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Charge transfer in cyclopolymerization and theoretical calculations for charge transfer in copolymerization

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Charge transfer in cyclopolymerization and theoretical calculations for charge transfer in copolymerization
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Vaz, Roy Joseph Noel, 1958-
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English
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x, 163 leaves : ill. ; 28 cm.

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Subjects / Keywords:
Carbon ( jstor )
Charge transfer ( jstor )
Copyrights ( jstor )
Ethers ( jstor )
Flasks ( jstor )
Geometric angles ( jstor )
Monomers ( jstor )
Polymers ( jstor )
Protons ( jstor )
Sodium ( jstor )
Charge transfer ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Polymers -- Electric properties ( lcsh )
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bibliography ( marcgt )
non-fiction ( marcgt )

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Thesis:
Thesis (Ph. D.)--University of Florida, 1985.
Bibliography:
Bibliography: leaves 159-162.
General Note:
Typescript.
General Note:
Vita.
Statement of Responsibility:
by Roy Joseph Noel Vaz.

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CHARGE TRANSFER IN CYCLOPOLYMERIZATION AND THEORETICAL CALCULATIONS FOR CHARGE TRANSFER
IN COPOLYMERIZATION






BY





ROY JOSEPH NOEL VAZ


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


1985














ACKNOWLEDGMENTS


I would like to express my deep gratitude to a scholar and

gentleman, Dr. G.B. Butler, for his help, stimulation and imparting of wisdom during the course of my stay at the University of Florida. I would like to extend my thanks and appreciation to members of the supervisory committee and to Dr. T.E. Hogen Esch for their time and

help.
Appreciation and thanks also go out to Dr. M. Zerner and

especially Dr. G. Purvis for their patience, time and help at the Quantum Theory Floor.

All the members of the Polymer Division are greatly acknowledged

for their patience and forbearance. Dr. A. Matsumoto is thanked for many helpful discussions.

Friends outside of chemistry are acknowledged for my maintenance of composure.
Thanks are due to Ms. Cindy Zimmerman for the typing of this manuscript.
Financial support from the Department of Chemistry and the National Science Foundation is acknowledged.














TABLE OF CONTENTS


Page
ACKNOWLEDGMENTS ................................................... ii

LIST OF TABLES ...................... ....... ............ ......... v

LIST OF FIGURES ................................. vii

ABSTRACT ................................. ix

CHAPTERS

I INTRODUCTION ......................................... 1

Cycl opol ymeri za ti on ..................................... 1
Charge Transfer ...................................... 7
Proposed Research ..................................... 12

II EXPERIMENTAL ........................................... 14

General Information ................. .... 14
Reagents and Sal vents..........................15
Synthesis of Monomers .. ................. 16
Synthesis of Model Compounds .................. 36
Miscellaneous Reactions ........... .... 44
Synthesis of Polymers ........... . ...... 47

III RESULTS AND DISCUSSION .............................. 53

NMR Analysis ........................................... 53
Synthesis of Monomers .................................. 53
Synthesis of Model Compounds ......................... 77
Comparison of Spectra ................................ 85
Polymer Synthesis and Characterization ................ 100
Conclusions on Polymerization of Monomers ............. 104
Frontier Molecular Orbital Analysis ................. 108

IV THEORETICAL CALCULATIONS .............................. 114

Introduction .............................114
Calculation Details...............................118
Discussion ..................... ...................... 135
Conclusions ........................................... 139









APPENDIX CNDO/2 DENSITY MATRICES AND GROSS CHARGE DENSITIES
FOR N-METHYLMALEIMIDE, METHYL VINYL ETHER, C2
AND C3, RESPECTIVELY .................................. 141

BIBLIOGRAPHY ............................................ ......... 159

BIOGRAPHICAL SKETCH .............................................. 163













LIST OF TABLES


Table

1 2 3 4 5 6 7 8 9 10 11 12 13 14


NMR NMR NMR NMR NMR NMR NMR NMR NMR NMR NMR NMR NMR NMR


assignments assignments assignments assignments assignments assignments assignments assignments assignments assignments assignments assignments assignments


for for

for for for for for

for for for for for for


compound compound compound compound compound compound compound compound compound compound compound compound compound


Carbon-13 and proton Proton and carbon-13 Proton and carbon-13 Proton and carbon-13 Proton and carbon-13 Carbon-13 and proton Carbon-13 and proton Carbon-13 and proton Carbon-13 and proton Carbon-13 and proton Proton and carbon-13 Proton and carbon-13 Proton and carbon-13 Proton and carbon-13


Page

(2) ..... 60

(4) ..... 64

(5) ..... 64

(6) ..... 65

(7) ..... 65

(14) .... 70

(9) ..... 70

(11) .... 71

(10)....73

(16)....79

(20) .... 83

(19) .... 83

(18) .... 84

(21) .... 87


15 Comparative proton and carbon chemical shifts for
compounds (3) and (16) .................................... 89

16 Comparative proton and carbon chemical shifts for
compounds (8) and (17) .................................... 90
17 Comparative proton and carbon chemical shifts for
compounds (15) and (21) ................................... 91


assignments for compound








18 Comparative carbon chemical shifts for fumaronitrile
and 2,4,6-trimethoxystyrene separate and mixed in a
1:1 molar ratio ........................................... 95

19 Comparative proton chemical shifts for fumaronitrile
and 2,4,6-trimethoxysytrene separate and mixed in a
1:1 molar ratio ........................................... 96

20 13C chemical shift differences with acceptors different...97

21 13C chemical shift differences with donors different ...... 97

22 Comparison of CNDO and PCILO deteripinations with
experimental data, AE-kcal/mole,R-A ...................... 117

23 Parameters of methyl vinyl ether ......................... 119

24 Parameters of N-methylmaleimide .......... 120

25 Coordinates of C2 and C3 ................................. 122
0
26 Bond angles and distances (A) of C2 ...................... 123

27 Bond angles and distances of C3 ... . .....125

28 Energy gradient values of last cycle and summary of
geometry optimization of cycles 95-106 for methyl
vinyl ether .............................................. 127

29 Energy gradient values of last cycle and summary of
geometry optimization of cycles 38-46 for
N-me thylmaleimi de ........................ 128

30 Energy gradient values of last cycle and summary of
geometry optimization of cycles 155-156 for C2 ........... 129

31 Energy gradient values of last cycle and summary of
geometry optimization of cycles 167-170 for C3 ........... 130

32 CNDO energy and difference in energy corresponding to
various distances between molecules N-methylmaleimide
and methyl vinyl ether ................................... 133
33 PCILO energy and difference in energy corresponding to
various distances between molecules N-methylmaleimide
and methyl vinyl ether ................................... 137

34 Coordinates of the comglex (Ec*) with the moieties
at a distances of 7.0 A .................................. 138













LIST OF FIGURES


Figure Page

1 Reaction coordinates proposed as a result of product
distribution study in the cyclization of radicals XII
and XIII .. ............................................... 8

2 Evidence for charge transfer between acrylonitrile and
styrene in the presence of ZnCl2 ....................... 11

3 Apparatus for the pyrolysis of chloroacetone cyanohydrin
acetate .... ............................................ 23
4 Proton spectrum of the pyrolysis products with the
integration (in CDCI3) ................................... 24

5 HPLC chromatograph. Separation of 2-phenylallyl 2'cyanoallyl ether ..................................... 27

6 Proton (60 MHz) spectrum in CDCl3 ...................... 32

7 HPLC chromatograph. Separation of 2-phenyl 2'carboethoxyal lyl ether .................................... 37

8 Information regarding C 13 NMR chemical shifts of
substituted alkenes .............................. .. 54
9 Proton (100 MHz) spectrum and noise decoupled C 13
spectrum of compound (1) in CDC13 ......................... 58
10 Proton (100 MHz) spectrum (in CDCI3) ang C 13 noise decoupled 25 MHz spectrum (in benzene-d ) of compound
(3) .............................. ..................... . 61
11 Proton spectrum (100 MHz)(in benzene-d6) and C 13 noise decoupled spectrum (25 MHz)(in CDCl3) of compound (8) ..... 66

12 25 MHz decoupled and multiplicity determination C 13 spectra for compound (8) ............................... 67

13 Carbon-13 (25 MHz) spectrum of the pyrolysis of 1-bromo-2,2-dimethoxy propane ............................. 74







14 Proton spectrum (60 MHz) in CDC13 (15) .................... 75

15 Noise and off-resonance decoupled C 13 spectra in
CDC13 (15) ................................... ........ .. 76

16 Proton (100 MHz) NMR spectrum (in CDCl3) and carbon-13
(25 MHz) NMR spectrum (in CDCI3) of compound (17) ......... 81 17 25 MHz decoupled and multiplicity determination
sequence C 13 spectra (21) ... ............................ 86

18 Analysis for explanation of observed shifts ............... 92

19 Synthesis scheme used for 2,4,6-trimethoxystyrene ......... 93 20 UV of compound (15)(conc = 10-5 M) in t-butyl
alcohol at different temperatures ......................... 99

21 GPC curves for polymers (in DMF) formed at different
temperatures .............................. ...... ........ 101

22 Proton NMR for polymers (in CDCl3) formed at 400 C
and 600 C ................................................ 102

23 Carbon-13 NMR spectra for polymers formed at 400 C
and 600 C ................................................ 103

24 GPC curves for polymers (in DMF) formed at R.T. and
400 C .................................................... 105
25 Frontier orbital energies and coefficients of
ethylene and monosubstituted ethylenes ................. 109

26 Representation of the systems studied .................... 111

27 Z-axis view of ZINDO geometry optimized molecules ........ 121 28 Z-axis view of ZINDO geometry optimized molecules ........ 131 29 Plot of AEcompI Ec - (E1 + E2) vs. distance ............ 134
30 Plot of AEcompl* = Ec*(r) - Ec*(-) vs. distance .......... 136


viii













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

CHARGE TRANSFER IN CYCLOPOLYMERIZATION AND
THEORETICAL CALCULATIONS FOR CHARGE TRANSFER IN COPOLYMERIZATION

BY

ROY JOSEPH NOEL VAZ

August, 1985

Chairman: Dr. George B. Butler Major Department: Chemistry

Continuing studies on the mechanism of cyclopolymerization lead to the inclusion of charge transfer complexes in the monomer in order

to influence the ring size. It was anticipated that if a donor and acceptor group were substituted at the C2 and C2, positions, respectively, of an allyl ether, an intramolecular complex would be formed.

Monomers selected for the study were 2-chloroallyl 2'-phenylallyl ether, 2-carboethoxyallyl 2'-phenylallyl ether, 2-cyanoallyl 2'phenylallyl ether and 2-carboethoxyallyl 2'-methoxyallyl ether. Intramolecular charge transfer complexation was proved by omitting the point of unsaturation having the donor group. For this study 2carboethoxyallyl 2'-phenylpropyl ether, 2-cyanoallyl 2'-phenylpropyl ether and 2-carboethoxyallyl 2'-methoxypropyl ether were synthesized








and the carbon-13 and proton NMR spectra were compared with those of the corresponding monomers in order to determine "charge transfer."

The monomers were polymerized with 2,2'-azobisisobutyronitrile in benzene and only 2-carboethoxyallyl 2'-phenylallyl ether gave a linear cyclopolymer soluble in most organic solvents. 2-Chloroallyl 2'phenylallyl ether did not afford any polymer and 2-cyanoallyl 2'phenylallyl ether and 2-carboethoxyallyl 2'-methoxyallyl ether afforded branched polymer when the percentage conversion and percent monomer concentration were kept low. This was determined via gel permea ti on chromatography.

The polymer of 2-carboethoxyallyl 2'-phenyallyl ether consisted largely of five-membered rings at 40� C and six-membered rings at 60� C. This ring distribution supports intramolecular "charge transfer" complexation at lower temperatures and the normal

cyclopolymerization dominating at higher temperatures corresponding to the charge transfer complex breaking up.

Theoretical calculations such as geometry optimizations were

carried out on N-methylmaleimide and methyl vinyl ether and possible complexes involving them in order to support charge transfer between these two molecules.













CHAPTER I
INTRODUCTION


Cyclopolymeri zation

History
Early in the history of Polymer Science, a general principle was established by StandingerI that polymerization of nonconjugated dienes leads to crosslinked and therefore non-soluble, nonlinear polymers or copolymers. An exception to this widely accepted principle was observed by Butler,2 who found that a variety of diallyl quarternary ammonium salts polymerized to yield soluble, and hence linear polymers containing little or no residual unsaturation. To account for these, Butler and Angelo3 suggested a

polymerization mechanism that involves an alternating intermolecularintramolecular chain propagation. The six-membered structure proposed for radical initiated cyclopolymerization of 1,6 dienes was based upon the generally accepted hypothesis advanced by Flory4 regarding the predominance of the more stable radical in controlling the course of vinyl polymerization. Intervening studies have shown

that in numerous cases cyclopolymerizations do not adhere to this hypothesis but lead to cyclic structures derived via propagation through the less stable intermediate, i.e., reactions proceeded via kinetic rather than thermodynamic control (Scheme 1).




2













M.



X M* thermo.x I X X





kinetic

4,PL1
X _.__ POLYMER


Scheme 1: Butler scheme for cyclopolymerization.








It has been shown that suitable monomers undergo

cyclopolymerization via all of the well known methods of initiation of polymerization.2
A type of copolymerization constitutes a significant portion of the cyclopolymerization literature.2 This process, referred to as cyclocopolymerization, incorporates both comonomers into the developing cyclic structure. The most extensively studied example of this unusual type of copolymerization is the cyclocopolymer of divinylether and maleic anhydride. This copolymer has been extensively studied for its biological properties.5

Monomers having two different functional groups have been studied in cyclopolymerization.2

Cyclopolymerization of diene monomers leading to larger (7) rings has also been studied.2

Mechanism of Radical Cyclopolymerization

Important aspects of the process are embodied in a kinetic study carried out on methacrylic anhydride.6 This study showed that the intramolecular cyclization step is higher in energy by 2.6 kcal/mole

than the intermolecular step. The rate of cyclization, however, was found to be considerably faster than the intermolecular propagation step in support of a very high steric factor favoring cyclization. Bimolecular reactions involve substantial loss of translational entropy whereas intramolecular reactions only involve the loss of

internal rotational degrees of freedom and are therefore favored. The thermochemical approach to the explanation of ring sizes failed.








Less favored ring sizes may be formed in cyclopolymerization and the less stable radical may predominate in the cyclization. The model hex-5-enyl radical (I) (Scheme 2) has been studied extensively and various propositions7 with regard to the formation of the less stable radical (IV) being formed faster have come under consideration. Notably they could be listed as:

(1) entropy of activation8,9,10

(2) unfavorable non-bonded interaction11

(3) stereo electronic factors

(1) The entropy change associated with the loss of rotational freedom in intramolecular reactions becomes unfavorable with increasing size of the ring being formed. The magnitude of this difference (- 3.4 cal mol-1�K) at ordinary temperatures is far too small to account for the degree of regioselectivity exhibited by the ring closure reaction and hence is not a dominant factor though it could not be ruled out. The favorable enthalpy of activation (- 1.7 kcal/mole) is also not a dominant factor.

(2) The Julia-LeBel hypothesis. An unfavorable non-bonded

interaction between the pseudo-axial proton at C2 and the syn proton at C6 will destablize the transition state (VIII) for 1,6 ring closure by comparison with (IX) for five-membered ring formation. The magnitude of the interaction (< 0.8 kcal mo1-1) is not sufficient to account for the high preference for 1,5 ring closure besides alkenyl radicals (X) having no pseudo-axial proton at C2 undergo regiospecific formation of a five-membered ring.12




5








Br

BBu SnH

I kl:/ I 6








IV



vIv
4,


vivii
VIII






HH

H

VIIIIX







x >99%


Scheme 2: Reactions of the hex-5-enyl radical (M).








(3) The stereo electronic theory contends that the strain engendered in accommodating the mandatory disposition of reactive centers within the transition complex for 1,5 ring closure outweighs those steric and thermochemical factors expected to favor the formation of the more stable possible product. It involves the

structure (XI) where the dominant interaction for attack of an alkyl radical on an olefinic bond involves overlap of the semi-occupied 2p orbital with one lobe of the vacant w* orbital.13,14

A structural feature which affects the ability of an unsaturated radical to accommodate the intimate transition complex for addition will necessarily affect also the rate and regroselectivity of ring closure, e.g., shorter bonds (C-O,C-N) favors 1,5 ring closure.











