\OfS\ULGRQH f S\ULGRQH J PROHf DQG YLQ\OS\ULGLQH J PROHf WDNHQ LQ O2P/ RI HWKDQRO ZHUH UHIOX[HG IRU K 7KH UHDFWLRQ PL[WXUH ZDV FRROHG DQG HWKHU ZDV DGGHG WR WKH PL[WXUH WR JLYH J bf RI FRPSRXQG f PS & ,5 &+%Uf FP + 105 &'&f W + +]f W + +]f G + +]f G + +]f G + +]f G + +]f $QDO FDOHG IRU &+1 & + 1 )RXQG & + 1 3UHSDUDWLRQ RI 'LPHWK\ODONR[\S\ULGLQHV 3UHSDUDWLRQ RI GLPHWK\OS\ULG\O SKHQDF\O (WKHU f 3UHSDUHG IROORZLQJ WKH VDPH SURFHGXUH DV GHVFULEHG IRU f EXW XVLQJ SKHQDF\O EURPLGH LQ SODFH RI PHWK\OSKHQ\O FKORURPHWK\O VXOILGH JDYH J bf RI FRPSRXQG f PS & ,5 &+% U f FP + 105 '062GJf V +f V +f V +f P +f $QDO FDOHG IRU FL+@B1 &n K 1 )RXQG & + 1

PAGE 135

[ 3UHSDUDWLRQ RI ELVGLPHWK\OS\ULGLQR[\fPHWKDQH f 3UHSDUHG IROORZLQJ WKH VDPH SURFHGXUH DV GHVFULEHG IRU FRPSRXQG f EXW XVLQJ GLPHWK\OS\ULGRQH LQ SODFH RI S\ULGRQH JDYH J bf RI FRPSRXQG f PS & ,5 &+%Uf FPn ;+ 105 &'&f V +f V +f V +f $QDO FDOHG IRU +@B 1r & + 1 )RXQG & + 1 3UHSDUDWLRQ RI $ONR[\S\ULGLQH 0RGHO &RPSRXQGV 3UHSDUDWLRQ RI SKHQR[\S\ULGLQH f &KORURS\ULGLQH K\GURFKORULGH J PROHf ZDV GLVVROYHG LQ GLPHWK\O VXOIR[LGH P/f DQG SKHQRO J PROHf DQG VRGLXP K\GUR[LGH SHOOHWV Jf ZHUH DGGHG DQG KHDWHG JHQWO\ DW r& RYHUQLJKW 7KH PL[WXUH ZDV FRROHG DQG SRXUHG LQWR LFH DQG ZDWHU Jf DQG H[WUDFWHG ZLWK HWKHU PDQ\ WLPHV XQWLO WKH HWKHU OD\HU LV FRORUOHVV 7KH HWKHU H[WUDFWV ZHUH DOO FRPELQHG DQG GULHG ZLWK DQK\GURXV PDJQHVLXP VXOIDWH ILOWHUHG DQG WKH VROYHQW HYDSRUDWHG JDYH J bf RI FRPSRXQG fPS r& OLW>&%@ PS & f ,5 &+% U f FP + 105&'&f 6 P +f G + +]f $QDO FDOHG IRU &A+J12 & r + n, )RXQG & + 1

PAGE 136

3UHSDUDWLRQ RI S\ULGLQR[\fHWKDQRO f 7KH VDPH SURFHGXUH DV GHVFULEHG DERYH IRU FRPSRXQG f H[FHSW SKHQRO ZDV UHSODFHG E\ HWK\OHQH JO\FRO JDYH J bf RI FRPSRXQG f PS r& ,5 &+% U A f FP + 105 '062GJf 6 P +f EV +f G + +]f EV +f $QDO FDOHG IRU &+J1 & + 1 )RXQG & + 1 3UHSDUDWLRQ RI DPLQRSKHQR[\fS\ULGLQH f 7KH VDPH SURFHGXUH DV GHVFULEHG DERYH IRU FRPSRXQG f ZDV XVHG H[FHSW SKHQRO ZDV UHSODFHG E\ DPLQRSKHQRO WR JLYH J bf RI FRPSRXQG f PS r& ,5 &+%U f FP + 105 '062GJf E +f P +f G + +]f $QDO FDOHG IRU n+AA + 1 )RXQG & + 1

PAGE 137

&+$37(5 5($55$1*(0(17 ,1 $0,'(6 2;<*(1 72 1,752*(1 0,*5$7,21 2) $/.$+& 5 +&$ 7 $+&@ 7KH JUHDWHU VWDELOLW\ RI WKH DPLGH KDV EHHQ UDWLRQDOL]HG RQ WKH EDVLV RI QVWDELL]DWLRQ HQHUJ\ >7 -$0 -2&@ DQG FUIUDPHZRUN VWDELOL]DWLRQ HQHUJ\ >0,@ +RZHYHU IRU KHWHURF\FOLF DQDORJXHV RI DPLGHV VXFK DV S\ULGRQHV WKH GLIIHUHQFH LQ HQHUJ\ EHWZHHQ WKH DPLGH DQG WKH LPLGDWH IRUP LV VPDOOHU >-$0@ 7KH HTXLOLEULXP EHWZHHQ WKH DPLGH DQG WKH LPLGDWH FDQ EH FDWDO\]HG WKHUPDOO\ RU E\ DFLGV RU DON\O KDOLGHV 5 25 f f 7KH WKHUPDO UHDUUDJHPHQW RI PHWKR[\S\ULGLQH WR 1 PHWK\OS\ULGRQH KDV EHHQ VKRZQ WR EH LQWHUPROHFXODU >-$0 -&6@ $OWKRXJK WKH HDUOLHU ZRUNHUV KDYH

PAGE 138

IRXQG WKH UHDFWLRQ WR EH FDWDO\]HG E\ EHQ]R\O SHUR[LGH DQG WKDW ROG VDPSOHV RI PHWKR[\S\ULGLQH UHDUUDQJH DW D PXFK IDVWHU UDWH WKDQ IUHVK VDPSOHV SUREDEO\ GXH WR K\GURSHUR[LGH IRUPDWLRQf >-$0@ WKH ODWHU ZRUNHUV IRXQG YHU\ PLQRU FKDQJHV LQ WKH UDWH E\ DGGLQJ EHQ]R\O SHUR[LGH RU EHQ]RTXLQRQH WR WKH UHDFWLRQ PL[WXUHV >-&6@ )RU PHWKR[\S\ULGLQH WKH R[\JHQ WR QLWURJHQ PHWK\O PLJUDWLRQ 6FKHPH f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