XI


Substituents at C5(XII) do not enhance 1,6 ring closure but rather

retard 1,5 ring closure,15 suggesting that the formation of the transition complex involves considerable configurational change at C5, and that it is this change toward sp3 hybridization which is effected by substituents (through B strain). However, when the substituent at C5 is capable of interacting strongly with an adjacent radical center, it may increase the rate of 1,6 ring closure;








nevertheless, it will still retard the rate of 1,5 ring closure. Thus the phenyl substituted radical (XIII) undergoes 1,6 ring closure more rapidly than the parent, but 1,5 ring closure occurs more slowly16 (Fig. 1).
Substituents at C1 expected to exert a strong conjugative effect on the adjacent radical center often afford mainly products of 1,6 ring closure. Such results17 are not incompatible with the concept of stereo electronic control since 1,5 ring closure is the kinetically controlled process, but being truly reversible,10 it is often superceded by slow but essentially irreversible 1,6 ring closure. Also the transition complexes for these weakly exothermic reactions may lie towards the product end of the ring closure reaction coordinate making stereo-electronic effects less important unlike normally, when ring closure proceeds through a very early

transition state in which there is little change of configuration at C1 or C6 and little transfer of spin density.11


Charge-Transfer

It was Mulliken18 who first proposed a theory to account for bonding in complexes (donor-acceptor) which do not conform to the Lewis acid-Lewis base description. Mulliken19 proposed that chargetransfer complexes arise from interaction between donor molecules and acceptor molecules having high-energy filled orbitals (i.e., low ionization potentials, ID) and acceptors having low energy unfilled orbitals (i.e., high electron affinities, EA) viz:
















XII

N


0.26 kc/m


7 kc/m


7 kc/m


ki 43 at 400C k2l

ka a rate constant for five-mmnted ring membered ring formation.


-13 Ic/m


kl
-2a 0.55 at 40*C


formation; k2 x rate constant for six-


Fig. 1: Reaction coordinates proposed as a result of product
distribution study in the cyclization of radicals XII and
XIII.


CSHI









D + A [ [AD ++ A-D+]. [A-0+ AD] ground state excited state


Dewar and Thompson20 suggested that other aspects of these

intermolecular combinations, notably the enthalpies of formation, are very similar to those expected on the basis of Van der Waals forces including dipole-dipole, dipole-induced-dipole and dispersion forces. Also, the only requirement that a charge-transfer transition occur is that the species involved be close together. A transition could occur equally well if the components were held together by simple Van der Waals forces, and there is ample evidence for socalled charge-transfer spectra. Kosower21 reviewed the possibilities for involvement of charge transfer complexes in organic reactions as exemplified by the following scheme:


-hv
or radiationless I products D + A D,A h D+,A D + A
complex or A covalent adduct

+
D*,A D ,A (triplet) + products (triplet)
or D,A*


The spontaneous thermal reactions of electron rich olefins with electron poor olefins gives a wide diversity of organic and polymer molecules as shown in the scheme below.22









D D D


A A A





D A D


D

EH

AI
D D D
A
+


A DD


2 +c 'r + *rcycloadducts


D = donor: OR, NR2, Aryl, etc.

A = acceptor: CN, COOCH3, etc.



These spontaneous reactions have been attributed to initiation by charge-transfer complexes or by ion-radicals arising by electron transfer from donor olefin to acceptor olefin.23 This has been shown not to be true.24 They may be on the reaction path but not in the initiation step.

Butler and Olson25 studied the role of the charge-transfer complex in the propagation step of the copolymerization N-(alkyl) maleimide with vinyl ethers.

Seymour et al.26 have shown the existence of a charge transfer complex between acrylonitrile complexed to a Lewis acid (ZnCl2) and styrene. The Lewis acid enhances charge transfer. The details are shown in Figure 2.


Z
























H H




H H
H H Zn12


benzene protons 7.18--7.23 ppm


acrylonitrile protons 5.9---* 5.6 ppm


U.V. spectrum showed shoulder at 214nm which vanished on heating.
(t-butanol)


Fig. 2: Evidence for charge transfer between acrylonitrile and
styrene in the presence of ZnC12.








The stereochemistry of the complex in the presence of strong or multiple donors and acceptor substituents has been visualized23,24

such that it could lead to a tetramethylene zwitterion with one end of zwitterion carbon having the donor and the positive charge and the other end having the acceptor and the negative charge. This would lead to the isolation of 1-donor-2-acceptor cyclobutane molecules. This zwitterion is proposed24 to be the live intermediate which leads to small molecules and initiates polymerization.

Frontier molecular orbital theory27 has been invoked to explain

the reactivity and consequent stereochemistry of the products in copolymerization of alkenes substituted with an electron donor and an electron acceptor. It has also been used to explain the ring-size in cyclopolymerization since thermodynamic stability is determined by the energies of all the filled orbitals, but kinetic stability is mostly determined by the highest occupied molecular orbital.


Proposed Research

A combination of sections A and B would lead one to propose cyclopolymerization of molecules having intramolecular charge transfer between alkene groups substituted with a donor and an acceptor group and polymerization of the intramolecular complex leading to the intramolecular zwitterion as shown in the following scheme:




13









complex 0
0 +0
Ar A
D D D



(M

A

D
polymer with 5 membered rings




If the donor was phenyl, and there was no charge transfer interaction one would expect six-membered ring formation to predominate since the rate of five-membered ring formation was relatively inhibited and the six-membered ring formation favored as explained earlier.16 The initiation due to the "tetramethylene zwitterion" would complicate matters.24 However, the single donor and acceptor groups used here would be relatively weak such that the equilibrium forming the zwitterion would lie largely to the left. A radical initiator would favor five-membered ring formation via almost concerted addition, as shown in the scheme above. This is based upon a similar mechanism proposed by Butler and Olson.25













CHAPTER II
EXPER IMENTAL


General Information

All temperatures are uncorrected and are reported in degrees centigrade; melting points (m.p.) were determined in open capillary tubes using a Thomas-Hoover melting point apparatus. Pressures are expressed as millimeters (mm) of mercury. Elemental analyses were performed by Atlantic Microlabs, Inc., Atlanta, Georgia.

Number average molecular weights (Mn) of polymers were

determined by vapor pressure osmometry (VPO) on a Wescan Model 230 Recording Vapor Pressure Osmometer Apparatus.

All preparative separations were performed with an Altex Model

332 programmable gradient system fitted with a constant wavelength ultraviolet (UV) detector (254 nanometer (nm)). A Lobar B 24 inch column (E. Merck) with 40-63 U LiChroprep Si60 Silica gel was used. The solvent used was hexane with rinsing of the column done with 4:1 to 3:1 methylene chloride:methanol.

Infrared spectra (IR) were recorded on a Perkin-Elmer 281

infrared spectrophotometer. Spectra of liquids were obtained neat as a smear on sodium chloride plates, and those of solids were obtained as KBr pellets. Vibrational transition frequencies are reported in wavenumbers (cm-1 ) using the 1601 cm-1 line of a polystyrene film as
a standard. The intensity of the bands were assigned the following








classifications: weak (w), medium (m), shoulder (sh), strong (s), broad (br).

Proton nuclear magnetic resonance (NMR) spectra (60 MHz) were recorded on a Varian EM-360L spectrometer. Carbon-13 (C 13)(25.0 MHz) and 100 MHz proton NMR spectra were obtained on a JEOL JNM-FX-100 instrument. Chemical shifts are given in parts per million (ppm) on a 6-scale downfield from tetramethyl silane (TMS) or solvent peaks as internal references (int ref)(chloroform-d (CDCI3) 13C = 77.0; benzene-d6 ( -d6) 13C = 128.0 dimethyl sulfoxide-d6 (DMSO-d6) 13C = 39.5).28

Multiplicities of proton and off-resonance decoupled carbon-13 resonances are designated as singlet (s), doublet (d), triplet (t), quartet (q), pentet (p), multiplet (m) or broad (br).

Ultraviolet spectra were measured with a Perkin-Elmer 330 spectropho tome ter.
Analytical gas chromatography was done on a open-column capillary HP 5880A series gas chromatograph.

Gel permeation chromatography (GPC) was done on a Waters M 6000A high pressure liquid chromatograph pump with polystyrenedivinylbenzene (TSK gel) columns (i.e., the TSK gel G3000H and G4000H coupled with a guard column attached initially) made by TOYO SODA.


Reagents and Solvents

Reagents were obtained from Aldrich Chemical Co., Eastman Kodak Co., Fisher Scientific Co. or Mallinkrodt Inc. unless otherwise noted. Deuterated NMR solvents were obtained from Merck and Co. and








Aldrich Chemical Co. All gaseous reagents were obtained from Matheson Co. Nickel carbonyl was obtained from Strem Chemicals.

All solvents used for general application were of reagent grade or ACS grade quality. For special purposes, purification of solvents was carried out by following procedures reported in the literature.29

Thus, dimethyl sulfoxide was allowed to stand over barium oxide overnight and was distilled over the barium oxide under reduced pressure; benzene was purified by washing with H2SO4 (100 mLs/liter) until darkening was slight. 2-Phenylallyl alcohol was obtained in

the pure form by precipitating any polymer formed on the reagent's standing, and distilling the alcohol at 950-97� C/1.5 mm. The literature reported boiling point was (lit b.p.)30 116o_118� C/11 mm. 2,2'-Azobisisobutyronitrile was recrystallized twice from methanol.


Synthesis of Monomers

2-Chloroallyl 2'-Phenylallyl Ether (1)

The procedure followed for the synthesis of such compounds by

Baucom31 was generally used. To a flame dried, three necked, 100 mL, round bottomed flask fitted with a dropping funnel through which a constant flow of nitrogen was maintained, was added 1.80 g of 60% sodium hydride (1.08 g, 0.045 mole) in a mineral oil dispersion. The mineral oil was removed by washing with n-pentane (3x10 mLs). The pentane was added, the mixture stirred with a magnetic stirrer and then allowed to stand. The NaH separated out and the pentane and mineral oil drawn off with a disposable pipette. After three








repetitions 20 mLs of dry dimethylsulfoxide (DMSO) was added. 2Phenylallyl alcohol (5.65 g, 0.042 mole) in 10 mLs of DMSO was added through the dropping funnel slowly. Stirring was continued for four

hours (hrs) at room temperature (R.T.). This was then transferred to the dropping funnel and 10 mLs of DMSO and 2-chloroallyl chloride (4.66 g, 0.042 mole) was added to the flask. The alkoxide in the dropping funnel was then added slowly with stirring so that the temperature did not rise appreciably. Stirring was continued for twelve hours. Then water (10 mLs) was added to destroy the excess sodium hydride and the ether was extracted with pentane (3x75 mLs). The pentane extracts were combined and dried over magnesium sulfate. The ether was recovered after the pentane was drawn off on

a rotary evaporator and purified by preparative high pressure liquid chromatography.

One and four-tenth grams (16% yield) of the ether (1) was obtained. Gas chromatography showed it to be 97% pure.

1H NMR (CDCl3-TMS) 6: 4.072 (q,2H), 4.406 (m,2H), 5.353 (q,2H),

5.442 (m,lH), 5.550 (m,1H), 7.262-7.438 (br,m,5H). Note: The coupling constants in all of the above multiplets were < 1 Hz.
13C NMR (CDCl3-TMS, int ref CDC13) 6: 143.62, 138.41, 138.02, 128.32, 127.78, 125.98, 114.72, 113.36, 72.08.

IR (NaCl): 3080 (m), 3060 (m), 3030 (m), 2860 (s), 1635 (s), 1600 (w), 1570 (w), 1490 (s), 1440 (s,br), 1380 (m), 1365 (m), 1315 (sh,w), 1265 (m), 1245 (m), 1175 (s), 1120 (s), 1080 (s,br),1035 (s), 960 (m), 900 (s), 780 (s), 700 (s), 635 (s).








Elemental analysis: found (calculated) % C 68.72 (69.01), % H

6.29 (6.05), % Cl 17.03 (16.72).

Ethyl a-(Bromomethyl) Acrylate (2)

The method of K. Ramarajan et al.32 was followed. In a nitrogen flushed, three necked, 100 mL, round bottomed flask equipped with a magnetic stirrer. Dean-Stark trap and condenser were placed a(bromomethyl) acrylic acid (10 g, 0.0595 mole) and thiophene free benzene (75 mLs). Approximately 10 mLs of a binary azeotrope of benzene and water was distilled. The Dean-Stark trap was removed and

absolute ethanol (purified by boiling commercial absolute alcohol over magnesium turnings for 4 hrs in a nitrogen atmosphere) (25 mLs) and concentrated sulfuric acid (0.2 mLs) were added slowly. The contents of the flask were boiled in a nitrogen atmosphere for 36 hrs, the condensate being passed through 24 g of molecular sieves (Linde 3A) before being returned to the flask. About 30 mLs of a mixture of benzene and ethanol were removed from the reaction mixture by distillation (at 670 C). Then benzene (25 mLs) was added and another 30 mLs of benzene-ethanol mixture distilled (65-75� C). The residue was poured into water (50 mLs) and neutralized with solid sodium bicarbonate (ca. 4.8 g) until CO2 evolution ceased. The

resulting solution was extracted with three 25 mL portions of ether and the combined extracts dried over anhydrous sodium sulfate for 3 hrs. The ether was removed under reduced pressure on a rotary

evaporator and the crude-ester distilled to give a fraction at 39-40� C (0.9 mm) weighing 8.2 g (72% yield), lit b.p.32 39-40�C (0.9 mm)







1H NMR (CDCl3-TMS) 6: 1.26-1.40 (t,3H), 4.16-4.38 (q,2H), 4.19 (s,2H), 5.96 (s,1H), 6.32 (s,IH).
13C NMR (CDCI3-TMS, int ref CDC13) 6: 13.99, 61.11, 68.41, 125.01, 137.58, 165.75.

IR (NaCl): 2980 (s), 2930 (m), 2870 (m), 1725 (s), 1635 (m), 1445 (m,br), 1380 (m,br), 1310 (m), 1330 (m), 1270 (m), 1225 (m), 1185 (s), 1105 (s), 1025 (m), 950 (s), 900 (w), 875 (w), 855 (w), 810

(m), 720 (m), 680 (m).

2-Phenylallyl 2'-Carboethoxyallyl Ether (3)

The procedure followed by Baucom31 was used. To a flame dried, three necked, 100 mL, round bottomed flask, fitted with a dropping funnel through which a constant flow of nitrogen was maintained, was added 0.642 g of 60% NaH (0.385 g, 0.0161 mole) in a mineral oil dispersion. The mineral oil was removed by washing with n-pentane (3x10 mLs). The pentane was added, the mixture stirred with a magnetic stirrer and then allowed to stand. The NaH separated out and the pentane-mineral oil mixture drawn off with a disposable pipette. After three repetitions, 20 mLs of dry DMSO was added. 2Phenylallyl alcohol (2.152 g, 0.0161 mole) in 10 mLs DMSO was added through the dropping funnel slowly. Stirring was continued for four

hours at room temperature. The contents of the flask were then transferred to the dropping funnel and 10 mLs of dry DMSO containing 2-carboethoxyallyl bromide (3.104 g, 0.0161 mole) was added to the flask. The alkoxide (dark purple in color) in the dropping funnel was then added slowly with stirring so that the temperature did not rise appreciably. Stirring was then continued for 12 hrs. Then








water (10 mLs) was added to destroy the excess sodium hydride and the ether was extracted with pentane (3x75 mLs). The pentane fractions were then combined and dried over magnesium sulfate. The ether was recovered after the pentane had been removed under reduced pressure on a rotary evaporator. It was purified by preparative high pressure liquid chromatography. Ether (3)(0.80 g, 20% yield) was obtained.

1H NMR (CDCI3-TMS) 6: 1.217-1.360 (t,3H,J=7.2 Hertz (Hz)), 4.176-4.272 (q,2H,J=6.47 Hz), 4.249 (s,2H), 4.433 (t,2H,J
5.366 (q,lH,J 13C NMR (benzene-d6, int ref pd6) 6: 14.11, 60.45, 68.54, 72.78, 113.96, 124.83, 126.44, 128.54, 128.68, 138.23, 139.21, 144.67, 165.53.

IR (NaCl): 3060 (w), 2980 (s), 2930 (m), 2900 (m), 2870 (m), 1720 (s), 1635 (m,br), 1600 (w), 1495 (m), 1445 (s), 1380 (s,br), 1305 (s), 1270 (s), 1175 (s), 1155 (s), 1120 (s), 1095 (s), 1035 (s), 950 (m), 910 (m), 860 (w), 815 (w), 780 (s), 695 (s).

Elemental analysis: found (calculated): % C 72.96 (73.17), % H

7.33 (7.32).

Chloroacetone Cyanohydrin (4)

The procedure followed by Ferris and Marks33 was used. To a solution of sodium bisulfite (62.4 g, 0.6 mole) in water (160 mLs) was added dropwise chloroacetone (46.2 g, 0.5 mole) in a three necked, 2 L, round bottomed flask fitted with a thermometer, mechanical stirrer and dropping funnel. The addition was controlled in order to keep the temperature below 35� C. When all the







chloroacetone had been added, the temperature was cooled to about 25* C and 200 mLs of ethyl ether was added. Then a solution of sodium cyanide (29.4 g, 0.6 mole) in water (80 mLs) was added dropwise at 25-30* C with vigorous mechanical stirring. When all the cyanide

solution had been added, the ether layer was separated immediately and the aqueous layer extracted with ethyl ether (2x100 mLs). The

combined ether solutions were dried over magnesium sulfate. The crude cyanohydrin was recovered after the ether had been removed under reduced pressure on a rotary evaporator. Cyanohydrin (44.5 g, 74.2% yield)(4) was recovered by distillation b.p. 73-75o C/1.5 mm (lit b.p.33 73-740 C/1.5 mm).
1H NMR (CDCl3-TMS) 6: 1.708 (s,3H), 3.681 (s,2H), 4.309 (s,lH).

13C NMR (CDCl3-TMS, int ref CDCl3) 6: 24.80, 50.05, 68.72, 119.50.

IR (NaCl): 3400 (s,br), 3000 (m), 2970 (m), 2945 (m), 2250 (m), 1450 (s), 1430 (s), 1380 (s,br), 1280 (m), 1245 (s), 1150 (s,br), 1080 (s), 960 (s), 870 (s), 770 (s), 730 (w), 695 (m), 685 (m).

Chloroacetone Cyanohydrin Acetate (5)

The procedure followed by Ferris and Marks33 was used. To a

three necked, 250 mL, round bottomed flask fitted with a thermometer, a dropping funnel and a drying tube was added chloroacetone cyanohydrin (4) (44.5 g, 0.372 mole) and 1 mL of concentrated sulfuric acid. To this was added dropwise at 60-70* C with vigorous stirring, acetic anhydride (41 g, 0.40 mole) through the dropping funnel. When all the anhydride had been added, the mixture was

stirred for 30 minutes (mins) and then poured into ice water (600








mLs). The resulting mixture was neutralized with solid sodium

bicarbonate and extracted with ethyl ether (3x100 mLs). The combined extracts were then dried over magnesium sulfate and the ether finally removed under reduced pressure on a rotary evaporator. Chloroacetone cyanohydrin acetate (5)(32.4 g, 54% yield) was obtained after distillation at 57-59* C/0.3 mm (lit b.p.33 57-59" C/0.3 mm).
1H NMR (CDCI3-TMS) 6: 1.85 (s,3HO, 2.15 (s,3H), 3.90 (s,2H).

13C NMR (CDCl3-TMS, int ref CDCI3) 6: 20.61, 22.76, 46.83, 70.62, 116.38, 168.38.
c-(Chloromethyl )acrylonitrile (6)

This was obtained by the method used by Ferris and Marks.33 The apparatus used is shown in Figure 3. The tube at 2500 C was primarily to vaporize the chloroacetone cyanohydrin acetate. Chloroacetone cyanohydrin acetate (120 g, 0.743 mole) was dropped at the rate of 1 drop/5 seconds. The condenser was used in case the columns did get blocked up. The product, a brown oil, was poured

into water (500 mL) and was neutralized with solid sodium bicarbonate. This was then extracted with ethyl ether (3x200 mLs), the combined portions dried over magnesium sulfate and the ether taken off under reduced pressure on a rotary evaporator. The residue was then fractionally distilled with a Vigreux condenser and the fraction at 75-85�/40 mm collected. This portion (35 g) consisted of 60% a-(chloromethyl) acrylonitrile (6) and 40% of cis- and trans-$chloro-c-methacrylonitrile (7). The percentages were obtained from the integration in the proton NMR (Fig. 4).










N2gas








i i=


in H20



out H20
~I

0 9 pyrex glass beads
o 0 o 0
0 o heating coils at 2500C
a


III> porcelain burro saddles
Squartz tube
Hoskins Electric Furnace FD303A at 500�C




~ N2 gas out passed through traps in dry ice/ isopropanol and liq. N2




collecting flask immersed in dry ice/ isopropanol




Fig. 3: Apparatus for the pyrolysis of chloroacetone cyanohydrin acetate.












CN Cl
cis & trans
H


60 I.0


cis

-~'LJ


b ,c


K9_


a I


ppm


Fig. 4: Proton spectrum of the pyrolysis products with the integration (in CDCL3)


CN



C1


� L








Lit b.p.33 of cis-8-chloro-a-methacrylonitrile 57.5-580/20 mm, trans-B-chloro-a-methacrylonitrile 47-480/40 mm, a-(chloromethyl) acrylonitrile 61.5-62.5�/18 mm.
1H NMR (CDCl3-TMS) a (6): 4.160 (m,2H,J 13C NMR (CDC13-TMS, int ref CDCl3) 6 (6): 43.23, 113.26,

115.65, 133.29; (7) cis: 18.42, 116.23, 119.79, 131.78; (7) trans: 15.45, 116.23, 119.79, 135.14.

IR (NaCI): 3080 (s), 2960 (m), 2930 (w), 2225 (s), 1750 (w,br), 1605 (s), 1440 (s), 1400 (m), 1380 (w), 1305 (w), 1270 (m), 1220 (w), 1160 (w), 1025 (s), 960 (s), 850 (s), 775 (s), 710 (s). 2-Phenylallyl 2'-Cyanoallyl Ether (8)

The method employed by Baucom31 for the synthesis of such

compounds was used. To a flame dried, three necked, 100 mL, round bottomed flask fitted with a dropping funnel and through which a constant flow of nitrogen was maintained was added 0.780 g of 60% NaH (0.473 g, 0.0197 mole) in a mineral oil dispersion. The mineral oil was removed with pentane in the manner described in the synthesis of 2-phenylallyl-2'-chloroallyl ether. Then dry DMSO (25 mLs) was added. Through the dropping funnel was slowly added 2-phenylallyl alcohol (2.640, 0.0197 mole) in dry DMSO (10 mLs) and stirred using a magnetic stirrer at room temperature for 4 hrs. The alkoxide was then transferred to the dropping funnel and was added slowly to 3.33 g of 60% 2-cyanoallyl chloride (2 g, 0.0197 mole) with 40% of (7) in








DMSO (10 mLs) so that the temperature did not rise appreciably. Stirring was continued for 12 hrs. Water (10 mLs) was then added and the ether was extracted with pentane (3x75 mLs). The pentane extracts were combined and dried over magnesium sulfate. The pentane was removed under reduced pressure on a rotary evaporator. The ether was purified by preparative high pressure liquid chromatography (Fig. 5). Compound (8)(0.94 g, 24% yield) was recovered.
1H NMR (benzene d6-TMS) 6: 3.492 (t,2H), 3.988 (m,2H), 5.150 (q,lH), 5.243 (m,2H), 5.370 (m.lH), 7.086-7.367 (m,5H). Note: The coupling constants in all of the above multiplets are < 1 Hz.
13C NMR (CDCl3-TMS, int ref CDCI3) 6: 143.33, 138.21, 131.34, 128.42, 127.98, 126.03, 120.33, 117.02, 115.11, 72.61, 69.96.

IR (NaCl): 3080 (m), 3060 (w), 2925 (m), 2860 (m), 2230 (m), 1750 (w,br), 1630 (m), 1610 (w), 1575 (w), 1495 (m), 1445 (m), 1410

(m), 1305 (w), 1120 (s), 1090 (s), 1025 (m), 950 (s), 915 (s), 850

(w), 780 (s), 710 (s).

Chemical analysis: found (calculated): % C 77.92 (78.35), % H

6.46 (6.58), % N 6.73 (7.03).

Bromoacetone (9)

The procedure used here was one followed by Levene.34 A three necked, 2L, round bottomed flask was fitted with a mechanical stirrer, a reflux condenser and a dropping funnel. To this was added water (800 mLs), acetone (250 mLs) and glacial acetic acid (186 mLs). With stirring, the mixture was heated to about 65� C on an oil bath. Through the dropping funnel, bromine (177 mls, 3.65 mole) was

















2-phenylallyl 2'-cyanoa.llYl ether


flow rate 5 mL/min of hexane.


LA


time




Fig. 5: HPLC chromatograph.
cyanoallyl ether.


55 mins.


Separation of 2-phenylallyl 2'-


| !


i


inJ ect A , -i f








added dropwise, the dropping being regulated by the disappearance of color from the preceding drop. After addition was complete, it was diluted with cold water (400 mLs) cooled in an ice-water mixture and neutralized with solid sodium carbonate (- 500 g). The oil which separated out was collected and the aqueous layer extracted with ethyl ether (2x400 mLs). The extracts together with the oil was dried over sodium sulfate. The ether was removed by distillation

(since bromoacetone is a bad lachrymator, care should be taken accordingly) and not on a rotary evaporator. The residue containing compound (cpd)(9) as well as 1,1-dibromoacetone was distilled and bromoacetone (200 g, 40% yield) was recovered at 86-87�/60 mm. lit b.p.34 40-42�/13 mm
1H NMR (CDCl3-TMS): 3.90 (s,2H), 2.40 (s,3H).

13C NMR (CDCI3-TMS, int ref CDCI3): 26.98, 34.82, 199.68. 1-Bromo-2,2-dimethoxy Propane (10)

The procedure of Jacobson et al.35 was used for this

synthesis. To a 250 mL, round bottomed flask fitted with a drying tube was added 95 mLs of 95% bromoacetone (< 0.5 mole)(5% of 1,1dibromoacetone), trimethyl orthoformate (60 mLs, 0.55 mole), methanol

(25 mLs) and concentrated sulfuric acid (10 drops). After stirring for 2 hrs, the mixture was basified with triethylamine (2 mLs) and

then attached to a water pump to remove most of the unreacted methyl formate. The resulting reaction mixture was added to an ice cold solution of sodium hydroxide (20 g) in methanol (200 mLs) destroying the unketalized 1,1-dibromoacetone. This mixture was then partitioned between pentane (300 mLs) and water (200 mLs). The








aqueous layer was extracted with pentane (2x50 mLs) and the three pentane layers combined, washed with water (50 mLs) and dried over potassium carbonate. Removal of the pentane by distillation at atmospheric pressure and distillation under vacuo of residue gave 75 g (0.41 mole > 80% yield) of 1-bromo-2,2-dimethoxypropane boiling at 83* C/80 mm. lit b.p.35 156* C/760 ram.
1H NMR (CDCI3-TMS) 6: 1.45 (s,3H), 3.20 (s,6H), 3.35 (s,2H).

13C NMR (CDCI3-TMS, int ref CDCI3) 6: 20.61, 34.55, 48.69, 99.76.

IR (NaCl): 2950 (sbr), 2840 (m), 1460 (m), 1425 (m), 1380 (m), 1270 (m), 1250 (m), 1215 (m), 1170 (m), 1165 (m), 1110 (s), 1075 (s), 1045 (s), 925 (w), 880 (m), 830 (m), 745 (m), 675 (m). Diisopropylethylammonium p-toluenesulfate (11)

The procedure of Jacobson et al.35 was followed. To a 100 mL

round bottomed flask was added p-toluenesulfonic acid monohydrate (3.80 g, 0.02 mole) in anhydrous methanol (10 mLs). To this was added diisopropylethylamine (2.80 g, 0.022 mole). The resulting solution was concentrated in vacuo, yielding an oil which crystallized on standing. The solid was crushed and the last traces of solvent removed by subjecting it to vacuo (0.01 mm). Five and five-tenth grams (92% yield) of (11) was obtained of m.p. 85-86* C (lit. m.p.35 87-88.50 C)
1H NMR (CDCI3-TMS): 1.37 (m,15H), 2.35 (s,3H), 2.8-3.3 (m,2H),

3.3-3.9 (m,2H), 7.17 (d,2H), 7.82 (d,2H), 9.18 (br,S,1H).
13C NMR (CDCl3-TMS, int ref CDCl3): 12.09, 16.86, 18.23, 20.96, 42.40, 53.97, 125.59, 128.27, 139.19, 143.04.








3-Bromo-3-methoxypropane (12)

Method A. The method followed by Hoffman and Greenwood36 was

used initially but this method proved laborious. A three necked, 500 mL, round bottomed flask was fitted with a thermometer, a mechanical stirrer and a dropping funnel and to it was added N-bromosuccinimide (50 g, 0.281 mole) in carbontetrachloride (150 mLs). The flask was heated in an oil bath so that the temperature of the mixture was about 550 C. Heating was stopped and 2-methoxypropane (20 mLs) was added. The 2-methoxypropane was initially dried over CaCl2 and distilled. The addition, with vigorous stirring, was done so that the temperature inside the flask was maintained. After addition was complete, the reaction mixture was cooled to ca. 100 C by immersion in an ice-water mixture. The suspension was filtered to remove the precipitated succinimide and concentrated at the water pump for 15 mins by immersion of the flask in warm water. This removed unreacted 2-methoxypropene, methanol, methyl acetate and some CCI4. The remaining solution was washed with potassium hydroxide (2x300 mLs of IN) and then ice cold water (2x100 mLs). Base destroys 1-bromo-2methoxy-2-succinimidopropane and bromoacetone. Alkaline conditions

also discourages the hydrolysis of any bromoketal to bromoacetone and methanol and suppresses the addition of water to enol ethers. Washing with water neutralizes the solution. The organic layer was dried over CaCl2 and stirred over Na2CO3. The solution so prepared contains mainly CC14 (50%), 2-methoxyally bromide (30-35%) and 1bromo-2-methoxypropene (13) (- 14%). The percentages were determined by analytical gas chromatography. The carbon tetrachloride was








removed by distillation leaving a yellow residue containing about 55% 2-methoxypropene and 28% 1-bromo-2-methoxypropene with an unidentifiable residue.

Method B. The procedure here was that followed by Jacobson et al.35 This method provided a more stoichiometrically clean product with minimal exposure of the unstable 2-methoxyallyl bromide to room temperature and light.

A distillation apparatus with a 100 mL, round bottomed flask containing 1-bromo-2,2-dimethoxypropene (50 g, 0.2732 mole) and diisopropylethylammonium p-toluene sulfonate (1 g) was fitted with a 12 inch, 15 mm diameter vigreux column with heating coils and a short-path distillation assembly. The flask was heated at 150-190� C in an oil bath while distilling of the methanol at the rate of 1 drop/2 seconds. This rate is used so as to keep the complete time of

reaction to less than an hour and a half. Complete removal of the methanol was shown by a rise in the head temperature to > 750 C. The fraction collected between temperatures of 85-1300 C had the highest percentage (67%) of 2-methoxyallyl bromide. The total fraction (> 850 C) had the following percentages as calculated from the investigation of the proton NMR (Fig. 6):

% 2-methoxyallyl bromide: 45

% 1-bromo-2-methoxy propene (13): 15

% 1-bromo-2,2-dimethoxypropane/starting material): 40.5
1H NMR (CDCI3-TMS) 6 (12): 4.3 (d,1H), 4.15 (d,iH), 3.9 (s,2H),

3.65 (s,3H); (13): 5.2 (s,br,lH), 3.55 (s,3H), 1.95 (s,3H).














C 1 2
OCH3 O H H
17-)d r :

Br 3 C r 3


h5 : 15 ho.5


5 Ih


Fig. 6: Proton (60 MHz) spectrum in CDC]3


I w)








13C NMR (CDCI3-TMS, int ref CDCI3) 6 (12): 31.63, 55.41, 85.29, 159.03; (13): 18.47, 55.02, 77.58, 157.17.

IR (NaCl): 3000 (m), 2950 (m), 1725 (s), 1420 (m), 1390 (m), 1360 (s), 1275 (m), 1240 (m), 1215 (sh,m), 1150 (s), 1005 (w), 700

(w), 660 (w,br).

2-Carboethoxyallyl Alcohol (14)

The procedure of Rosenthal et al.7 was used. Caution: Nickel carbonyl used here is very toxic. Appropriate handling measures were taken. A 2L, five necked, round bottomed flask was equipped with a mechanical stirrer, a thermometer, a dropping funnel, a gas inlet which almost touches the bottom, and a dry ice-cooled condenser. In it was placed 95% ethanol (700 mLs) and the flask was cooled in a dry ice/isopropanol bath. Through the inlet nickel carbonyl was passed with nitrogen as a carrier until the amount of Ni(CO)4 added (measured by weight difference of the laboratory bottle) was approximately 86 g (0.50 mole). Then was added hydroquinone (10 g) and acetic acid (120 g, 2 mole), and the flask was heated with an oil bath to 550 C with stirring. Through the dropping funnel was added initially 2 g of propargyl alcohol (112 g, 2 mole total) and the color darkened and the internal temperature rose (ca. 2 mins). At this point the heating mantle was removed and the remainder of the propargyl alcohol added dropwise such that the refluxing was under control. The temperature at the end of the addition was 75-80� C. The solution was allowed to stir for 30 mins and then concentrated sulfuric acid (28 mLs, 0.5 mole) was added slowly with stirring via the dropping funnel. Green nickel sulfate hexahydrate








precipitated. The contents were filtered at a water pump through a bromine trap, into a 2 L, round bottomed flask. Concentrated sulfuric acid (10 mLs) was added and the solution was refluxed for 12 hrs, the condensate being passed through a soxhlet-extractor containing anhydrous magnesium sulfate. The reaction solution was then cooled and sodium hydroxide (106 mLs, 5 N) was added to neutralize the acid. An equal volume of water was added and the solution was extracted with chloroform (4x250 mLs). The combined extracts were dried and the chloroform removed under reduced pressure on a rotary evaporator. The liquid residue was distilled to give cpd

(14) (93.6 g, 36 % yield) b.p. 55-57� C/0.7 mm. lit b.p.37 72.50 C/1.5 mm.
1H NMR (CDCl3-TMS) 6: 1.3 (t,3H), 2.7 (s,lH), 4.25 (q,2H), 4.3 (s,2H), 5.8 (s,br,1H), 6.25 (s,br,lH).
13C NMR (CDCI3-TMS, int ref CDCI3) 6: 13.89, 60.58, 61.55, 124.81, 139.58, 166.09.

IR (NaCl): 3440 (s,br), 2980 (s), 2930 (m), 2900 (m), 2870 (w), 1705 (s), 1635 (m), 1445 (m), 1380 (s,br), 1305 (s,br), 1270 (s), 1220 (m), 1170 (s,br), 1095 (m), 1055 (s), 1035 (s,sh), 945 (m), 850

(w), 810 (m).