PAGE 139

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

PAGE 140

LPLGDWHV WKH WKHUPDO UHDUUDQJHPHQW RI JURXSV IURP R[\JHQ WR QLWURJHQ NQRZQ DV &KDSPDQ UHDUUDQJHPHQW KDV EHHQ VKRZQ WR EH LQWUDPROHFXODU IRU WKH DU\O JURXS PLJUDWLRQ DQG LQWHUPROHFXODU IRU WKH DON\O JURXS PLJUDWLRQ >0, &5 &&@ $V LQGLFDWHG HDUOLHU LQ &KDSWHU WKH WKHUPDO UHDUUDQJHPHQW RI 1S\ULGLQR[\PHWK\OfS\ULGRQH f WR ELV 1S\ULGRQ\OfPH WKDQH f WRJHWKHU ZLWK WKH DYDLODELOLW\ RI GHXWHULXP ODEHOOHG FRPSRXQGV RI f OHG WR WKLV ZRUN GLVFXVVHG LQ WKLV FKDSWHU f f 7KH DLP RI WKH SUHVHQW ZRUN ZDV WR VWXG\ WKH QDWXUH RI WKH WKHUPDO PLJUDWLRQ RI WKH DON\O JURXS LQ WKLV VHOHFWHG DONR[\S\ULGLQH f DQG LWV VXLWDEO\ GHXWHUDWHG GHULYDWLYH DQG XVH 105 DQG PDVV VSHFWURVFRSLF WHFKQLTXHV WR DQDO\VH WKH SURGXFWV LQ SDUWLFXODU WR GLVWLQJXLVK EHWZHHQ LQWHU DQG LQWUDPROHFXODU UHDUUDQJHPHQW

PAGE 141

5HVXOWV DQG 'LVFXVVLRQ 7KH QDWXUH RI PLJUDWLRQ LQWHU RU LQWUDPROHFXODU LV JHQHUDOO\ HOXFLGDWHG E\ FURVVRYHU H[SHULPHQWV >0,@ 7KH XVH RI GHXWHUDWHG GHULYDWLYH LQ FURVVRYHU H[SHULPHQWV FRXSOHG ZLWK DQDO\VLV RI SURGXFWV E\ PDVV VSHFWURPHWU\ PDNHV LW DQ HOHJDQW SURFHGXUH WR VWXG\ WKH LQWHU RU LQWUDPROHFXODULW\ RI WKH UHDUUDQJHPHQW >-$0@ &KRRVLQJ WKH FRPSRXQGV IRU FURVVRYHU H[SHULPHQWV UHTXLUHV Lf WKH WZR FRPSRXQGV PXVW UHDFW DW YHU\ VLPLODU UDWHV LLf WKH PLJUDWLQJ JURXSV PXVW KDYH HVVHQWLDOO\ HTXDO UHDFWLYLW\ WRZDUGV HLWKHU RI WKH WZR UHDFWDQWV DQG LLLf TXDQWLWDWLYH HVWLPDWLRQ RI DQ\ PL[HG SURGXFWV ZKLFK DUH IRUPHG 7KH SRLQWV Lf DQG LLf ZHUH XQLTXHO\ DWWDLQHG E\ ODEHOOLQJ WKH VWDUWLQJ FRPSRXQG ERWK DW WKH PLJUDWLQJ DV ZHOO DV WKH QRQPLJUDWLQJ JURXSV 3RLQW LLLf ZDV RYHUFRPH E\ DQDO\VLQJ WKH SURGXFWV E\ D PDVV VSHFWURPHWHU +HUH FRPSRXQGV FKRVHQ IRU WKH VWXG\ ZHUH 1 S\ULGLQR[\PHWK\OfS\ULGRQH f DQG LWV WHWUDGHXWHUDWHG GHULYDWLYH 1GLGHXWHURS\ULGLQR[\PHWK\f GLGHXWHURS\ULGRQH f

PAGE 142

2 f &RPSRXQG f DQG f ZHUH REWDLQHG DV LQGLFDWHG LQ FKDSWHU 7KH H[FKDQJH RQ FRPSRXQG f KDV WR EH FDUULHG RXW DW r& WR JHW FRPSRXQG f IRU LI WKH H[FKDQJH ZDV FDUULHG RXW DW URRP WHPSHUDWXUH LW PDLQO\ JDYH 1 S\ULGLQR[\PHWK\OfGLGHXWHURS\ULGRQH WKH PDVV VSHFWUXP )LJXUH f VKRZHG LW WR EH b GLGHXWHUDWHGf 7KH PDVV VSHFWUXP RI FRPSRXQG f VKRZHG LW WR EH b WHWUDGHXWHUDWHG )LJXUH f IRU IXUWKHU GHWDLOV DERXW WKLV H[FKDQJH RQ FRPSRXQG f VHH FKDSWHU f 2Q KHDWLQJ DW r& WKH DON\O JURXS LQ FRPSRXQG f UHDUUDQJHV IURP R[\JHQ WR QLWURJHQ IRUPLQJ ELV 1 S\ULGRQ\OfPHWKDQH f DV WKH PDMRU SURGXFW DORQJ ZLWK WZR

PAGE 143

LQQ U79WfUUM +U$U777_fU7 ,62 "I LWUSL7LQ ULU\QWWOL UQ A77777nLWQ MXUIL LPM ), )UU f 2I PR LVR LRQ "QQ )LT 0DVV 6SHFWUXP RI Df 13\ULGLQR[\PHWK\fS\ULGRQH Ef 1 3\ULGLQR[\PHWK\OfGLGHXWHURS\ULGRQH DQG Ff 1 'LGHXWHUR S\ ULGLQR[\PH WK\fGLGHXWH U RS\ULGRQH