2-Methoxyallyl 2'-Carboethoxyallyl Ether (15)
The procedure used was similar to the one followed for the

synthesis of compound (8). In a flame dried, three necked, 100 mL, round bottomed flask, fitted with a dropping funnel and through which a flow of nitrogen was maintained, was placed 0.8107 g of 60% sodium hydride (0.4864 g, 0.0203 mole) in a mineral oil dispersion. The







mineral oil was removed in the manner described in the synthesis of compound (8). Then dry DMSO (25 mLs) was added. To this was added 2-carboethoxyallyl alcohol (2.634 g, 0.0203 mole) in dry DMSO (10 mLs) very carefully, or else the quick reaction leads to excess foam formation. After a deep red/orange color was observed (2 hours), 5.1 g of 60% 2-methoxyallyl bromide (3.06 g, 0.0203 mole) in dry DMSO (10 mLs) was added dropwise through the dropping funnel. Stirring was continued at room temperature for 12 hrs, water (10 mLs) was added, and the ether extracted with pentane (3x75 mLs). The combined pentane extracts were dried over sodium sulfate and the pentane removed under reduced pressure on a rotary evaporator. The ether
(15) (1.01 g, 24.6% yield) was obtained by fractional distillation and was the fraction distilled at 600 C/0.07 mm.
1H NMR (COCI3-TMS) 6: 1.2 (t,3H), 3.5 (q,2H), 3.55 (s,3H), 4.15 (s,2H), 4.15 (m,2H), 4.55 (s,2H), 5.90 (s,br,lH), 6.24 (s,br,1H).
13C NMR (COCI3-TMS, int ref CDCI3) 6: 15.11, 55.02, 64.28, 66.28, 68.57, 83.92, 125.93, 137.29, 158.15, 165.36.

IR (NaCl): 2960 (m), 2870 (m,sh), 1715 (s), 1665 (m), 1635 (m), 1450 (m), 1380 (m), 1305 (m), 1255 (m), 1220 (m), 1155 (m), 1100 (s), 950 (m), 880 (m), 820 (m), 740 (w), 680 (m).

Elemental analysis: not done since monomer was unstable, but elemental analysis of polymer was done.








Synthesis of Model Compounds

2-Carobethoxyallyl 2'-Phenylpropyl Ether (16)

The procedure followed here was similar to the one used for the synthesis of compound (15). In a flame-dried, three necked, 100 mL, round bottomed flask fitted with a dropping funnel and through which a flow of nitrogen was kept was placed 0.8187 g of 60% sodium hydride (0.4912 g, 0.02047 mole) in a mineral oil dispersion. The mineral

oil was removed in a manner similar to that used for the synthesis of compound (15). Then dry DMSO (25 mLs) was added and through the dropping funnel 2-phenylpropyl alcohol (2.78 g, 0.02047 moles) in dry DMSO (10 mLs) was carefully added dropwise. The resulting solution was stirred magnetically at room temperature for 4 hrs. The alkoxide solution was then transferred to the dropping funnel and added to 2carboethoxyallyl bromide (3.95 g, 0.02047 moles) in dry DMSO (10 mLs)

dropwise such that there was no appreciable rise in temperature. The reaction mixture was allowed to stir for 12 hrs. Water (10 mLs) was added to destroy the unreacted sodium hydride and the ether was extracted with pentane (3x75 mLs). The combined pentane extracts were dried over magnesium sulfate and removed under reduced pressure on a rotary evaporator. The ether (16) (2.03, 40% yield) was recovered by preparative high pressure liquid chromatography (Fig. 7) after distillation at 1180 C/0.7 nmm.
1H NMR (CDCI3-TMS) 6: 0.936 (t,3H,J=7.21 Hz), 1.221 (d,3H),

3.320 (d,2H,J=3.79 Hz), 3.212-3.407 (m,1H), 3.967 (q,2HO, 4.151 (s,br,2H), 5.7291 (q,lH,J























2-phenylpropyl 2' -carboethoxe1lyl ether


























inj ect


15mins 0


Fig. 7: HPLC chromatograph.
Carboethoxyallyl ethe


Separation of 2-phenylpropyl 2'-


time








13C NMR (benzene-d6, int ref benzene-d6) 6: 14.11, 18.39,

40.37, 60.41, 69.37, 76.88, 124.54, 127.71, 128.54, 138.38, 144.67, 165.63.

IR (NaCl): 3030 (m), 2980 (s), 2940 (m), 2900 (m), 2870 (m),

1720 (s), 1640 (m), 1605 (w), 1495 (m), 1455 (m), 1380 (m), 1305 (s), 1270 (s), 1175 (s), 1105 (s), 1025 (m), 950 (m), 860 (w), 820 (w), 760 (m), 700 (s).

Elemental analysis: found (calculated) % C 72.80 (72.58); % H

7.84 (8.06).

2-Phenylpropyl 2'-Cyanoallyl Ether (17)

The procedure followed was similar to that used for the

synthesis of compound (16). In a flame dried, three necked, 100 mL, round bottomed flask fitted with a dropping funnel, and through which a flow of nitrogen was maintained, was placed 1.1034 g of 60% sodium hydride (0.6621 g, 0.02759 moles) in a mineral oil dispersion. The mineral oil was removed in the manner described in the synthesis of compound (16). To this was then added dry DMSO (25 mLs) and then 2phenylpropyl alcohol (3.752 g, 0.02759 moles) in dry DMSO (10 mLs) dropwise through the dropping funnel such that excessive foaming was avoided. The reaction mixture was stirred magnetically for 4 hrs and then transferred to the addition funnel. Then 4.67 g of 60% 2cyanoallyl chloride (2.8 g, 0.02759 moles) (other 40% being cis and trans-8-chloro-a-methacrylonitrile) in dry DMSO (10 mLs) was placed in the flask and the alkoxide added dropwise such that the temperature did not rise appreciably. Stirring was continued for 4 hrs at the end of which the unreacted sodium hydride was destroyed








with water (10 mLs) and the ether (17) extracted with pentane (3x75 mLs). The pentane extracts were combined and dried over magnesium sulfate and the pentane removed under reduced pressure on a rotary evaporator. The ether (17) (2.49 g, 45% yield) was purified by preparative high pressure liquid chromatography.
1H NMR (COCl3-TMS) 6: 1.30 (d,3H), 3.10 (p,lH), 3.55 (d,2H),

4.10 (s,2H), 5.90 (s,1H), 6.0 (s,lH), 7.30 (s,5H).
13C NMR (CDCI3-TMS, int ref CDCI3) 6: 18.03, 39.91, 70.23, 76.76, 117.11, 120.47, 126.52, 127.25, 128.37, 131.00, 143.77.

IR (NaCl): 3030 (m), 2965 (m), 2930 (m,sh), 2870 (m), 2225 (m), 1640 (w), 1605 (m), 1495 (m), 1450 (s), 1410 (w), 1390 (w), 1375 (w), 1110 (s), 1025 (w), 1015 (w), 950 (m), 660 (m), 700 (s).

Chemical analysis: found (calculated): % C 77.22 (77.61); % H

7.21 (7.46) % N 7.12 (6.97).

a-Methoxypropionic Acid (18)

The procedure followed here was that used by Leggetter and

Brown38 and Reeve and Saddle39 who followed the method of Fuson and Wojcik40 for the preparation of ethoxyacetic acid. In a three necked, 1000 mL, round bottomed flask fitted with a condenser and a dropping funnel was placed methanol (300 mLs). Through the condenser

was added metallic sodium (0.652 g atoms) cut into bits, such that the solution refluxed gently. Then 2-chloropropionic acid (46.9 g,

0.326 moles) in methanol (40 mLs) was added through the dropping funnel such that the mixture refluxed gently. After the acid was added, the solution was heated for 30 mins so that refluxing









continued. The excess alcohol was then removed by distillation initially and finally by passing steam into the residue. The aqueous solution was cooled and concentrated hydrochloric acid (30.4 mLs) was added. The precipitated sodium chloride was removed by filtration and washed with ethyl ether (2x25 mLs). The original filtrate was

saturated with dry sodium sulfate and was then extracted with the ether which was used for washing the precipitate together with additional (2x25 mLs) ether. The combined ether extracts were dried over sodium sulfate and removed by distillation at atmospheric pressure. The acid (18) (26.9 g, 80% yield) was recovered by distillation under reduced pressure 95-96� C/12 mm. lit b.p.38 108110�/30 mm
1H NMR (CDCI3-TMS) 6: 1.50 (d,3H), 3.45 (s,3H), 4.0 (q,1H), 10.85 (s,1H).
13C NMR (COCl3-TMS, int ref CDCI3) 5: 17.93, 57.60, 75.83, 178.37.

Methyl a-Methoxypropionate (19)

The procedure used was that used by Fuson and Wojcik40 for the synthesis of ethyl ethoxyacetate. In a three necked, 250 mL, round bottomed flask fitted for a gas inlet and an outlet to a sodium hydroxide solution (SN) was placed a-methoxypropionic acid (23 g,

0.2233 moles) and methanol (50 mLs). The solution was stirred with a magnetic stirrer bar and hydrogen chloride gas was passed into the solution via the inlet, which dipped into the solution, for 5 hrs.

The flask was cooled with an ice-water mixture since heat is evolved. It was then allowed to stand for 24 hrs to ensure








completion of the reaction at room temperature. The solution was cooled, and a saturated solution of sodium carbonate added slowly to avoid excessive foaming until the mixture was faintly alkaline to litmus. The ester (19) was extracted with ethyl ether (4x100 mLs) and the extracts combined and dried over anhydrous potassium carbonate. The ether was then distilled at atmospheric pressure and the ester (19) (16.2 g, 62% yield) recovered at 140-142� C/760 mm. lit b.p.39 142� C/760 mm.
1H NMR (CDCl3-TMS) 6: 1.45 (d,3H), 3.40 (s,3H), 3.78 (s,3H),

3.85 (m,1H).
13C NMR (CDCI3-TMS, int ref CDCI3) 6: 18.32, 51.85, 57.60, 76.32, 173.50.

2-Methoxy Propanol (20)

The method employed here was that used by Reeve and Saddle39 and adapted from the method of Fickett, Garner and Lucas41 for the reduction of a-chloropropionyl chloride and Moffett's42 method for the reduction of a-(1-pyrrolidyl)propionate. In a three necked, 500 mL, round bottomed flask fitted with a reflux condenser, mechanical stirrer with a mercury seal and dropping funnel was placed lithium aluminum hydride (9.1742 g, 0.2412 moles) and dry ethyl ether (200 mLs). The mixture was refluxed for 3 hrs to effect solution. To this was added methyl c-methoxypropionate (46.75 g, 0.3962 mole) in dry ethyl ether (100 mLs), at first a few drops until a white precipitate appeared and after cooling the solution down to 0* C with an ice-water mixture, the remainder. The addition was completed in 20 mins and stirring was continued for 30 mins. The excess








LiAlH4 was decomposed by adding methyl acetate (21.5 mLs) slowly with stirring. This was followed by the addition of hydrochloric acid (258 mLs, 6N). The aqueous layer was separated, made strongly alkaline with sodium hydroxide (430 mLs, 6N) and the alcohol extracted with ethyl ether (2x250 mLs). The original ether layer together with the extracts were combined and dried over anhydrous

potassium carbonate. The ethyl ether was removed by distillation at atmospheric pressure and the alcohol (20) (37.4 g, 58% yield) recovered by distillation of the residue at 133-1350 C/760 mm. lit b.p.39 135� C/760 mm.
1H NMR (CDCl3-TMS) 6: 1.117 (d,3H), 2.621 (s,lH), 3.388 (s,3H),

3.494 (d,2H), 3.49 (m,1H).
13C NMR (CDCl3-TMS, int ref CDCI3) 6: 15.11, 56.24, 65.94, 77.39.
IR (NaCl): 3400 (m,br), 2970 (m), 2930 (m,br), 2820 (m), 1630 (w,br), 1450 (m), 1370 (m), 1350 (m), 1235 (m), 1190 (m), 1140 (s), 1080 (s), 1040 (s,sh), 980 (m), 890 (m), 825 (w), 800 (m). 2-Methoxypropyl 2'-Carboethoxyallyl Ether (21)

The procedure followed was similar to that followed for the

synthesis of compound (17). In a flame dried, three necked, 100 mL, round bottomed flask, fitted with a dropping funnel and through which a flow of nitrogen was maintained, was placed 0.7047 g of 60% sodium hydride (0.4228 g; 0.0176 moles) in a mineral oil dispersion. The mineral oil was removed in a manner described in the procedure for the synthesis of compound (17). Dry DMSO (25 mLs) was added and stirred with a magnetic stirrer bar. To this was carefully added








dropwise 2-methoxypropanol (1.58 g, 0.0176 moles) in dry DMSO (10 mLs). Stirring was continued for 4 hrs. The alkoxide solution was then transferred to the dropping funnel and in the flask was placed 2-carboethoxyallyl bromide (3.4 g, 0.0176 moles) in dry DMSO (10 mLs). The alkoxide solution was added dropwise such that the temperature did not change appreciably. Stirring was continued for 12 hrs. Water (10 mLs) was added to destroy the unreacted NaH. The ether (21) was then extracted with pentane (3x75 mLs) and the combined extracts dried over magnesium sulfate. The pentane was then removed under reduced pressure on a rotary evaporator and the ether

(21) (1.78, 50%) was recovered by distillation at 550 C/0.06 mm.
1H NMR (CDCl3-TMS) 6: 1.159 (d,3H), 1.304 (t,3H), 3.397 (s,3H),

3.478 (d,2HO, 3.353-3.489 (m,lM), 4.234 (s,2HO, 4.226 (q,2H), 5.885 (q,1H,J 13C NMR (CDCI3-TMS, int ref CDCI3) 6: 14.08, 16.37, 56.68, 60.53, 69.35, 74.47, 75.78, 125.30, 137.34.

IR (NaCl): 2970 (m), 2920 (m), 2895 (m,sh), 2860 (m,sh), 1710

(s), 1630 (w), 1450 (m), 1370 (m), 1300 (s), 1365 (s), 1170 (s), 1150

(s), 1100 (s), 1020 (m), 945 (m), 850 (w), 810 (m), 680 (w).

Elemental analysis: found (calculated): % C 59.03 (59.41); % H

8.96 (8.91).








Miscellaneous Reactions

2-Chloro-2-propenyl Acetate43 (22)

2,3-Dichloropropene (16.679 g, 0.1503 moles), sodium acetate

(15.428 g, 0.188 mole), glacial acetic acid (8 mLs) and pyridine (0.5

mLs) were put into a tube and sealed. The tube was heated in an oil bath at 140-1500 C for 12 hrs. It was then opened after cooling and

the contents of the tube extracted with ether (3x100 mLs). The combined extracts of ether were then washed with dil. sulfuric acid (100 mLs, 10%) and then a saturated solution of sodium bicarbonate (100 mLs). The extracts were dried overnight over magnesium sulfate. The ether removed under reduced pressure on a rotary evaporator and the ester (22) distilled at 142-147* C. lit b.p.43 143-145G C) (11.1 g, 55% yield).
1H NMR (CDCI3-TMS) 6: 2.126 (s,3H), 4.651 (s,2H), 5.412 (s,lH),

5.441 (s,1H).
13C NMR (CDCl3-TMS, int ref CDCl3) 6: 20.52, 65.84, 114.72, 135.83, 169.89.

2-Chloro-2-propenol (23)43

2-Chloro-2-propenylacetate (22) (28.4 g, 0.21 moles) and

methanol (35.5 mLs) containing 1% HCl was refluxed in a 100 mL round bottomed flask for twelve hours. The methanol was distilled off.

The solution was then poured into water (100 mLs) and sodium bicarbonate (1.1 g) added to neutralize the acid. The alcohol was extracted with ether (3x100 mLs) and the combined ether extracts dried over magnesium sulfate. The ether was removed under reduced








pressure on a rotary evaporator and the alcohol (23) distilled at 135-1370 C (lit b.p.43 1300 C) (15.2 g, 78% yield)
1H NMR (CDCl3-TMS) 6: 3.25 (s,lH, exch. with D20), 4.15 (s,2H),

5.35 (s,lH), 5.50 (s,lH).
13C NMR (CDCl3-TMS, int ref CDCI3) 6: 65.5, 111.9, 140.6. 2-Chloroallyl Ether (24)

The procedure followed was similar to that followed for the

synthesis of compound (21). In a flame dried, three necked, 100 mL, round bottomed flask fitted with a dropping funnel through which a flow of nitrogen was maintained, was placed 0.8107 g of 60% sodium hydride (0.4864 g, 0.02027 moles) in a mineral oil dispersion. The mineral oil was removed in a manner described in the procedure for the synthesis of compound (8). Dry DMSO (25 mLs) was added and stirred with a magnetic stirrer bar. To this was added 2-chloroallyl alcohol (23) (2.249 g, 0.0243 moles) in DMSO (10 mLs) carefully dropwise. Stirring was continued for 4 hrs. The alkoxide solution was then transferred to the dropping funnel and in the flask was placed 2,3-dichloropropene (2.70 g, 0.024 moles) in DMSO (10 mLs). The alkoxide solution was added dropwise such that the temperature did not change appreciably. Stirring was continued for 12 hrs. Water (10 mLs) was added and the ether (24) was extracted with pentane (3x75 mLs) and the combined extracts dried over magnesium sulfate. The pentane was removed under reduced pressure on a rotary evaporator and the ether (24) (1.2 g, 36% yield) recovered by preparative high pressure liquid chromatography.








1H NMR (CDCI3-TMS) s: 4.12 (s,4H), 5.42 (s,2H), 5.52 (m.2H).

13C NMR (CDCl3-TMS, int ref CDCI3) 6: 72.42, 113.80, 137.48.

IR (NaCl): 2860 (w), 1635 (m), 1440 (w), 1385 (w), 1365 (w), 1255 (w), 1270 (w), 1180 (m), 1090 (s), 1035 (w), 890 (s), 720 (m), 640 (m).

Elemental analysis: found (calculated): % C 43.51 (43.11); % Cl 41.92 (42.51); % H 4.85 (4.80). Ethyl-a-(bis-2-chloroallyl )-malonate (25)

The method of Hill and Fischer44 was used. In a three necked, 250 mL, round bottomed flask, fitted with a mechanical stirrer, a dropping funnel and a condenser was placed ethanol (75 mLs). To it was added sodium (4.2 g, 0.1826 gr. atom) slowly to keep the mixture refluxing gently. After the sodium was dissolved diethylmalonate (29 g, 0.183 mole) was added dropwise through the dropping funnel. Stirring was continued for an hour and then 2,3-dichloropropene (44.4 g, 0.4 mole) was added and stirring continued for 12 hrs at room temperature. The sodium chloride which precipitated was filtered off and the ethanol removed under reduced pressure on a rotary evaporator. Water (40 mLs) was added and compound (24) extracted with ether (4x50 mLs). The combined ether extracts were dried over magnesium sulfate. The ether was removed under reduced pressure on a rotary evaporator and compound (24) (34.4 g, 61% yield) distilled at 107� C/0.75 mm.
1H NMR (CDCI3-TMS) 6: 1.266 (t,6H), 3.16 (s,4H), 4.22 (q,4H),

5.343 (br,s,4H).








13C NMR (CDCI3-TMS, int ref CDCI3) 6: 13.74, 40.52, 55.31, 61.79, 117.74, 136.90, 169.50.



Synthesis of Polymers

Polymerization of 2-Chloroallyl 2'-Phenylallyl Ether

2-Chloroallyl 2'-Phenylallyl ether (1) (0.926 g, 0.0044 moles) with benzene (1.389 g) and 2,2'-Azobisisobutyronitrile (AIBN) (0.046 g, 5% w/w of monomer) were divided equally and put into two polymerization tubes and taken through five freeze-thaw cycles on a mercury diffusion vacuum line for degassing, and sealed. These were

then immersed, with shaking, in a water bath at 40� C and an oil bath at 600 C, respectively.
The tubes were opened after 4 days and poured into methanol

(2x100 mLs). There was no precipitation. On evaporation of the methanol and benzene, the monomer (1) was recovered. The proton NMR

did not show any new peaks and the integration ratios were maintained as in the monomer.

Polymerization of 2-Carboethoxyallyl 2'-Phenylallyl Ether

2-Carboethylallyl 2'-Phenylallyl ether (3) (1.036 g, 0.0042

moles), benzene (1.554 g) and AIBN (0.0518 g, 5% w/w of monomer) were

divided equally and put into two polymerization tubes and taken through five freeze-thaw cycles on a mercury-diffusion vacuum line. These were then immersed, with shaking, in an oil bath at 60� C and a

water bath at 40� C. After 4 days, the tubes were opened and the polymer precipitated into methanol (2x100 mLs). The yields were as follows:










408 C polmerization: 0.292 (56%)

600 C polymerization: 0.441 g (85%)

The polymers were soluble in DMSO, benzene, dimethylformamide,

acetone, chloroform.

40� C polymerization sample:
IH NMR (CDCI3-TMS) 6: 0.95, 1.24, 2.1, 3.0, 4.1, 7.1 (Fig. 20).

13C NMR (CDCI3-TMS, int ref CDCl3) 6: 13.35-14.10, 26.34-28.58, 40.30, 41.62, 44.71, 51.17, 60.72, 72.66, 126.03-128.32, 140.41144.99, 173.55-174.96 (Fig. 21).

IR (KBr): 2980 (m), 2850 (m), 1730 (s), 1630 (w), 1600 (w),

1580 (w), 1495 (m), 1470 (m), 1445 (m), 1380 (m), 1245 (m), 1200 (m), 1110 (s), 1025 (m), 965 (w), 890 (w), 850 (w), 760 (m), 695 (m).

60� C polymerization:
IH NMR (CDCI3-TMS) 6: 0.95, 1.24, 1.625, 2.1, 3.0, 4.1, 7.1 (Fig. 15 of Discussion and Results).
13C NMR (CDCI3-TMS, int ref CDCl3) 6: 13.35-14.10, 30.16, 40.60, 41.72, 44.84, 50.20, 60.72, 72.37, 126.03-128.37, 140.65143.97, 173.69.

IR (KBr) same as for polymer formed at 40� C.

VPO (benzil standard): 6550.

Elemental analysis: found (calculated): % C 71.07 (73.17); % H

7.33 (7.32).
Polymerization of 2-Cyanoallyl 2'-Phenylallyl Ether at 40%

2-Cyanoallyl 2'-Phenylallyl ether (8) (1.09 g, 0.0055 mole),

benzene (1.635 g) and AIBN (0.0545, 5% w/w of monomer) were divided equally and placed in two polymerization tubes and taken through five








freeze-thaw cycles on a mercury diffusion vacuum line for degassing, and sealed. They were then immersed with shaking, in an oil bath at 600 C and a water bath at 40� C, respectively. The tube in the 600 C bath developed a white precipitate within 30 mins and was removed after 2 hrs and the polymer was precipitated into methanol (100

mLs). The tube at 400 C developed a precipitate in about 2 hrs and the polymer was precipitated into methanol (100 mLs) after 6 hrs. The polymers in both cases were insoluble in DMSO, benzene dimethylformamide, acetone, and chloroform. The percentage conversions in the two cases were as follows: 400 C polymerization

0.32 g (59%); 60: C polymerization 0.37 g (68%).

IR (similar for both cases except for relative intensities)

(KBr): 3040 (m), 3020 (m), 2910 (m), 2850 (m), 2225 (w), 1625 (w), 1600 (w), 1580 (w), 1490 (m), 1465 (m), 1445 (m), 1380 (m), 1240 (m), 1095 (s), 960 (m), 885 (w), 835 (w), 760 (m), 695 (s).

Elemental analysis: found (calculated): % C 75.24 (78.35); % H

6.46 (6.58), % N 6.73 (7.03).

Polymerization of 2-Cyanoallyl 2'-Phenylallyl Ether at 10%

2-Cyanoallyl 2'-Phenylallyl ether (8) (1.08 g, 0.0054 moles),

benzene (9.81 g) and AIBN (0.0545 g, 5% w/w of monomer) were divided equally into three polymer tubes and taken through five freeze-thaw cycles on a mercury diffusion vacuum line for degassing and sealed. They were then immersed, with shaking, in a water bath at R.T. for 5 days, a water bath at 40� C for 8 hrs and a water bath at 600 C for 1 hr. The conversion was kept low in all three cases. The polymers

formed in the three cases were precipitated in methanol (3x100 mLs).








The percent yields were as follows:

polymerization at R.T.: 0.092 g (26%) polymerization at 400 C: 0.078 g (22%) polymerization at 60� C: 0.05 g (14%)

The polymers were soluble in DMSO, dimethyl formamide, acetone and chloroform.

The IR spectra were similar to the polymers formed in the previous experiment done at 40% monomer concentration.

Polymer sample formed at R.T.:
1H NMR (CDCI3-TMS) 6: 1.2574, 1.5638, 3.0627 (br), 4.1204,

4.4428, 5.3620, 5.5240, 6.0263, 7.33.

Polymer sample formed at 400 C:
1H NMR (CDCI3-TMS) 6: 1.258, 1.724, 2.315 (br), 3.126 (br),

3.917, 4.120, 4.442, 5.350, 5.576, 6.020, 7.334.

Polymer sample formed at 600 C:
1H NMR (CDCI3-TMS) 6: 1.257, 1.547, 1.725, 2.317, 3.100, 3.92

4.133, 4.40, 5.366, 5.54, 6.023, 7.334. Polymerization of 2-Carboethoxyallyl 2'-Methoxyallyl Ether

2-Carboethoxyallyl 2'-Methoxyallyl ether (15) (0.553 g, 0.0028 moles), benzene (0.8295 g) and AIBN (0.0277 g, 5% w/w of monomers) were placed in a polymerization tube and taken through five freezethaw cycles on a mercury diffusion vacuum line for degassing and

sealed. This was then immersed, with shaking, in a water bath at 4( for 2 days. The polymer was precipitated in methanol (100 mLs). A similar procedure was followed for 0.475 g (0.0024 moles) of cpd


)�


t,








(15), benzene (0.7125 g) and AIBN (0.0238 g, 5% w/w of monomer). The

water bath was however at 600 C.

The percentage yields were as follows: polymer formed at 40* C: 0.45 g (81%) polymer formed at 600 C: 0.39 g (82%)

Both polymer samples were soluble in benzene, chloroform,

acetone, DMSO and DMF.

Sample formed at 40* C:
1H NMR (CDCl3-TMS) 6: 1.152, 1.349 (sh), 1.862, 2.261, 3.222,

3.557, 4.081, 4.265.
13C NMR (CDCl3-TMS, int ref CDCI3) 6: 14.96, 20.27, 27.19, 42.30 (br), 481.69, 49.51, 54.73, 65.74, 83.04, 99.47, 173.65.

IR (KBr): 2970 (m), 2940 (m), 2870 (m), 1725 (s), 1670 (w),

1635 (w), 1445 (w), 1375 (m), 1300 (w), 1230 (w), 1100 (s), 845 (w), 810 (w), 745 (w).
Elemental analysis: found (calculated): % C 57.36 (59.96); % H

7.88 (8.06).

Sample polymerized at 600 C:
1H NMR (CDCI3-TMS) 6: 1.133, 1.340, 1.873, 2.171, 3.218, 3.560,

4.081, 4.250.
13C NMR (CDCI3-TMS, int ref CDCl3) 6: 15.01, 20.37, 27.19, 48.25, 49.17, 54.78, 66.28, 83.04, 99.47, 173.65.

IR (KBr): same as 40�C polymerization sample.




52


Attempted Polymerization of 2-Chloroallyl Ether

2-Chloroallyl ether (0.98 g, 0.0059 moles), benzene (1.47 g) and AIBN (0.049 g, 5% of monomer) were placed in a polymer tube. It was taken through five freeze-thaw cycles on a mercury diffusion vacuum line and sealed. It was then immersed in a water bath at 60� C for 4 days. The contents were then poured into methanol (100 mLs) but no precipitate was obtained. A viscous liquid was obtained after removing the methanol but was not identified.














CHAPTER III
RESULTS AND DISCUSSION


NMR Analyses

The assignments of unsaturated carbons have been rationalized using the resonance structures as shown in Figure 8.45 As shown in the top resonance structure with an electron releasing group, a negative charge in one of the contributing resonance structure would shift the carbon a to the methoxy group to a lower 6 value and, along

the same arguments, the carbon a to the methoxy group to a higher 6 value. Similarly an electron withdrawing group would lower electron density on the carbon a to the electron with drawing group as shown in the bottom resonance structure of the above mentioned figure. This analysis has been used in conclusions regarding "charge transfer" or a biased electron delocalization in related structures.

A similar analysis could be drawn up for assigning hydrogens in the proton NMR.


Synthesis of Monomers
The Williamson reaction46a was the base reaction in the

synthesis of the four monomers. The reaction is depicted in general terms below.
















OCH 3





OCH3


84.2 153.2


0
__/


+ o - CH
3


1 2 0
129.3


150.7


Fig. 8: Information regarding C 13 NMR chemical shifts of
substituted alkenes.


0-










RX + R'OH


ba se sol vent


base
R'OH - : R'O-


ROR'


RX
30 R'OR (S N1)


Hence for each ether the following combination of reactants could be

used.


(RX,R'OH) or (R'X,ROH) for the same ether ROR'


For the monomers synthesized the ease of synthesis of the halide and the corresponding alcohol dictated the combination used.

For the allylic ethers prepared, whenever the unsaturated point

had an electron-withdrawing group attached in the halide, the alkoxide in DMSO was added to the halide in DMSO and whenever the unsaturation point had an electron donating group attached in the halide, it (in a DMSO solution) was added to the alkoxide. This was due to the possible attack of the alkoxide as shown.


0


D 0


giving side reactions thereby










2-Phenylallyl 2'-Chloroallyl Ether (1)

(Scheme 3) The combination used here for the Williamson

reaction was 2-phenylallyl alcohol47 and 2-chloroallyl chloride due to the availability of both reagents. The 2-phenylallyl alkoxide formed by sodium hydride was added to 2-chloroallyl chloride. The product, 2-phenylallyl 2'-chloroallyl ether (1), was isolated by high pressure liquid chromatography since an attempt at fractional distillation did not give a very efficient separation from the unreacted 2-phenylallyl alcohol. The 2-phenylallyl 2'-chloroallyl ether structure was confirmed via proton NMR and carbon-13 NMR (as shown in Fig. 9), IR and elemental analysis. The assignments were

confirmed by an INEPT48 spectrum which showed negative peaks at 6 = 72.077, 113.058 and 114.722 ppm. The assignments for carbon 1 and carbon 3 were done on the basis of electron density at the double bond itself and on the analysis discussed at the beginning of this chapter. The infrared spectra showed peaks at 1635 and 1600 cm-1 corresponding to the C=C stretch of the a-phenyl allyl and 2chloroallyl moiety respectively.

The proton assignments were based on general assignment principles as well as integration ratios.

As can be seen, the two sets of unsaturated carbons do not

differ widely as regards electron density as can be concluded from Figure 9 and the initial analysis.





















-0/C

0 C1


-ci

cpd.CJ) 16% yield
l.c. separation



0


CO C H
2 2 5



Br


0


/0


NaH DMSO













SNai DMSO


OH OH


\C0 C0 2 H5

(3) 20% yield


separati


on CO2C2H5

C H OH
cpd.C31 (25

Br H , reflux


Scheme 3: Synthesis of compounds (1) and (3).


cpd. l.c.


COOH Br












0
3


16o 14,o 120 1o 80 60 20 0 PPM





0

HJH6
I Cl


8 6 5 '4


31 2 PPM


Fig. 9: Proton (100
of compound


MHz) spectrum
(1) in CDCI3.


and noise decoupled C 13 spectrum


8








2-Carboethoxyallyl 2'-Phenylallyl Ether (3)

(Scheme 3) The combination used in the synthesis was 2phenylallyl alcohol and 2-carboethoxyallyl bromide (2). The 2carboethoxyallyl bromide (2) was synthesized via the acid catalyzed esterification as reported32 from a-(bromomethyl)acrylic acid. The structure of (2) was confirmed by C 13 NMR, proton NMR and IR. The C 13 NMR and proton NMR assignments are listed in Table 1. Here again 2-phenylallyl alkoxide in DMSO was added to the 2-carboethoxyallyl

bromide as described.31 The monomer was isolated via preparative high pressure liquid chromatography since attempts to isolate the compound (3) via distillation under reduced pressure (upto 0.5 mm) seemed to polymerize it. The identity of the monomer was confirmed via carbon-13 and proton NMR spectra which are shown in Figure 10. The carbon assignments were confirmed by an INEPT spectrum showing negative peaks at 6 = 69.04, 73.28, 114.46 and 125.33 ppm and

-positive peaks at 6 = 14.61 and 60.95 ppm. The proton NMR spectrum showed four different peaks assigned as shown. The two sets of carbons do differ to a greater extent than in compound (1) as can be seen from the carbon spectra. The C=C stretch for the 2-phenylallyl

and the 2-carboethoxyallyl moiety occur at 1635 and 1600 cm-1 in the IR spectra.

2-Phenylallyl 2'-Cyanoallyl Ether (8)

(Scheme 4) The mechanism of the first step would be




0 HCN
HS3 Cl CI C








Table 1: Carbon-13 and proton NMR assignments for compound (2)


4 5
l / C0 2CH 2CH3 H2/--*

Br


4 5 6 CO 2CH 2CH3

2 2

Br


proton 6: (CDCI3)


1.26-1.40 4.16-4.38
4.19 5.96
6.32


carbon 6:
(CDCI3)


13.99 61.11 68.41
125.01 137.58 167.75












5_2

T

C811 I Cl


180 i6o Io 120 100 80 60 o 20 o PP(


0
H --, 8 2


,6 2 1 0


Fig. 10: Proton (100 MHz) spectrum
decoupled 25 MHz spectrum


(in CDC1 ) ang C 13 noise (in benzine-d ) of compound (3).


I I I I � � � I I'


I mQQ






















Cl
0


NaH
DMSO


OH


cpd.C8) 24% yield l.c. separation


CN


cpd.C6) 6o%
CI


NC H
\--/40

Cl

28% yield


50e C

N2

cis & trans cpd. C7)


0

0




-A
NC C1

cpd. (5)


Synthesis of compound (8).