PAGE 144

PLQRU SURGXFWV 1S\ULG\OfS\ULGRQH f DQG S\ULGRQH VFKHPH f 7KH SURGXFWV ZHUH VHSDUDWHG E\ FROXPQ FKURPDWRJUDSK\ DQG LGHQWLILHG E\ WKH XVXDO DQDO\WLFDO PHWKRGV )RU f WKH PHOWLQJ SRLQW DQG VSHFWUDO GDWD DJUHHG ZLWK LWV OLWHUDWXUH YDOXHV >5&@ 7KH 105 VSHFWUXP RI WKH VWDUWLQJ PDWHULDO f DQG WKH SURGXFWV f DQG f DUH JLYHQ LQ )LJXUHV DQG UHVSHFWLYHO\ f f f 6FKHPH 6LQFH FRPSRXQG f KDV DQ 1VXEVWLWXWHGS\ULGRQH ULQJ LW FDQ E\ UHVRQDQFH DFW VLPLODU WR DQ DOO\O JURXS f DQG FDQ XQGHUJR D FDWLRQLF D]D&ODLVHQ UHDUUDQJHPHQW WR f ZKLFK DUH UHFHQWO\ UHSRUWHG WR EH RI JUHDW V\QWKHWLF XWLOLW\ >-$0 -$0@ IROORZHG E\ DQRWKHU D]D&RSH &ODLVHQf UHDUUDQJHPHQW WR JLYH ELV 1

PAGE 145

R )LJ 0+] A+ 105 6SHFWUXP RI 13\ULGLQR[\PHWK\OfS\ULGRQH LQ '062Gf

PAGE 146

3LJ  0+F A+ 105 6SHFWUXP RI WKH 0DMRU 3URGXFW RI 5HDUUDQJHPHQW %LV1 S\U/GRQ\fPH WKDQH LQ '062GJf

PAGE 147

)LJ 0+] A+ 105 6SHFWUXP RI WKH 0LQRU 3URGXFW 2EWDLQHG 13\ULG\Of S\ULGRQH LQ '062GAf

PAGE 148

S\ULGRQ\OfPHWKDQH SRVVLEOH RQO\ DIWHU WKH WZR ULQJV WKDW f 7KH VHFRQG D URWDWLRQ DURXQG LV IURP f WR UHDUUDQJHPHQW LV WKH ERQG FRQQHFWLQJ VFKHPH f f f 6FKHPH )URP WKH WKHUPRO\VLV PL[WXUH RI f QR LQWHUPHGLDWH OLNH f ZDV LVRODWHG ZKLFK VKRXOG KDYH EHHQ IRUPHG LI LW KDG JRQH WKURXJK D &ODLVHQ UHDUUDQJHPHQW XQOHVV WKH VHFRQG &ODLVHQ UHDUUDQJHPHQW ZDV PXFK IDVWHU WKDQ WKH WDXWRPHULF HTXLOLEUDWLRQ SURFHVV

PAGE 149

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f DQG WROXHQHVXOIRQLF DFLG DFLGf ZHUH IRXQG WR FDWDO\]H WKH R[\JHQ WR QLWURJHQ PLJUDWLRQ LQ FRPSRXQG f =LQF FKORULGH FDWDO\]HG WKH UHDUUDQJHPHQW DQG UHGXFHG WKH UHDUUDQJHPHQW WHPSHUDWXUH E\ r& ZKHUHDV WROXHQHVXOIRQLF DFLG FDWDO\]HG WKH UHDUUDQJHPHQW HYHQ LQ UHIOX[LQJ EHQ]HQH $FLGV DQG /HZLV DFLGV FDWDO\VLV LV FRPPRQ IRU &ODLVHQ UHDUUDQJHPHQWV >-$0 6 5@ DV ZHOO DV R[\JHQ WR QLWURJHQ PLJUDWLRQ RI DON\O JURXSV LQ S\ULGRQHV >-&6 &&@ $Q DWWHPSW ZDV PDGH WR WHVW WKH SRVVLEOLW\ RI &ODLVHQ UHDUUDQJHPHQW E\ LQWURGXFLQJ D SKHQ\O ULQJ LQ SODFH RI WKH S\ULGLQH ULQJ 6XFK D FRPSRXQG 1SKHQR[\PHWK\OfS\ULGRQH

PAGE 150

f ZDV SUHSDUHG DV LQGLFDWHG HDUOLHU LQ FKDSWHU KRZHYHU f RQ WKHUPRO\VLV JDYH HLWKHU WKH VWDUWLQJ PDWHULDO EDFN RU XQFKDUDFWHUL]DEOH WDUU\ SURGXFWV (OXFLGDWLRQ RI 0HFKDQLVP RI 5HDUUDQJHPHQW E\ 3K\VLFDO 0HWKRGV ,Q HLWKHU FRPSRXQG f RU f RQO\ LI WKH FOHDYDJH ZDV EHWZHHQ 2&IA LW FDQ OHDG WR WKH UHDUUDQJHG SURGXFW XQOHVV LW ZDV D UDGLFDO UHDFWLRQ ZKLFK ZDV IRXQG QRW WR EH WKH FDVH VLQFH WKH UHDFWLRQ ZDV FDWDO\]HG E\ /HZLV DFLGV 7KDW ZDV ZK\ ZLWK FRPSRXQG f SURGXFWV RI WKH W\SH f DQG f ZHUH QRW IRUPHG DV VHHQ IURP WKH 0+] 105 VSHFWUXP f f

PAGE 151

$ GHWDLOHG DQDO\VLV RI WKH 0+] + 105 VSHFWUD RI WKH SURGXFWV REWDLQHG IURP WKH WKHUPRO\VLV RI Lf FRPSRXQG f LLf FRPSRXQG f DQG LLLf DQ HTXLPRODU PL[WXUH RI FRPSRXQGV f DQG f GLG QRW UHYHDO DQ\ FOXH WR WKH LQWHU RU LQWUDPROHFXODU QDWXUH RI WKH PLJUDWLRQ +HQFH LQ RUGHU WR GLVWLQJXLVK WKH LQWHU RU LQWUD PROHFXODULW\ RI WKH UHDFWLRQ WKH SURGXFWV ZHUH DQDO\]HG E\ PDVV VSHFWURPHWU\ )URP WKH PROHFXODU LRQ SHDN LQWHQVLWLHV LW VKRXOG EH SRVVLEOH WR VD\ LI WKH PLJUDWLRQ ZDV LQWHU RU LQWUDPROHFXODU )RU H[DPSOH LI IRU FRPSRXQG f WKH PROHFXODU LRQ RI WKH UHDUUDQJHG SURGXFW LV 0 WKHQ IRU FRPSRXQG f LW ZRXOG EH 0 1RZ LI WKH PLJUDWLRQ ZDV MXVW LQWUDPROHFXODU WKHQ PROHFXODU LRQ SHDNV RI 0 DQG 0 ZRXOG EH VHHQ 2Q WKH RWKHU KDQG LI LW ZDV LQWHUPROHFXODU WKHQ PROHFXODU LRQ SHDNV DW 0 0 DQG 0 ZRXOG EH REVHUYHG $Q H[DFW SLFWXUH ZRXOG EH DOVR WR FRQVLGHU WKH LVRWRSH SHDN LQWHQVLWLHV RI WKH PROHFXODU LRQV 6R DQ DQDO\VLV RI SHDN LQWHQVLWLHV LQ WKH UHJLRQ RI WR LQ WKH PDVV VSHFWUD RI SURGXFWV REWDLQHG RQ KHDWLQJ DW r& IURP Lf FRPSRXQG f DORQH 6FKHPH f LLf FRPSRXQG f DORQH 6FKHPH f DQG LLLf FRPSRXQGV f DQG f WRJHWKHU 6FKHPH f ZRXOG UHYHDO WKH LQWHU RU LQWUDPROHFXODULW\ RI WKH UHDFWLRQ

PAGE 152

2 f 2 '\A<' f 7KH PDVV VSHFWUDO GDWD IRU WKH PROHFXODU LRQ RI WKH SURGXFWV RI WKH WKUHH UHDFWLRQV DUH JLYHQ LQ 7DEOH )URP HQWULHV Lf DQG LLf RI 7DEOH LW LV VHHQ WKDW RQO\ HQWU\ LLf KDV SHDNV IURP P] 6R LI WKH UHDUUDQJHPHQW ZDV RFFXUULQJ LQWUDPROHFXODUO\ WKHQ WKH SHDNV IURP P] ZRXOG DOVR KDYH WKH VDPH UDWLR RI SHDN LQWHQVLWLHV )URP 7DEOH WKH SHDN LQWHQVLWLHV ZHUH FDOFXODWHG IRU DQ LQWUDPROHFXODU PLJUDWLRQ LQ LLLf IRU

PAGE 153

R R R f PH PH PH PH ,QWHU PROHFXODUf 6FKHPH

PAGE 154

FRPSRXQG f ZLWK UHIHUHQFH WR LLf DQG NHHSLQJ WKH SHDN LQWHQVLW\ RI P] DV WKH VWDQGDUG 7KH YDOXHV DUH JLYHQ LQ HQWU\ Lf RI 7DEOH 6XEWUDFWLQJ HQWU\ Lf RI 7DEOH IURP HQWU\ LLLf RI 7DEOH JDYH WKH YDOXHV JLYHQ LQ HQWU\ LLf RI 7DEOH )URP 7DEOH WKH SHDN LQWHQVLWLHV ZHUH FDOFXODWHG IRU DQ LQWUDPROHFXODU PLJUDWLRQ LQ LLLf IRU FRPSRXQG f ZLWK UHIHUHQFH WR Lf DQG NHHSLQJ WKH SHDN LQWHQVLW\ RI P] LQ HQWU\ LLf RI 7DEOH DV WKH VWDQGDUG 7KH YDOXHV DUH JLYHQ LQ HQWU\ LLLf RI 7DEOH 6XEWUDFWLQJ HQWU\ LLLf IURP LLf LQ 7DEOH JDYH WKH GLIIHUHQFH EHWZHHQ WKH FDOFXODWHG EDVHG RQ DQ LQWUDPROHFXODU PLJUDWLRQ DQG WKH H[SHULPHQWDOO\ REVHUYHG SHDN LQWHQVLWLHV 7KH PDJQLWXGH RI WKH GLIIHUHQFH LQ LQWHQVLWLHV UHYHDO WKDW WKHUH ZDV DQ DSSUHFLDEOH LQFUHDVH LQ LQWHQVLW\ IRU WKH 0 SHDN FOHDUO\ LQGLFDWLQJ WKDW WKH UHDUUDQJHPHQW ZDV LQWHUPROHFXODU 7KH PDJQLWXGH RI GLIIHUHQFH f IRU WKH SHDN DW P] ZDV IRXQG WR EH b RI WKH LQWHQVLW\ FDOFXODWHG IRU DQ LQWUDPROHFXODU UHDUUDQJHPHQW IRU WKH VDPH SHDN DW P] 7KH VDPH UHVXOWV ZHUH DOVR REWDLQHG E\ FRQVLGHULQJ D FRPSOHWH LQWHUPROHFXODU UHDUUDQJHPHQW DQG FDOFXODWLQJ WKH LQWHQVLWLHV ,I WKH UHDUUDQJHPHQW ZDV FRPSOHWHO\ bf LQWHUPROHFXODU WKHQ WKH SURGXFWV IRUPHG IRU HQWU\ LLLf RI 7DEOH ZRXOG EH DV LQGLFDWHG EHORZ

PAGE 155

f PRQRGHXWHUDWHG FRPSRXQG f§ PRQRGHXWHUDWHG SURGXFW f f GLGHXWHUDWHG FRPSRXQG f§ PRQRGHXWH UDWHG SURGXFW GLGHXWHUDWHG SURGFW f WULGHXWHUDWHG FRPSRXQG PRQRGHXWHUDWHG SURGFXW GLGHXWHUDWHG SURGFXW f f f§ GLGHXWHUDWHG SURGXFW 7KH PRQR GL DQG WULGHXWHUDWHG FRPSRXQGV PHQWLRQHG DERYH DUH WKH SDUWLDOO\ GHXWHUDWHG FRPSRXQGV SUHVHQW DORQJ ZLWK FRPSRXQG f )URP WKH SURGXFWV IRUPHG DV VKRZQ DERYH LW LV FOHDU WKDW QR WUL RU WHWUDGHXWHUDWHG FRPSRXQGV DUH IRUPHG 6R SHDNV DW P] DQG VKRXOG KDYH LQWHQVLW\ RQO\ DV WKDW IRU WKH 0O DQG 0 SHDNV RI WKH PROHFXODU LRQ SHDN DW P] ZKLFK ZDV FDOFXODWHG WR EH b DQG b UHVSHFWLYHO\ RI WKH LQWHQVLW\ RI PROHFXODU LRQ SHDN DW P] &RQVLGHULQJ WKH SHDN LQWHQVLW\ f IRU P] LQ HQWU\ LLLf RI 7DEOH DV WKH HTXLYDOHQW RI b ZDV FDOFXODWHG WR EH 1RZ VXEWUDFWLQJ WKLV YDOXH RI IRU P] IURP WKH FRUUHVSRQGLQJ SHDN LQWHQVLW\ LQ HQWU\ LLLf RI 7DEOH WKH YDOXH ZDV REWDLQHG