0 0 6a - 7C


cpd. (4)


NaHSO3 NaCN


0

II


C1


Scheme 4:








The identity of the chloroacetone cyanohydrin (4) was confirmed by carbon-13 and proton NMR and IR spectra and the assignments for the protons and carbons shown in Table 2. The chloroacetone cyanohdrin

acetate (5) was confirmed by carbon-13 and proton NMR spectra and the assignments for the protons and carbons shown in Table 3.

Compound (4) showed the CN stretch in the IR at 2250 cm-1.

2-Cyanoallyl chloride (6) was confirmed by carbon-13 and proton NMR and IR. The assignments for the protons and carbons are shown in Table 4. In the proton NMR H1 and H2 occur at the same chemical shift. They occur at 6 = 6.09 and 6.19 in CC14 and agree with the literature.49 The pyrolysis apparatus used in the synthesis was modified from the one used by M. Tsurnshima et al.50,51 The mixture of 2-cyanoallyl chloride (6) and B-chloro-a-methacrylonitrile (7) could be used directly since in (7) the chloride is attached to the double bond and could not be eliminated and the difference in rate of elimination of the allylic chloride in (6) to the allylic hydrogen in

(7) would be very great. Compound (7) is the first fraction collected during the liquid chromatographic separation of 2-cyanoallyl 2'-phenylallyl ether (8). The C 13 NMR and proton NMR assignments for the cis and trans isomer of 7 is listed in Table 5. 2Cyanoallyl 2'-phenylallyl ether (8) was identified by carbon-13 NMR, proton NMR, IR and elemental analysis, the first two spectra being shown in Figure 11. The INEPT spectrum (Fig. 12) helps identify the different carbons. The two sets of carbons do differ to a








Table 2: Proton and carbon-13 NMR assignments for compound (4).


OH
3

1 2 ON C


proton 6: (CDCI3)


1.708
3.681
4.309


OH

3
2
ON C


carbon s: (CDCI3)


24.80 50.05 68.72 119.50


Table 3: Proton and carbon-13 NMR assignments for compound (5).


0



2

CN C1


0


2c

ON
C1


1.85
2.15
3.90


carbon 6: (CDCI3)


20.61 22.76 46.83 70.62 116.38 168.38


proton 6: (CDCl3)








Table 4: Proton and carbon-13 NMR assignments for compound (6).



14


H2 CN H1 3

C1


proton 6:
(CDCI3)


4.160 3
6.116 1,2


1 2 CN
C5

C1


carbon 6:
(CDCI3)


43.23 113.26 115.65 133.29


Table 5: Proton and carbon-13 NMR assignments for compound (7).




NC 2


proton 6:
(CDCI3)


cis 2.018 6.667


trans
2.034 6.926


14
NC Cl 3/-


C-13 6: (CDCl3)


cis
18.42 116.23 119.79 131.78


trans 15.45 116.23 119.79 135.14












46
0


CN


16o 14o 120 100 80 60 4o 20 0 PPM H3 H5

0

2 CN


8 7 6 5 4f 3 2 1 0 PPM


Fig. 11: Proton spectrum (100 MHz) (in benzene d )
decoupled spectrum (25 MHz) (in CDCi3) 8f


and C 13 noise compound (8).



















0


65 14


C 6H5


16o 14~0 120 100 80 6o 0 20 0 PPM










CH2') .. .........

CH, CH-- +


' rI,, ,


VI
-- -~--~


-WT - ' - wi . - - - " t"


Fig. 12: 25 MHz decoupled and multiplicity determination C 13
spectra for compound (8).


,LII | � � ,J


- I . .. . . .








greater extent than even compound (3). The infrared spectrum shows

the CN stretch at 2230 cm-1.

2-Carboethoxyallyl 2'-Methoxyallyl ether (15)

(Scheme 5) The combination used here for the Williamson reaction was 2-carboethoxyallyl alcohol (14) and 2-methoxallyl bromide (12). The syntheses of the synthons46b of the other combination were not reported. 2-Carboethoxyallyl alcohol was prepared via the method of Rosenthal et al.37


4H-C-C-CH2-OH + Ni(CO)4 + 2CH3CO2H + 550, C2H5OH

4CH2=C-CH20H + Ni(CH3CO2)2 + 2[H1

C02H

H2SO4 02C2H5
CH2=C-CH2OH + C2H5OH -CH2=C-CH2OH

CO 2H -H20


The identity of the ethyl-a-(hydroxymethyl)acrylate (14) was confirmed via C 13 NMR, proton NMR and IR. The assignments for the carbons and protons are listed in Table 6. The first method for the synthesis of 2-methoxyallyl bromide via bromination using Nbromosuccinimide of Greenwood and Hoffman36 was successful but the method of Jacobson et al.35 was preferred. The drawback of the method of Greenwood et al. was that one obtained a carbon

tetrachloride solution of the 2-methoxyallyl bromide contaminated with products resulting from the addition of succinimide to the enol















OMe


OMe
Brf


Br


0






cpd. C15) 25% yield


Ni Co)

OH CH 3Co H,

H20, 55 C


CO2 C 2H5


NaH
- DMSO


COOH
7 H O

OH


OMe


CO C H OH


CO2 C 2H5



OH
cpd.(*14)


0 OMe


II


Br
cpd. C9)


OMe


CH30H ,H+


OMe



OMe cpd.
Br


N+HOTs


Cio)


0
190 C


" MeO Br
__OMe+ _h45% Br 15% cis
cpd. (13)


trans


Synthesis of compound (15).


0 II


Br 2 H+


Scheme 5:


- "[150*-








Table 6: Carbon-13 and proton NMR assignments for compound (14).


2 1 H CO2CH2CH3 H6/--') 3

OH 4


1.3 2.7


4.25 4.3 5.8 6.25


45 6 Co 2CH 2CH3
2 2



OH


1
4 (deuterium
exchange)
2
3
5
6


carbon 6: (CDCI3)


13.89 60.58 61.55 124.88 139.58 166.09


(or 3) (or 5)


Table 7: Carbon-13 and proton NMR assignments for compound (9).

0


1 A 2


12

Br
carbon 6: (CDCI3)


2.40 3.90


26.98 34.82 199.68


proton 6: (CDCI3)


proton 6:
(CDCI3)









Table 8: Carbon-13 and proton NMR assignments for compound (11).


T 8
9 01
3
0


1,2,3,4,5
9
8
6,7
10.13 11,12
14


carbon 6:
(CDCI3)


0


0


16 2



5


13 12


proton 6: (CDCI3)


2 6


-0-H


12.09 16.86
18.23 20.96 42.39 54.00 125.59 128.27 139.19 143.04


1.37 2.35
2.8-3.3
3.3-3.9
7.17 7.82 9.18








ether double bond. It also resulted in only 10-20% conversion to the desired 2-methoxyallyl chloride. The 1-bromo-2,2-dimethoxypropane

(10) was prepared from bromoacetone using the method described by Jacobson et al.35 Bromoacetone was synthesized from acetone and the identity was confirmed by carbon-13 NMR, proton NMR, and IR. The assignments for the carbons and protons are listed in Table 7. The catalyst used here was reported to be the most efficient35 and was

synthesized as per the method reported by Jacobson et al.35 The structure was confirmed by carbon-13 NMR and proton NMR. The assignments of these are listed in Table 8. 1-Bromo-2,2-dimethoxy propane (10) was confirmed by carbon-13 NMR, proton NMR and IR. The assignments for the carbons and protons are listed in Table 9.

The fraction collected between 85� C and 130� C had the highest percentage of 2-methoxyallyl bromide.12 This would seem true since 1-bromo-2,2-dimethoxy propane (10), the other major constituent, has a boiling point of 156� C. The proton NMR assignments for (12) and

(13) are listed in Figure 6 and the carbon-13 NMR spectrum and the assignments in Figure 13. The mixture could be used directly in the subsequent reaction for the synthesis of (14) since again the allylic bromine in (12) would be more easily displaced than the allylic hydrogen in 1-bromo-2-methoxypropene (13) and the bromine in (10) by 2-carboethoxyallyl alkoxide. 2-Methoxyallyl 2'-carboethoxyallyl ether (14) was prepared using the Williamson reaction and identified using C 13 NMR, proton NMR and IR. The spectra are shown in Figures 14 and 15. Figure 14 also shows the off-resonance decoupled C 13 spectrum. The structure was also confirmed by an INEPT spectrum.








Table 9: Carbon-13 and proton NMR assignments for compound (10).





OMe1 OMe2

3 4
2 1 3


OMeI OMe2 Br


proton 6: (CDC13)


1.45 3.20
3.35


carbon 6: (CDC13)


20.61 34.55
48.69 99.76



















8
12



11 Br
4

12

CH130 Er


. II.


"i .... I "
140


I...I..I..I..I..I.....I..I.. I.. I.................................. ..- -. .....................I. I, IIIII II


100 so


40


20 0 PPH


Fig. 13: Carbon-13 (25 MHz) spectrum of the pyrolysis of 1-bromo-2,2-dimethoxypropane
















oCH
H3Hh H 7


0
8
H5 6 COOCHICH2
2 3


H8

3
H 5H 6H 14


Fig. 14: Proton spectrum (60 MHz) in CDC13 (15).


H2


(I


PPM





76




ccl

eOOC HC H h ib
b 2 c 3
0




OC H3




C






d f Or IM1 1" 0 2 P 8o :60 10 120 100 80 60 20 0 "






























Fig. 15: Noise and off-resonance decoupled C 13 spectra in CDC3
(15).








Synthesis of Model Compounds

The model compounds were synthesized mainly to see if there was any charge transfer occurring in the free state of the monomer. Hence compounds were synthesized having structures similar to the monomers prepared. The monomer, 2-chloroallyl 2'-phenylallyl ether, was not pursued since it was not expected to show any "charge transfer" interaction due to its non-polymerizability. The two 2sets of carbons are comparable as per the carbon-13 NMR spectra. This would be expected since the chlorine group is electron releasing by resonance and electron withdrawing by induction, and field effects which contribution predominates would determine whether the chlorine group acts as an electron donating or an electron withdrawing group. It was decided therefore only to synthesize model compounds for compounds (3), (8) and (15). The model compounds would have an

unsaturation point only attached to the electron withdrawing group since if the unsaturation point was attached to the electron releasing group chemical shifts in the proton and carbon-13 NMR spectra would be extremely small. 2-Carboethoxyallyl 2'-Phenylpropyl Ether (16)

(Scheme 6) This was prepared by the Williamson reaction using 2-phenyl propanol and 2-carboethoxyallyl bromide (2), with sodium hydride as the base. The identity of the 2-carboethoxyallyl 2'phenylpropyl ether (16) was confirmed by C 13 NMR, proton NMR, IR and elemental analysis. The C 13 NMR and proton NMR assignments are

listed in Table 10.
















CO 2C 2H5




Br
--


pCO 26 C H Hi5

cpd. ('16) 4o% yield


CN



Cl


0<


CN

cpd.(17) 45% yield


Synthesis of compounds (16) and (17).


NaH

DMSO


NaH

DMSO


Scheme 6:








Table 10: Carbon-13 and proton NMR assignments for compound (16).


7 8 HC2 2 CH2CH3 H2 / 3


0



5 6 4


7 89
CO CH CH







0


0.936 1.221 3.320
3.212-3.407
3.967
4.151 5.7291 6.280
7.117-7.128


carbon :d6) (benzene d)


proton 6: (CDCl3)


14.11 18.39
40.37 60.41 69.37 76.87
124.54 127.71
128.54 138.38
144.67 165.53








An attempt to isolate (16) via distillation proved unsuccessful to purify it totally and preparative high pressure liquid chromatography had to be used. 2-Cyanoallyl 2'-Phenylpropyl Ether (17)

(Scheme 6) The Williamson reaction was utilized for this

synthesis. The 40:60 mixture of $-chloro-a-methacrylonitrile (7) and c-(chloromethyl)acrylonitrile (6) was used directly and (17) isolated via preparative high pressure liquid chromatography.

The compound (17) was isolated and identified via C 13 NMR,

proton NMR, IR and elemental analysis. The C 13 NMR and proton NMR

spectra are shown in Figure 16. 2-Carboethoxyallyl 2'-Methoxypropyl Ether (21)

(Scheme 7) The Williamson reaction was used here and the

reaction was carried out by adding 2-carboethoxyallyl bromide (2) in DMSO to 2-methoxyprop-oxide in DMSO. 2-Methoxypropanol was synthesized using standard reduction procedures from methyl-2methoxypropionate with lithium aluminum hydride.


0 LiAIH4

CH3--C< 0 CH3-C-CH2OH + CH3OH

OCH3 OCH3 OCH3


2-Methoxypropanol was identified by C 13 NMR, proton NMR and IR. The assignments for the C 13 NMR and proton NMR spectra are listed in Table 11.

The methyl-2-methoxypropionate (19) was obtained via

esterification of 2-methoxypropionic acid (18). The carbon-13 NMR













H6Q

0

HI \ H3


a 7 6


I.
1 .4 B PPM


23


0 CN


L ..


I . I I 1 160 146 INS


Fig. 16: Proton (100 MHz) NMR spectrum (in CDCI )
MHz) NMR spectrum (in CDCI3) of compoud


and carbon-13 (25
(17).


so


66


4,


to


0 I1%


I.. . . . . . . . . � I,,I,1-, ,,,,i .. I .. I ....VT I ... 1 ... I ... I I. vi... I'I19 1 11' 11 1 1 iI. I... I


S .4


I
a PIK






















- 0 OHR


OMe



cpd.C20) OH

1.

2.


-. MeO-Na
2. H+


LiAIH 4



NaH, DMSO
CO 2C 2H5


OMe




OH
cpd. 0.81 CH3OH, HCI(li OMe


cpd. C-12)


OMe Br


0 cpd.(21), 50% yield




- CO2 C2 H5


Synthesis of compound (21).


Scheme 7:









Table 11: Proton and carbon-13 NMR assignments for compound (20).
3
OMe



O 5


proton 6: (CODl3)




Table 12:


proton 6:


1.117 2.621 3.388
3.494
3.49


(D20 exchange)


C-13 6:
(CODC3)


15.11
56.24 65.94 77.39


Proton and carbon-13 NMR assignments for compound (19).

5


1.45 3.40
3.78 3.85


carbon 6:


18.32 51.85 57.60 76.32
173.50








Table 13: Proton and carbon-13 NMR assignments for compound (18).


3
OMe



OH5


proton 6: 1.50 1 carbon 6: 17.93 1
3.45 3 57.60 3 4.0 2 75.83 2 10.85 5 178.37 4








and proton NMR assignments used for the identification of (18) and

(19) are listed in Tables 12 and 13, respectively.

The 2-methoxypropionic acid (18) was obtained via a substitution of the chlorine in 2-chloropropionic acid.40


ClCH-CO2H + 2CH3ONa CH3OCH-CO2Na + NaCl + CH30H
I I
CH3 CH3


CH30CH-CO2Na + HCl --* CH30-CH-CO2H + NaCl
I I
CH3 CH3


C H3O-CH-CO2H + CH3OH CH3O-CH-CO2CH3 + H20

CH3 CH3


2-Carboethoxyallyl 2'-methoxypropyl ether (21) was purified via distillation. The identity was confirmed via carbon-13 NMR, proton NMR, IR and elemental analysis. The carbon-13 NMR spectrum and the INEPT spectrum with the assignments are shown in Figure 17 and the proton NMR assignments are listed in Table 14.



Comparison of Spectra

The carbon-13 chemical shifts of the unsaturated carbons of

interest in compounds (3), (8) and (15) and their respective models

(16), (17) and (21) are listed in Tables 15, 16 and 17. The protons for the models have decreased in chemical shift and the carbons have decreased (C1 to which the protons are attached < C3) and increased (C2 > C4) in chemical shifts with respect to the monomers. This is










COOCH CH S 7 28 3

3

0

654

OCH3
5 93


CDC13,


- 4 , rue --I


16o 14o 120 100 80 60 4o 20 ;PPM


Lt. . LJL


I i


CH, CH - +
3


Fig. 17: 25 MHz decoupled and multiplicity determination sequence
C 13 spectra (21).


6 Ad.1 I --- LIAWLAAIL ., W7wwwrrw*rw


laA-A-L .1L a.J


2


Co J ... .ai








Proton NMR assignments for compound (21).


C 2 CH2CH3 H2 3


0



98 6

OMe
7


proton 6: (CDCI3)


1.159 1.304 3.397 3.478
3.353-3.489
4.234 4.226 5.885 6.298


Table 14:








consistent in all three pairs. Assuming no intermolecular interaction due to the dilute conditions under which the NMR spectra

were obtained, one could conclude that intramolecular interaction amounting to "charge transfer" could be taking place. Referring back to Section A and Figure 8, if there had been no "charge transfer," relative to the molecule with charge transfer the double bond with the electron donating group would be more electron rich which could

be looked upon as another very weak electron donating group attached to the unsaturation. This would cause C1 to increase and C2 to decrease relative to the molecule having "charge transfer" if the weak electron donating group were attached to C1.

A similar analysis could be drawn for the double bond with the

electron withdrawing group which would cause C3 to decrease and C4 to increase. This latter case is, indeed, what is seen in the case of the monomers and their model compounds. A similar analysis could be drawn for the hydrogens attached to C1 in Tables 15, 16 and 17. They would decrease in chemical shift as would C10. However, certain deviations may be expected anyway since factors other than "charge transfer" would come into effect because the hydrogens would be

susceptible to steric interactions.