PAGE 156

)URP WKH FDOFXODWHG YDOXH IRU b LQWHUPROHFXODU PLJUDWLRQ f DQG WKH H[FHVV LQWHQVLW\ REVHUYHG REWDLQHG E\ VXEWUDFWLQJ WKH FDOFXODWHG YDOXH f IURP WKH H[SHULPHQWDOO\ REVHUYHG YDOXH f JLYHQ LQ HQWU\ LLLf RI 7DEOH IRU WKH SHDN DW P] f LW ZDV IRXQG WKDW WKH H[FHVV LQ LQWHQVLW\ ZDV b RI WKH FDOFXODWHG YDOXH &RPSRXQGV f DQG f DUH VROLGV DQG WKH UHDUUDQJHPHQW RFFXUUHG DW r& ZKHQ WKH VROLGV EHJDQ WR PHOW $W WKLV VWDJH WKHUH H[LVWV D SRVVLEOLW\ RI LQKRPRJHQLW\ LQ WKH PL[WUXH 6LQFH LQWHUPROHFXODU PLJUDWLRQV DUH YHU\ PXFK GHSHQGHQW RQ WKH HQYLURQPHQW DURXQG D PROHFXOH WKH LQKRPRJHQHLW\ LQ WKH PHOW RI WKH PL[WXUH PLJKW H[SODLQ WKH IRUPDWLRQ RI LQWHUPROHFXODUO\ UHDUUDQJHG SURGXFW RQO\ WR D OHVVHU H[WHQW DV VHHQ DERYH IURP WKH FDOFXODWLRQV GRQH $QRWKHU VWURQJ HYLGHQFH DJDLQVW DQ LQWUDPROHXFODU UHDUUDQJHPHQW ZDV WKDW WKH SURGXFW f ZDV QRW GHWHFWHG LQ WKH PDVV VSHFWURPHWHU ,I WKLV SURGXFW ZDV IRUPHG WKHQ WKHUH ZRXOG KDYH EHHQ SHDNV REVHUYHG DW P] ZLWK ORVV RI K\GURJHQ DWRPf DQG DW P] ZLWK ORVV RI PHWK\O JURXSf ZKLFK ZDV QRW REVHUYHG LQ WKH PDVV VSHFWUXP RI WKH SURGXFW )LJUXH f

PAGE 157

)LJ LHH 0DVV 6SH U XUQ RI WKH IOHD &UDQJHG 3URGXFW 2EWDLQHG IURP 13\ULGLQR[\PHWK\OfS\ULGRQH

PAGE 158

)LJ 0DVV 6SHFWUXP RI WKH 5HDUUDQJHG 3URGXFW 2EWDLQHG IURP 1'LGHXWHURS\ULGLQR[\PHWK\Of GLGHXWH URS\ULGRQH

PAGE 159

)LJ LHH 0DVV 6SHFWUXP RI WKH 5HDUUDQJHG 3URGXFW 2EWDLQHG IURP D 0L[WXUH RI 1n3\ULGLQR[\PHWK\Of S\ULGRQH DQG 1f§ WL O FORXWV UR f§ S\ LGLQR[\PH WK\ f§GLGHXWHURf§f§S\ULGRQH

PAGE 160

7DEOH 0DVV 6SHFWUDO 3HDN ,QWHQVLWLHV RI WKH 0ROHFXODU ,RQVD IRU WKH 5HDUUDQJHG 3URGXFWV IURP f f DQG D 0L[WXUH RI f DQG f P] LfE f§ f§ LLf& LLLfG f§ D 7KH SHDN LQWHQVLWLHV DUH JLYHQ LQ SHUFHQWDJH WR WKH WRWDO LQWHQVLW\ RI DOO WKH SHDNV EHWZHHQ P] IRXQG LQ D WKHUPRO\VLV SURGXFW E 7KHUPRO\VLV SURGXFW RI FRPSRXQG f DORQH F 7KHUPRO\VLV SURGXFW RI FRPSRXQG f DORQH G 7KHUPRO\VLV SURGXFW RI D PL[WXUH RI FRPSRXQGV f DQG f WRJHWKHU &RQFOXVLRQV 7KH WKHUPDO UHDUUDQJHPHQW RI DON\O JURXS IRU DQ DONR[\S\ULGLQH IURP R[\JHQ WR QLWURJHQ KDG EHHQ H[SHULPHQWDOO\ HVWDEOLVKHG WR EH LQWHUPROHFXODU ZKLFK ZDV VLPLODU WR WKH DFLG DV ZHOO DV WKH DON\O KDOLGH FDWDO\]HG DON\O PLJUDWLRQV >-&6@ 7KLV ZRUN DOVR LQGLFDWHV KRZ SRZHUIXO D WRRO D ODEHOOHG FRPSRXQG FRXOG EH LQ GHFLIHULQFL KH PHFKDQLVP RI D UHDFWLRQ

PAGE 161

7DEOH &DOFXODWHG 0DVV 6SHFWUDO 3HDN ,QWHQVLWLHV DQG WKH 'LIIHUHQFH %HWZHHQ WKH &DOFXODWHG DQG ([SHULPHQWDO 0DVV 6SHFWUDO 3HDN ,QWHQVLWLHV P] LfE LLf& G LQ f 'LIIHUHQFH D 6HH IRRW QRWH nDn IRU 7DEOH E &DOFXODWHG IRU DQ LQWUDPROHFXODU PLJUDWLRQ IURP LLf RI 7DEOH DQG P] SHDN LQ LLLf RI 7DEOH DV UHIHUHQFH 2EWDLQHG E\ VXEWUDFWLQJ HQWU\ Lf RI WKLV WDEOH IURP HQWU\ LLLf RI 7DEOH A &DOFXODWHG IRU DQ LQWUDPROHFXODU PLJUDWLRQ IURP HQWU\ Lf RI 7DEOH DQG P] SHDN LQ LLf RI WKLV 7DEOH DV UHIHUHQFH ([SHULPHQWDO 0HOWLQJ SRLQWV ZHUH UHFRUGHG RQ D %ULVWROLQH KRWVWDJH PLFURVFRSH DQG DUH XQFRUUHFWHG 7KH A+ 105 VSHFWUD ZHUH UHFRUGHG RQ D 9DULDQ / VSHFURPHWHI XVLQJ 7+6 DV WKH

PAGE 162

LQWHUQDO UHIHUHQFH DQG 105 VSHFWUD ZHUH UHFRUGHG RQ D -(2/ ); VSHFWURPHWHU DQG 9DUDQ ;/ VSHFWURPHWHU XVLQJ WKH VROYHQW '062GJf SHDN DV WKH UHIHUHQFH 7KH ,5 VSHFWUD ZHUH REWDLQHG RQ D 3HUNLQ(OPHU % VSHFWURSKRWRPHWHU 5HDUUDQJHPHQW RI $ON\O *URXS IURP 2[\JHQ WR 1LWURJHQ LQ 3\ULGRQHV *HQHUDO 3URFHGXUH 7KH S\ULGRQH f RU f RU D PL[WXUH RI f DQG f PJf ZDV KHDWHG DW r& IRU PLQXWHV DIWHU ZKLFK WKH GDUN PDVV ZDV VWLUUHG ZLWK FKORURIRUP DQG ILOWHUHG JDYH PJ bf RI WKH FRUUHVSRQGLQJ ELV 1 S\ULGRQ\OfPHWKDQH PS !r& DQG XVHG GLUHFWO\ IRU PDVV VSHFWUDO DQDO\VLV )LJXUHV DQG f 3UHSDUDWLRQ RI 1'LGHXWHURS\ULGLQR[\PHWK\Of GLGHXWHURS\ULGRQH f 7KH S\ULGRQH f PJf ZDV GLVVROYHG LQ '062GJ P/f DQG VRGLXP GHXWHUR[LGH 0 ,P/f ZDV DGGHG WR WKLV VROXWLRQ 7KH PL[WXUH ZDV NHSW RYHUQLJKW DW r& FRROHG DQG WKHQ SRXUHG LQWR LFH FROG GHXWHULXP R[LGH P/f 7KH VROLG IRUPHG ZDV ILOWHUHG DQG GULHG JLYLQJ PJ bf RI S\ULGRQH f 7KLV ZDV GLUHFWO\ XVHG IRU WKH UHDUUDQJHPHQW DQG WKH PDVV VSHFWUXP )LJXUH f VKRZHG WKH SURGXFW WR EH b WHWUDGHXWHUDWHG

PAGE 163

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f WKH PRVW IDYRUHG FRQIRUPDWLRQ RI WKH GLDF\O DPLQHV KDG WKH 5 JURXS RI RQH RI WKH DF\O XQLW VWHULFDOO\ KLQGHULQJ WKH DWWDFN DW WKH PHWK\OHQH RI WKH 1 &+1 XQLW RU LLf WKH FRQIRUPHU IDYRULQJ WKH GRXEOH

PAGE 164

VWDELOL]DWLRQ ZDV QRW WKH SUHGRPLQDQW FRQIRUPHU 'LSLYDOR\OLPLGD]ROLGLQH GLG QRW UHDFW XQGHU OLWKLDWLQJ FRQGLWLRQV +RZHYHU GLEHQ]R\OLPLGD]ROLGLQH GLEHQ]R\O DQG GLSLYDOR\OKH[DK\GURS\ULPLGLQH 7ULEHQ]R\OKH[DK\GURV\PWULD]LQH DQG WULSLYDOR\OKH[DK\GURV\PWULD]LQH VKRZHG UHDFWLRQ XQGHU OLWKLDWLQJ FRQGLWLRQV ,Q FKDSWHU WKH 105 VWXG\ HTXLOLEULD DQG NLQHWLFVf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f ,Q FRQIRUPHU SRSXODWLRQ WKH 105 VSHFWUD RI DOO DPLGHV DJUHHG ZLWK WKHLU FRUUHVSRQGLQJ n+ 105 VSHFWUDO GDWD

PAGE 165

H[FHSW WKDW WKH VLJQDOV IRU WKH OHDVW SRSXODWHG FRQIRUPHUV ZHUH QRW REVHUYHG 7KH UHODWLYH HQHUJ\ GLIIHUHQFH EHWZHHQ WKH GLIIHUHQW FRQIRUPHUV ZDV FDOFXODWHG IURP WKH SRSXODWLRQ UDWLRV REWDLQHG $OO DPLGHV H[FHSW WULSLYDOR\OKH[DK\GURV\P WULD]LQH VKRZHG RQO\ RQH FRDOHVFHQFH WHPSHUDWXUH 7KH HQHUJ\ RI DFWLYDWLRQ IRU WKH EDUULHU WR URWDWLRQ DURXQG DPLGH &f1 ERQGV ZDV FDOFXODWHG IURP WKH FRDOHVFHQFH WHPSHUDWXUH 7KH HQHUJ\ LQ JHQHUDO IRU EHQ]DPLGHV ZDV DURXQG NFDO PROH A DQG IRU SLYDODPLGHV DURXQG NFDO PROH ‘r‘ 7KH PHFKDQLVP RI URWDWLRQ RI WKH DPLGH JURXSV IURP WKHLU VSHFWUDO EHKDYLRU ZDV GLVFXVVHG 7KH URWDWLRQV ZLOO EH HLWKHU LQGLYLGXDO RU FRQFHUWHG VDPH RU GLIIHUHQW GLUHFWLRQf )RU WULSLYDOR\OKH[DK\GURV\PWULD]LQH RQO\ RQH FRQIRUPDWLRQDO LVRPHU WKH V\PPHWULFDOf ZDV REVHUYHG LQGLFDWLQJ WKDW LQ WKDW PROHFXOH WKH URWDWLRQ DURXQG WKH DPLGH &f1 ERQGV PD\ EH FRQFHUWHG RU FRUUHODWHGf RU WKH URWDWLRQV PD\ EH VHTXHQWLDO ZLWK WKH XQV\PPHWULFDO FRQIRUPDWLRQDO LVRPHU DV D VKRUW OLYHG LQWHUPHGLDWH LQ WKH WUDQVLWLRQ VWDWH RI WKH WRSRPHUL]DWLRQ SURFHVV RI WKH V\PPHWULFDO FRQIRUPDWLRQDO LVRPHU )XUWKHUPRUH LW ZDV VSHFXODWHG IRU f§ WULSLYDOR\OKH[DK\GURV\PWULD]LQH WKH OHDVW HQHUJHWLF SURFHVV IRU WRSRPHUL]DWLRQ RI WKH V\PPHWULFDO FRQIRUPDWLRQDO