The magnitude of the shift in the carbon-13 NMR would be

expected to be small as could be derived from an experiment done by mixing 2,4,6-trimethoxystyrene52 with fumaronitrile. The scheme for preparation used for the synthesis of 2,4,6-trimethoxystyrene is shown in Figure 19. The proton and carbon-13 NMR chemical shifts of two separate compounds and a mixture in a 1:1 molar ratio are shown









Comparative proton and carbon chemical shifts for compounds (3) and (16).


Hl 2 CO2C2H5
H22


0
S20k


H3 CO2 C 2H5




0


R. T.

H1
H2 C1 C2


R. T.

H3 H4 C3 C4


benzene-d6

6.284 5.802 124.83 138.23


benzene-d6

6.280 5.729 124.54 138.38


CDCL3

6.302 5.856 125.59 137.34decr.


incr.


CDCL3

5.238 5.754 125.15 137.43 -


Table 15:









Comparative proton and carbon chemical shifts for compounds (8) and (17).


H1 1 CN H2/T


0

0







H3 \i"CN




0


R.T.

H1
H2 C1
C2


benzene-d6


5.243 130.19 120.79


CDCL3


5.979 131.39120.23-


decr.


incr.


R.T.

H3 H4 C3 C4


benzene-d6

5.242 5.170 129.80 121.03


CDCL3

5.955 5.869 131.00 120.47 -


Table 16:




Full Text

PAGE 1

CHARGE TRANSFER IN CYCLOPOLYMERIZATION AND THEORETICAL CALCULATIONS FOR CHARGE TRANSFER IN COPOLYMERIZATION BY ROY JOSEPH NOEL YAZ 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

PAGE 2

ACKNOWLEDGMENTS I would like to express my deep gratitude to a scholar and gentleman. Dr. G.B. Butler, for his help, stimulation and imparting of wisdom during the course of my stay at the University of Florida. I would like to extend my thanks and appreciation to members of the supervisory committee and to Dr. T.E. Hogen Esch for their time and help. Appreciation and thanks also go out to Dr. M. Zerner and especially Dr. G. Purvis for their patience, time and help at the Quantum Theory Floor. All the members of the Polymer Division are greatly acknowledged for their patience and forbearance. Dr. A. Matsumoto is thanked for many helpful discussions. Friends outside of chemistry are acknowledged for my maintenance of composure. Thanks are due to Ms. Cindy Zimmerman for the typing of this manuscript. Financial support from the Department of Chemistry and the National Science Foundation is acknowledged.

PAGE 3

TABLE OF CONTENTS Page ACKNOWLEDGMENTS ii LIST OF TABLES LIST OF FIGURES v ii ABSTRACT i x CHAPTERS I INTRODUCTION 1 Cyclopolymeri za tion 1 Charge Transfer 7 Proposed Research 12 II EXPERIMENTAL 14 General Information 14 Reagents and Solvents 15 Synthesis of Monomers 16 Synthesis of Model Compounds 36 Miscellaneous Reactions 44 Synthesis of Polymers 47 III RESULTS AND DISCUSSION 53 NMR Analysis 53 Synthesis of Monomers 53 Synthesis of Model Compounds 77 Comparison of Spectra 85 Polymer Synthesis and Characterization 100 Conclusions on Polymerization of Monomers 104 Frontier Molecular Orbital Analysis 108 IV THEORETICAL CALCULATIONS 114 Introduction 114 Calculation Details 118 Discussion 135 Conclusions 139

PAGE 4

APPENDIX CNDO /2 DENSITY MATRICES AND GROSS CHARGE DENSITIES FOR N-METHYLMALEIMIDE, METHYL VINYL ETHER, Co and c 3 , respectively ; 141 BIBLIOGRAPHY BIOGRAPHICAL SKETCH i v

PAGE 5

LIST OF TABLES Table Page 1 Carbon-13 and proton NMR assignments for compound (2).. ...60 2 Proton and carbon-13 NMR assignments for compound (4).. ...64 3 Proton and carbon-13 NMR assignments for compound (5).. ...64 4 Proton and carbon-13 NMR assignments for compound (6).. ...65 5 Proton and carbon-13 NMR assignments for compound (7).. ...65 6 Carbon-13 and proton NMR assignments for compound (14). ...70 7 Carbon-13 and proton NMR assignments for compound (9).. ...70 8 Carbon-13 and proton NMR assignments for compound (11). ...71 9 Carbon-13 and proton NMR assignments for compound (10). ...73 10 Carbon-13 , and proton NMR assignments for compound (16). ...79 11 Proton and carbon-13 NMR assignments for compound (20). ...83 12 Proton and carbon-13 NMR assignments for compound (19). ...83 13 Proton and carbon-13 NMR assignments for compound (18). ...84 14 Proton and carbon-13 NMR assignments for compound (21). ...87 15 Comparative proton and carbon chemical shifts for 16 17 compounds (3) and (16) Comparative proton and carbon chemical shifts for compounds (8) and (17) Comparative proton and carbon chemical shifts for compounds (15) and (21) .89 .90 .91 v

PAGE 6

13 Comparative carbon chemical shifts for fumaroni tri le and 2,4,6-trimethoxystyrene separate and mixed in a 1:1 molar ratio 95 19 Comparative proton chemical shifts for fumaroni trile and 2,4,6-trimethoxysy trene separate and mixed in a 1:1 molar ratio 96 20 iJ C chemical shift differences with acceptors different. . .97 21 C chemical shift differences with donors different 97 22 Comparison of CNDO and PCILO determinations with experimental data, AE-kcal /mole,R-A 117 23 Parameters of methyl vinyl ether 119 24 Parameters of N-methylmaleimide 120 25 Coordinates of C 2 and C 3 122 26 Bond angles and distances (A) of C 2 123 27 Bond angles and distances of C 3 125 28 Energy gradient values of last cycle and summary of geometry optimization of cycles 95-106 for methyl vinyl ether 127 29 Energy gradient values of last cycle and summary of geometry optimization of cycles 38-46 for N-methylmaleimide 128 30 Energy gradient values of last cycle and summary of geometry optimization of cycles 155-156 for C 2 129 31 Energy gradient values of last cycle and summary of geometry optimization of cycles 167-170 for C 3 130 32 CNDO energy and difference in energy corresponding to various distances between molecules N-methylmaleimide and methyl vinyl ether 133 33 PCILO energy and difference in energy corresponding to various distances between molecules N-methylmaleimide and methyl vinyl ether 137 34 Coordinates of the comglex (E c *) with the moieties at a distances of 7.0 A 138 vi

PAGE 7

2 3 4 5 6 7 8 9 10 11 12 13 LIST OF FIGURES Page Reaction coordinates proposed as a result of product distribution study in the cyclization of radicals XII and XIII 8 Evidence for charge transfer between acrylonitrile and styrene in the presence of ZnCl 2 11 Apparatus for the pyrolysis of chloroacetone cyanohydrin acetate 23 Proton spectrum of the pyrolysis products with the integration (in CDC1 3 ) 24 HPLC chromatograph. Separation of 2-phenylallyl 2'cyanoallyl ether 27 Proton (60 MHz) spectrum in C0C13 32 HPLC chromatograph. Separation of 2-phenyl 2'carboethoxyallyl ether 37 Information regarding C 13 NMR chemical shifts of substituted alkenes 54 Proton (100 MHz) spectrum and noise decoupled C 13 spectrum of compound (1) in CDC1 3 58 Proton (100 MHz) spectrum (in CDC1 3 ) and C 13 noise decoupled 25 MHz spectrum (in benzene-d°) of compound (3) 61 Proton spectrum (100 MHz) (in benzene-d 6 ) and C 13 noise decoupled spectrum (25 MHzMin CDCI3) of compound (8) 66 25 MHz decoupled and multiplicity determination C 13 spectra for compound (8) 67 Carbon-13 (25 MHz) spectrum of the pyrolysis of l-bromo-2, 2-dime thoxy propane 74 vii

PAGE 8

14 Proton spectrum (60 MHz) in CDC1 3 (15) 75 15 Noise and off-resonance decoupled C 13 spectra in CDCI3 (15) 76 16 Proton (100 MHz) NMR spectrum (in 00013) and carbon-13 (25 MHz) NMR spectrum (in 00013) of compound (17) 81 17 25 MHz decoupled and multiplicity determination sequence C 13 spectra (21) 86 18 Analysis for explanation of observed shifts 92 19 Synthesis scheme used for 2,4,6-trimethoxystyrene 93 20 UV of compound (15) (cone = 10 -5 M) in t-butyl alcohol at different temperatures 99 21 GPC curves for polymers (in DMF) formed at different temperatures 101 22 Proton NMR for polymers (in CDClo) formed at 40° C and 60° C 102 23 Carbon-13 NMR spectra for polymers formed at 40° C and 60° C 103 24 GPC curves for polymers (in DMF) formed at R.T. and 40° C 105 25 Frontier orbital energies and coefficients of ethylene and monosubsti tuted ethylenes 109 26 Representation of the systems studied Ill 27 Z-axis view of ZINDO geometry optimized molecules 121 28 Z-axis view of ZINDO geometry optimized molecules 131 29 Plot of AE compl = E c (Ej + E 2 ) vs. distance 134 30 Plot of A E compl * = E c *(r) E c *(°°) vs. distance 136

PAGE 9

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 CHARGE TRANSFER IN CYCLOPOLYMERIZATION AND THEORETICAL CALCULATIONS FOR CHARGE TRANSFER IN COPOLYMERIZATION BY ROY JOSEPH NOEL VAZ August, 1985 Chairman: Dr. George B. Butler Major Department: Chemistry Continuing studies on the mechanism of cyclopolymerization lead to the inclusion of charge transfer complexes in the monomer in order to influence the ring size. It was anticipated that if a donor and acceptor group were substituted at the C 2 and C 2 * positions, respectively, of an ally! ether, an intramolecular complex would be formed. Monomers selected for the study were 2-chloroal lyl V -phenylallyl ether, 2-carboethoxyallyl 2‘ -phenylallyl ether, 2-cyanoallyl 2‘phenylallyl ether and 2-carboethoxyallyl 2' -methoxyal lyl ether. Intramolecular charge transfer complexation was proved by omitting the point of unsaturation having the donor group. For this study 2carboethoxyallyl 2 1 -phenylpropyl ether, 2-cyanoallyl 2 '-phenyl propyl ether and 2-carboethoxyallyl 2' -methoxypropyl ether were synthesized

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and the carbon-13 and proton NMR spectra were compared with those of the corresponding monomers in order to determine "charge transfer." The monomers were polymerized with 2,2' -azobisisobutyroni tri le in benzene and only 2-carboethoxyallyl 2 1 -phenylallyl ether gave a linear cyclopolymer soluble in most organic solvents. 2-Chloroallyl 2'phenylallyl ether did not afford any polymer and 2-cyanoallyl 2‘phenylallyl ether and 2-carboethoxyallyl 2‘ -methoxyallyl ether afforded branched polymer when the percentage conversion and percent monomer concentration were kept low. This was determined via gel permeation chromatography. The polymer of 2-carboethoxyallyl 2'-phenyallyl ether consisted largely of five-membered rings at 40° C and six-membered rings at 60° C. This ring distribution supports intramolecular "charge transfer" complexation at lower temperatures and the normal cyclopolymerization dominating at higher temperatures corresponding to the charge transfer complex breaking up. Theoretical calculations such as geometry optimizations were carried out on N-methylmaleimide and methyl vinyl ether and possible complexes involving them in order to support charge transfer between these two molecules. x

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CHAPTER I INTRODUCTION Cyclopolymerization History Early in the history of Polymer Science, a general principle was established by Standinger 1 that polymerization of noncon jugated dienes leads to crosslinked and therefore non-soluble, nonlinear polymers or copolymers. An exception to this widely accepted principle was observed by Butler, 2 who found that a variety of dial 1 y 1 quarternary ammonium salts polymerized to yield soluble, and hence linear polymers containing little or no residual unsaturation. To account for these, Butler and Angelo^ suggested a polymerization mechanism that involves an alternating intermoleculat — intramolecular chain propagation. The six-membered structure proposed for radical initiated cyclopolymerization of 1,6 dienes was based upon the generally accepted hypothesis advanced by Flory^ regarding the predominance of the more stable radical in controlling the course of vinyl polymerization. Intervening studies have shown that in numerous cases cyclopolymerizations do not adhere to this hypothesis but lead to cyclic structures derived via propagation through the less stable intermediate, i.e., reactions proceeded via kinetic rather than thermodynamic control (Scheme 1). 1

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2 Scheme 1: Butler scheme for cyclopolymerization.

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3 It has been shown that suitable monomers undergo cyclopolymerization via all of the well known methods of initiation O of polymerization. A type of copolymerization constitutes a significant portion of the cyclopolymerization literature. 2 This process, referred to as cyclocopolymerization, incorporates both comonomers into the developing cyclic structure. The most extensively studied example of this unusual type of copolymerization is the cyclocopolymer of divinylether and maleic anhydride. This copolymer has been extensively studied for its biological properties. 6 Monomers having two different functional groups have been studied in cyclopolymerization. ^ Cyclopolymerization of diene monomers leading to larger (> 7 ) rings has also been studied. 2 Mechanism of Radical Cyclopolymerization Important aspects of the process are embodied in a kinetic study carried out on methacrylic anhydride. 6 This study showed that the intramolecular cyclization step is higher in energy by 2.6 kcal/mole than the intermolecular step. The rate of cyclization, however, was found to be considerably faster than the intermolecular propagation step in support of a very high steric factor favoring cyclization. Bimolecular reactions involve substantial loss of translational entropy whereas intramolecular reactions only involve the loss of internal rotational degrees of freedom and are therefore favored. The thermochemical approach to the explanation of ring sizes failed.

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4 Less favored ring sizes may be formed in cyclopolymerization and the less stable radical may predominate in the cyclization. The model hex-5-enyl radical (I) (Scheme 2) has been studied extensively and various propositions 7 with regard to the formation of the less stable radical (IV) being formed faster have come under consideration. Notably they could be listed as: (1) entropy of activation®’ 9 ’ 1 ® (2) unfavorable non-bonded interaction 11 (3) stereo electronic factors (1) The entropy change associated with the loss of rotational freedom in intramolecular reactions becomes unfavorable with increasing size of the ring being formed. The magnitude of this difference (~ 3.4 cal mol -1 °K) at ordinary temperatures is far too small to account for the degree of regioselectivi ty exhibited by the ring closure reaction and hence is not a dominant factor though it could not be ruled out. The favorable enthalpy of activation (~ 1.7 kcal/mole) is also not a dominant factor. (2) The Julia-LeBel hypothesis. An unfavorable non-bonded interaction between the pseudo-axial proton at C 2 and the syn proton at Cg will destablize the transition state (VIII) for 1,6 ring closure by comparison with (IX) for fi ve-membered ring formation. The magnitude of the interaction (< 0.8 kcal mol -1 ) is not sufficient to account for the high preference for 1,5 ring closure besides alkenyl radicals (X) having no pseudo-axial proton at undergo • • • 1 ? regiospecific formation of a fi ve-membered ring.

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5 Scheme 2: Reactions of the hex-5-enyl radical (I).

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6 (3) The stereo electronic theory contends that the strain engendered in accommodating the mandatory disposition of reactive centers within the transition complex for 1,5 ring closure outweighs those steric and thermochemical factors expected to favor the formation of the more stable possible product. It involves the structure (XI) where the dominant interaction for attack of an alkyl radical on an olefinic bond involves overlap of the semi-occupied 2p orbital with one lobe of the vacant tt* orbital. 13,14 A structural feature which affects the ability of an unsaturated radical to accommodate the intimate transition complex for addition will necessarily affect also the rate and regroselectivity of ring closure, e.g., shorter bonds (C-O.C-N ) favors 1,5 ring closure. XI Substituents at Cg(XII) do not enhance 1,6 ring closure but rather retard 1,5 ring closure, 15 suggesting that the formation of the transition complex involves considerable configurational change at C 5 , and that it is this change toward sp 3 hybridization which is effected by substituents (through B strain). However, when the substituent at is capable of interacting strongly with an adjacent radical center, it may increase the rate of 1,6 ring closure;

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7 nevertheless, it will still retard the rate of 1,5 ring closure. Thus the phenyl substituted radical (XIII) undergoes 1,6 ring closure more rapidly than the parent, but 1,5 ring closure occurs more slowly 10 (Fig. 1). Substituents at expected to exert a strong conjugative effect on the adjacent radical center often afford mainly products of 1,6 ring closure. Such results 17 are not incompatible with the concept of stereo electronic control since 1,5 ring closure is the kinetically controlled process, but being truly reversible, 1 ® it is often superceded by slow but essentially irreversible 1,6 ring closure. Also the transition complexes for these weakly exothermic reactions may lie towards the product end of the ring closure reaction coordinate making stereo-electronic effects less important unlike normally, when ring closure proceeds through a very early transition state in which there is little change of configuration at Cj or Cg and little transfer of spin density. 11 Charge-Transfer It was Mul liken 18 who first proposed a theory to account for bonding in complexes (donor-acceptor ) which do not conform to the Lewis acid-Lewis base description. Mulliken 19 proposed that chargetransfer complexes arise from interaction between donor molecules and acceptor molecules having high-energy filled orbitals (i.e., low ionization potentials, Iq) and acceptors having low energy unfilled orbitals (i.e., high electron affinities, E^) viz:

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8 k , a rote constant fer five-membered ring formation; membered ring formation. k 2 * rate constant for sixFig. 1: Reaction coordinates proposed as a result of product distribution study in the cyclization of radicals XII and XIII.