PAGE 166

LVRPHU ZRXOG EH WKDW LQ ZKLFK WZR DPLGH ERQGV URWDWH LQ RQH GLUHFWLRQ ZKLOH WKH WKLUG RQH URWDWHV LQ WKH RSSRVLWH GLUHFWLRQ 7KH K\GURJHQGHXWHULXP +'f H[FKDQJH EHKDYLRU RI GLIIHUHQW 1 DQG VXEVWLWXWHG YLQ\ORJRXV DPLGHV VXFK DV WKH S\ULGRQHV ZDV GLVFXVVHG LQ FKDSWHU 7KH PDLQ DLP ZDV WR H[SODLQ WKH DPELHQW WHPSHUDWXUH K\GURJHQ GHXWHULXP H[FKDQJH DW WKH SRVLWLRQV RI WKH S\ULGLQH ULQJ LQ 1 S\ULGLQR[\PHWK\OfS\ULGRQH $ QXPEHU RI 1VXEVWLWXWHG S\ULGRQHV DQG VXEVWLWXWHG R[\S\ULGLQHV ZHUH LQYHVWLJDWHG ,W ZDV IRXQG WKDW D KHWHURDWRP 6f DW WKH JSRVLWLRQ RI WKH 1DON\O VLGH FKDLQ LQFUHDVHG WKH +' H[FKDQJH UDWH RI WKH SURWRQV ILYH IROG FRPSDUHG WR 1PHWK\OS\ULGRQH $QG DOVR D KHWHURDWRP ZLWK DQ H[FKDQJHDEOH K\GURJHQ RU DQ DFLGLF &+ DW WKH \SRVLWLRQ RI WKH DON\O VLGH FKDLQ LQFUHDVHG WKH +' H[FKDQJH UDWH RI WKH SURWRQV FRPSDUHG WR PHWKR[\S\ULGLQH 7KH PHFKDQLVWLF VWXG\ RI DON\O JURXS PLJUDWLRQ IURP R[\JHQ WR QLWURJHQ LQ YLQ\ORJRXV DPLGHV VXFK DV WKH S\ULGRQHV ZDV GLVFXVVHG LQ FKDSWHU 7KH UHDUUDQJHPHQW RI 1S\ULGLQR[\PHWK\OfS\ULGRQH DW r& JDYH ELV1 S\ULGRQ\OfPHWKDQH 7KH UHDUUDQJHPHQW SURGXFWV IURP Lf 1 S\ULGLQR[\PHWK\OfS\ULGRQH LLf 1GLGHXWHUR

PAGE 167

S\ULGLQR[\PHWK\OfGLGHXWHURS\ULGRQH DQG LLLf D PL[WXUH RI 1S\ULGLQR[\PHWK\OfS\ULGRQH DQG 1 GLGHWXH URS\ULGLQR[\PHWK\OfGLGHWXHURS\ULGRQH ZHUH DQDO\VHG E\ PDVV VSHFWURPHWU\ 7KH PROHFXODU LRQ SHDNV IURP P] WR f RI Lf DQG LLf ZHUH XVHG WR FDOFXODWH WKH LQWHQVLWLHV RI WKH PROHFXODU LRQ SHDNV IRU LLLf DQG FRPSDUHG ZLWK WKH H[SHULPHQWDOO\ REVHUYHG YDOXHV 7KH FRPSDULVRQ VKRZHG D ODUJH LQFUHDVH DW P] LQGLFDWLQJ WKDW WKH WKHUPDO UHDUUDQJHPHQW RI DON\O JURXSV IURP R[\JHQ WR QLWURJHQ LQ DONR[\S\ULGLQHV ZDV LQWHUPROHFXODU

PAGE 168

%,%/,2*5$3+< 7KH V\VWHP DGRSWHG IRU UHIHUHQFHV LV WKH RQH GHVLJQDWHG E\ .DWULW]N\ DQG 5HHV LQ WKHLU ERRN &RPSUHKHQVLYH +HWHURF\FOLF &KHPLVWU\ 3HUJDPRQ 3UHVV 1HZ
PAGE 169

&% &KHP %HU && &KHP 6RF &KHP &RPPXQ &O &KHP ,QG &-& &DQ &KHP &5 &KHP 5HY *&, *D]] &KLP ,WDO +&$ +HOY &KLP $FWD -$0 $P &KHP 6RF -&3 &KHP 3K\V -&6 &KHP 6RF -&6%f &KHP 6RF %f -&63,f &KHP 6RF 3HUNLQ 7UDQV -&63f &KHP 6RF 3HUNLQ 7UDQV -+& +HWHURF\FO &KHP -05 0DJ 5HVRQ -2& 2UJ FKHP -20 2UJDQRPHW &KHP -3& 3K\V &KHP 0 0RQDWVK &KHP 0, 0LVFHOODQHRXV >ERRNMRXUQDO@ 00 0DFURPROHXFOHV 205 2UJ 0DJ 5HVRQ 25 2UJ 5HDFW 5& 5RF] &KLP 6 6\QWKHVLV 7 7HWUDKHGURQ 7/ 7HWUDKHGURQ /HWW

PAGE 170

&% ( .RHQLJV DQG + *UHLQHU &KHP %HU -2& : &DPSEHOO ) $FNHUPDQ DQG % &DPSEHOO 2UJ &KHP -2& ( 2FKLDL 2UJ &KHP -&3 : 3KLOOLSV &KHP 3K\V -$0 % :LEHUJ 7 0 6KU\QH DQG 5 5 .LQWQHU $P &KHP 6RF -&6 &DGRJDQ &KHP 6RF $ 0 % %RXUQD]HO $QQ &KLP 3DULVf -&6 ) 0 (ONREDLVL DQG : +LFNLQERWWRP &KHP 6RF &5 5 5RJHU DQG 1HLOVRQ &KHP 5HY -$0 &UDP & $ .LQJVEXU\ DQG % 5LFNERUQ $P &KHP 6RF -3& 0 7 5RJHUV DQG & :RRGEUH\ 3K\VLFDO &KHP $+& $ 5 .DWULW]N\ DQG 0 /DJRZVNL $GY +HW &KHP -$0 / $ /D 3ODQFKH DQG 0 7 5RJHUV $P &KHP 6RF -$0 &UDP DQG / *RVVHU $P &KHP 6RF -2& 5 % 0RIIHWW 2UJ &KHP 0, % 3XOOPDQ DQG $ 3XOOPDQ 4XDQWXP %LRFKHPLVWU\ ,QWHUVFLHQFH 1HZ
PAGE 171

-$0 / $ /D 3ODQFKH DQG 0 7 5RJHUV $P &KHP 6RF -2& ) 'LQDQ DQG + 7LHFNHOPDQQ 2UJ &KHP 0, / $ &RKHQ DQG % :LWNRS LQ 0ROHFXODU 5HDUUDQJHPHQWV 3 GH 0D\R HG YRO ,QWHUVFLHQFH 1HZ
PAGE 172

-$0 $ =ROWHZLF] DQG & / 6PLWK $P &KHP 6RF -2& $ 5XVVHO DQG 6 $ :HLQHU 2UJ &KHP -2& 5 0 0RULDUW\ DQG 0 .OHLJPDQ 2UJ &KHP 7/ + $ 6WDDE DQG /DXHU 7HWUDKHGURQ /HWW $-& 5 ) (YDQV $XVW &KHP &% + 3DXOVHQ DQG 7RGW &KHP %HU && 7KDFNHU DQG 7 / 9 8OEULFKW &KHP 6RF &KHP &RPP && 3 %HOOLQJKDP & -RKQVRQ DQG $ 5 .DWULW]N\ &KHP 6RF &KHP &RPP +&$ & $ *URE DQG + :LONHQV +HO &KLP $FWD -&6%f 3 %HOOLQJKDP & -RKQVRQ DQG $ 5 .DWULW]N\ &KHP 6RF %f -$0 $ =ROWHZLF] DQG & / 6PLWK $P &KHP 6RF -$0 + 6 *XWRZVN\ -RQDV DQG 7 + 6LGGDOO ,,, $P &KHP 6RF &-& < / &KRZ & &RORQ DQG 1 6 7DP &DQ &KHP &3% < .DXD]RH DQG <
PAGE 173

-&6% f 3 %HOOLQJKDP & -RKQVRQ DQG $ 5 .DWULW]N\ &KHP 6RF %f 0, 7RSLFV LQ 6WHUHRFKHPLVWU\ 9RO HG ( / (OLHO DQG 1 / $OOLQJHU ,QWHUVFLHQFH 1HZ
PAGE 174

-$0 1 5RLWPDQ DQG &UDP $P &KHP 6RF && % & &KDOOLV DQG $ )UHQNHO &KHP 6RF &KHP &RPP && : $ 7KRPDV DQG 0 :LOOLDPV &KHP 6RF &KHP &RPP -&63f / /XQD]]L ) 3HGXOOL 0 7LHFFR DQG & $ 9HUDFLQL &KHP 6RF 3HUNLQ 7UDQV -2& 0RQWDQGR DQG 3 )LQRFFKLDUR -2UJ &KHP 00 0RQWDQGR 3 )LQRFFKLDUR 3 0DUDYLJQD DQG & 2YHUEHUJHU 0DFURPROHXFOHV $+& ( &DOI DQG / *DUQHWW $GY +HW &KHP -+& % .DQJ 6HQ DQG %6 7K\DJDUDMDQ +HW &KHP $+& $ (OYLGJH 5 -RQHV & 2n%ULHQ ( $ (YDQV DQG + & 6KHSSDUG $GY +HW &KHP %&60 .LWDQR DQG .XFKLWVX %XOO &KHP 6RF -DSDQ -$0 ( / (OLHO $ $ +DUWPDQQ DQG $ $EDWMRJORX $P &KHP 6RF -$0 & +
PAGE 175

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f 6 'DYLHV DQG : $ 7KRPDV &KHP 6RF 3HUNLQ 7UDQV -05 +RIQHU 6 6WHSKHQVRQ DQG %LQVFK 0DJ 5HV

PAGE 176

0, 6DGWOHU 6WDQGDUG &DUERQ 105 6SHFWUDf 6SHFWUXP QXPEHUV DQG $*(f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f &LUULQFLRQH : +LQ] DQG 5 $ -RQHV &KHP 6RF 3HUNLQ 7UDQV -&63Lf ) %DEXGUL 6 )ORULR $ 5HKR DQG 7UDSDQL &KHP 6RF 3HUNLQ 7UDQV 7/ $ 5 .DWULW]N\ 5 .KDQ DQG $ 6FKZDU] 7HWUDKHGURQ /HWW 7/ 8 0RULQGHU D Q + T :H U! Q H U V W U R P 7HWUDKHGURQ /HWW 0 -HUU\ 0DUFK $GYDQFHG 2UJDQLF &KHPLVWU\ WKLUG HGLWLRQ :LOH\,QWHUVFLHQFH 1HZ
PAGE 177

%,2*5$3+,&$/ 6.(7&+ 5DPLDK 0XUXJDQ ZDV ERUQ RQ -XO\ DW 0DGXUDL D FLW\ LQ 7DPLO 1DGX VWDWH LQ ,QGLD +H UHFHLYHG KLV %DFKHORU RI 6FLHQFH VSHFLDOf GHJUHH LQ FKHPLVWU\ IURP $PHULFDQ &ROOHJH DIILOLDWHG WR 0DGXUDL 8QLYHUVLW\f LQ $SULO 7KHQ KH UHFHLYHG KLV 0DVWHU RI 6FLHQFH GHJUHH LQ FKHPLVWU\ ZLWK VSHFLDOL]DWLRQ LQ RUJDQLF FKHPLVWU\f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

PAGE 178

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

PAGE 179

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

PAGE 180

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

PAGE 181

2L220

PAGE 182

n?? PHWDOODWLRQFRQIR22PXUX


3-93'\\
metallationconfoOOmuru