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9 D + A 5=^ [AD ++ AV] . [A“D + «+ AD] ground state excited state Of) Dewar and Thompson^ suggested that other aspects of these intermolecular combinations, notably the enthalpies of formation, are very similar to those expected on the basis of Van der Waals forces including dipole-dipole, dipole-induced-dipole and dispersion forces. Also, the only requirement that a charge-transfer transition occur is that the species involved be close together. A transition could occur equally well if the components were held together by simple Van der Waals forces, and there is ample evidence for socalled charge-transfer spectra. Kosower^ reviewed the possibilities for involvement of charge transfer complexes in organic reactions as exemplified by the following scheme: D + A D,A complex -hv or radiationless hv or A I products D + ,A“— D + + A" (triplet) + D*,A or D,A* covalent adduct D + ,A (triplet) products The spontaneous thermal reactions of electron rich olefins with electron poor olefins gives a wide diversity of organic and polymer molecules as shown in the scheme below. ^

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10 D = donor: OR, NR2, Aryl, etc. A = acceptor: CN, COOCH3, etc. These spontaneous reactions have been attributed to initiation by charge-transfer complexes or by ion-radicals arising by electron transfer from donor olefin to acceptor olefin. 23 This has been shown not to be true. 24 They may be on the reaction path but not in the initiation step. Butler and Olson 23 studied the role of the charge-transfer complex in the propagation step of the copolymerization N-(alkyl) maleimide with vinyl ethers. o/r Seymour et al. have shown the existence of a charge transfer complex between acryloni tri le complexed to a Lewis acid (ZnCl 2 ) and styrene. The Lewis acid enhances charge transfer. The details are shown in Figure 2.

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11 > ZnCl 2 N benzene protons 7-l8— *7.23 ppm acrylonitrile protons 5.9 — * 5-6 ppm Fig. 2: Evidence for charge transfer between acrylonitrile and styrene in the presence of ZnCl 2 .

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12 The stereochemistry of the complex in the presence of strong or multiple donors and acceptor substituents has been visualized 23 * 24 such that it could lead to a tetra methylene zwitterion with one end of zwitterion carbon having the donor and the positive charge and the other end having the acceptor and the negative charge. This would lead to the isolation of l-donor-2-acceptor cyclobutane molecules. This zwitterion is proposed 24 to be the live intermediate which leads to small molecules and initiates polymerization. Frontier molecular orbital theory 27 has been invoked to explain the reactivity and consequent stereochemistry of the products in copolymerization of alkenes substituted with an electron donor and an electron acceptor. It has also been used to explain the ring-size in cyclopolymerization since thermodynamic stability is determined by the energies of all the filled orbitals, but kinetic stability is mostly determined by the highest occupied molecular orbital. Proposed Research A combination of sections A and B would lead one to propose cyclopolymerization of molecules having intramolecular charge transfer between alkene groups substituted with a donor and an acceptor group and polymerization of the intramolecular complex leading to the intramolecular zwitterion as shown in the following scheme:

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13 If the donor was phenyl, and there was no charge transfer interaction one would expect six-membered ring formation to predominate since the rate of five-membered ring formation was relatively inhibited and the six-membered ring formation favored as explained earlier. 16 The initiation due to the "tetr a methylene zwitterion" would complicate 24 matters. However, the single donor and acceptor groups used here would be relatively weak such that the equilibrium forming the zwitterion would lie largely to the left. A radical initiator would favor five-membered ring formation via almost concerted addition, as shown in the scheme above. This is based upon a similar mechanism proposed by Butler and 01 son.

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CHAPTER II EXPERIMENTAL General Information All temperatures are uncorrected and are reported in degrees centigrade; melting points (m.p.) were determined in open capillary tubes using a Thomas-Hoover melting point apparatus. Pressures are expressed as millimeters (mm) of mercury. Elemental analyses were performed by Atlantic Microlabs, Inc., Atlanta, Georgia. Number average molecular weights (Mn) of polymers were determined by vapor pressure osmometry (VPO) on a Wescan Model 230 Recording Vapor Pressure Osmometer Apparatus. All preparative separations were performed with an Altex Model 332 programmable gradient system fitted with a constant wavelength ultraviolet (UV) detector (254 nanometer (nm)). A Lobar B 24 inch column (E. Merck) with 40-63 u LiChroprep Si60 Silica gel was used. The solvent used was hexane with rinsing of the column done with 4:1 to 3:1 methylene chloride:methanol . Infrared spectra (IR) were recorded on a Perkin-Elmer 281 infrared spectrophotometer. Spectra of liquids were obtained neat as a smear on sodium chloride plates, and those of solids were obtained as KBr pellets. Vibrational transition frequencies are reported in wavenumbers (cm h using the 1601 cm' 1 line of a polystyrene film as a standard. The intensity of the bands were assigned the following 14

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classifications: weak (w), medium (m), shoulder (sh), strong (s), broad (br). 15 • Proton nuclear magnetic resonance (NMR) spectra (60 MHz) were recorded on a Varian EM-360L spectrometer. Carbon-13 (C 13) (25.0 MHz) and 100 MHz proton NMR spectra were obtained on a JEOL JNM-FX-100 instrument. Chemical shifts are given in parts per million (ppm) on a 6-scale downfield from tetramethyl silane (TMS ) or solvent peaks as internal references (int ref ) (chloroform-d (CDC1 3 ) 13 C = 77.0; benzene-d 6 (-d 6 ) 13 C = 123.0 dimethyl sulfoxide-d 6 (DMS0-d 6 ) 13 C = 39. 5). 28 Multiplicities of proton and off-resonance decoupled carbon-13 resonances are designated as singlet (s), doublet (d), triplet (t), quartet (q), pentet (p), multiplet (m) or broad (br). Ultraviolet spectra were measured with a Perkin-Elmer 330 spectrophotometer. Analytical gas chromatography was done on a open-column capillary HP 5880A series gas chromatograph. Gel permeation chromatography (GPC) was done on a Waters M 6000A high pressure liquid chromatograph pump with polystyrenedivinyl benzene (TSK gel) columns (i.e., the TSK gel G3000H and G4000H coupled with a guard column attached initially) made by T0Y0 SODA. Reagents and Solvents Reagents were obtained from Aldrich Chemical Co., Eastman Kodak Co., risher Scientific Co. or Mallinkrodt Inc. unless otherwise noted. Oeuterated NMR solvents were obtained from Merck and Co. and

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16 Aldrich Chemical Co. All gaseous reagents were obtained from Matheson Co. Nickel carbonyl was obtained from Strem Chemicals. All solvents used for general application were of reagent grade or ACS grade quality. For special purposes, purification of solvents was carried out by following procedures reported in the 1 i terature. 29 Thus, dimethyl sulfoxide was allowed to stand over barium oxide overnight and was distilled over the barium oxide under reduced pressure; benzene was purified by washing with H 2 S0 4 (100 mLs/liter) until darkening was slight. 2-Phenylallyl alcohol was obtained in the pure form by precipitating any polymer formed on the reagent's standing, and distilling the alcohol at 95°-97° C/1.5 mm. The literature reported boiling point was (lit b . p . ) 30 116°-118° C/ll mm. 2,2 ' -Azobi si sobutyroni tri le was recrystal 1 ized twice from methanol . Synthesis of Monomers 2-Chloroallyl 2 1 -Phenylallyl Ether (1) The procedure followed for the synthesis of such compounds by Baucom was generally used. To a flame dried, three necked, 100 mL, round bottomed flask fitted with a dropping funnel through which a constant flow of nitrogen was maintained, was added 1.80 g of 60% sodium hydride (1.08 g, 0.045 mole) in a mineral oil dispersion. The mineral oil was removed by washing with n-pentane (3x10 mLs). The pentane was added, the mixture stirred with a magnetic stirrer and then allowed to stand. The NaH separated out and the pentane and mineral oil drawn off with a disposable pipette. After three

PAGE 27

17 repetitions 20 mLs of dry dimethyl sul foxide (DMSO) was added. 2Phenylallyl alcohol (5.65 g, 0.042 mole) in 10 mLs of DMSO was added through the dropping funnel slowly. Stirring was continued for four hours (hrs) at room temperature (R.T.). This was then transferred to the dropping funnel and 10 mLs of DMSO and 2-chloroallyl chloride (4.66 g, 0.042 mole) was added to the flask. The alkoxide in the dropping funnel was then added slowly with stirring so that the temperature did not rise appreciably. Stirring was continued for twelve hours. Then water (10 mLs) was added to destroy the excess sodium hydride and the ether was extracted with pentane (3x75 mLs). The pentane extracts were combined and dried over magnesium sulfate. The ether was recovered after the pentane was drawn off on a rotary evaporator and purified by preparative high pressure liquid chroma tography. One and four-tenth grams (16% yield) of the ether ( 1 ) was obtained. Gas chromatography showed it to be 97% pure. l H NMR (CDCI 3 -TMS) <5: 4.072 (q,2H), 4.406 (m,2H), 5.353 (q,2H), 5.442 (m,lH), 5.550 (m,lH), 7.262-7.438 (br,m,5H). Note: The coupling constants in all of the above multiplets were < 1 Hz. 13 C NMR (CDC1 3 -TMS, int ref CDC1 3 ) 5: 143.62, 138.41, 138.02, 128.32, 127.78, 125.98, 114.72, 113.36, 72.08. IR (NaCl): 3080 (m), 3060 (m), 3030 (m), 2860 (s), 1635 (s), 1600 (w), 1570 (w), 1490 (s), 1440 (s,br), 1380 (m), 1365 (m), 1315 ( sh,w) , 1265 (m), 1245 (m), 1175 (s), 1120 (s), 1080 (s,br),1035 (s), 960 (m), 900 (s), 780 (s), 700 (s), 635 (s).

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18 Elemental analysis: found (calculated) % C 68.72 (69.01), % H 6.29 (6.05), % Cl 17.03 (16.72). Ethyl a-(Bromomethyl ) Acrylate (2) The method of K. Ramarajan et al. 32 was followed. In a nitrogen flushed, three necked, 100 mL, round bottomed flask equipped with a magnetic stirrer. Dean-Stark trap and condenser were placed a( bromomethy 1 ) acrylic acid (10 g, 0.0595 mole) and thiophene free benzene (75 mLs). Approximately 10 mLs of a binary azeotrope of benzene and water was distilled. The Dean-Stark trap was removed and absolute ethanol (purified by boiling commercial absolute alcohol over magnesium turnings for 4 hrs in a nitrogen atmosphere) (25 mLs) and concentrated sulfuric acid (0.2 mLs) were added slowly. The contents of the flask were boiled in a nitrogen atmosphere for 36 hrs, the condensate being passed through 24 g of molecular sieves (Linde 3A) before being returned to the flask. About 30 mLs of a mixture of benzene and ethanol were removed from the reaction mixture by distillation (at 67° C). Then benzene (25 mLs) was added and another 30 mLs of benzene-ethanol mixture distilled (65-75° C). The residue was poured into water (50 mLs) and neutralized with solid sodium bicarbonate (ca. 4.8 g) until C0 2 evolution ceased. The resulting solution was extracted with three 25 mL portions of ether and the combined extracts dried over anhydrous sodium sulfate for 3 hrs. The ether was removed under reduced pressure on a rotary evaporator and the crude-ester distilled to give a fraction at 39-40° C (0.9 mm) weighing 8.2 g ( 72 % yield), lit b.p. 32 39-40°C (0.9 mm)

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19 NMR (CDC1 3 -TMS) 5: 1.26-1.40 (t,3H), 4.16-4.38 (q,2H), 4.19 (s,2H), 5.96 (s,lH), 6.32 (s,lH). 13 C NMR (CDC1 3 -TMS, int ref C0C1 3 ) 6: 13.99, 61.11, 68.41, 125.01, 137.58, 165.75. IR (NaCl ) : 2980 (s), 2930 (m), 2870 (m) , 1725 (s), 1635 (m), 1445 (m,br), 1380 (m.br), 1310 (m), 1330 (tn), 1270 (m), 1225 (m) , 1185 (s), 1105 (s), 1025 (m), 950 (s), 900 (w), 875 (w), 855 (w), 810 (tn), 720 (m), 680 (m). 2-Phenylal lyl 2'-Carboethoxyallyl Ether (3) The procedure followed by Baucom 31 was used. To a flame dried, three necked, 100 mL, round bottomed flask, fitted with a dropping funnel through which a constant flow of nitrogen was maintained, was added 0.642 g of 60% NaH (0.385 g, 0.0161 mole) in a mineral oil dispersion. The mineral oil was removed by washing with n-pentane (3x10 mLs). The pentane was added, the mixture stirred with a magnetic stirrer and then allowed to stand. The NaH separated out and the pentane-mineral oil mixture drawn off with a disposable pipette. After three repetitions, 20 mLs of dry 0MS0 was added. 2Phenylal lyl alcohol (2.152 g, 0.0161 mole) in 10 mLs DMS0 was added through the dropping funnel slowly. Stirring was continued for four hours at room temperature. The contents of the flask were then transferred to the dropping funnel and 10 mLs of dry DMS0 containing 2-carboethoxyallyl bromide (3.104 g, 0.0161 mole) was added to the flask. The alkoxide (dark purple in color) in the dropping funnel was then added slowly with stirring so that the temperature did not rise appreciably. Stirring was then continued for 12 hrs. Then

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20 water (10 mLs) was added to destroy the excess sodium hydride and the ether was extracted with pentane (3x75 mLs). The pentane fractions were then combined and dried over magnesium sulfate. The ether was recovered after the pentane had been removed under reduced pressure on a rotary evaporator. It was purified by preparative high pressure liquid chromatography. Ether (3) (0.80 g, 20% yield) was obtained. l H NMR (CDCI 3 -TMS) 6 : 1.217-1.360 (t,3H,J=7.2 Hertz (Hz)), 4.176-4.272 (q,2H,J=6.47 Hz), 4.249 (s,2H), 4.433 (t,2H,J
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21 chi oroace tone had been added, the temperature was cooled to about 25° C and 200 ml_s of ethyl ether was added. Then a solution of sodium cyanide (29.4 g, 0.6 mole) in water (80 mLs) was added dropwise at 25-30° C with vigorous mechanical stirring. When all the cyanide solution had been added, the ether layer was separated immediately and the aqueous layer extracted with ethyl ether (2x100 mLs). The combined ether solutions were dried over magnesium sulfate. The crude cyanohydrin was recovered after the ether had been removed under reduced pressure on a rotary evaporator. Cyanohydrin (44.5 g, 74.2% yield) (4) was recovered by distillation b.p. 73-75° C/1.5 mm (lit b.p. 33 73-74° C/1.5 mm). X H NMR (CDC1 3 -TMS) 6: 1.708 (s,3H), 3.681 (s,2H), 4.309 (s,lH). 13 C NMR (CDC1 3 -TMS, int ref CDC1 3 ) 5: 24.80, 50.05, 68.72, 119.50. IR (NaCl ) : 3400 (s,br), 3000 (m), 2970 (m), 2945 (m), 2250 (m), 1450 (s), 1430 (s), 1380 (s.br), 1280 (m), 1245 (s), 1150 (s,br), 1080 (s), 960 (s), 870 (s), 770 (s), 730 (w), 695 (m), 685 (m). Chloroacetone Cyanohydrin Acetate (5) The procedure followed by Ferris and Marks 33 was used. To a three necked, 250 mL, round bottomed flask fitted with a thermometer, a dropping funnel and a drying tube was added chloroacetone cyanohydrin (4) (44.5 g, 0.372 mole) and 1 mL of concentrated sulfuric acid. To this was added dropwise at 60-70° C with vigorous stirring, acetic anhydride (41 g, 0.40 mole) through the dropping funnel. When all the anhydride had been added, the mixture was stirred for 30 minutes (mins) and then poured into ice water (600

PAGE 32

22 mLs). The resulting mixture was neutralized with solid sodium bicarbonate and extracted with ethyl ether (3x100 mLs). The combined extracts were then dried over magnesium sulfate and the ether finally removed under reduced pressure on a rotary evaporator. Chloroacetone cyanohydrin acetate (5) (32.4 g, 54% yield) was obtained after distillation at 57-59° C/0.3 mm (lit b.p . 33 57-59° C/0.3 mm). l H NMR (CDC1 3 -TMS) 6 : 1.85 (s,3H0, 2.15 (s,3H), 3.90 (s,2H). 13 C NMR (CDCI 3 -TMS, int ref C0C1 3 ) <5: 20.61, 22.76, 46.83, 70.62, 116.38, 168.38. a-(Chloromethyl )acry!oni trile ( 6 ) This was obtained by the method used by Ferris and Marks . 33 The apparatus used is shown in Figure 3. The tube at 250° C was primarily to vaporize the chloroacetone cyanohydrin acetate. Chloroacetone cyanohydrin acetate (120 g, 0.743 mole) was dropped at the rate of 1 drop/5 seconds. The condenser was used in case the columns did get blocked up. The product, a brown oil, was poured into water (500 mL) and was neutralized with solid sodium bicarbonate. This was then extracted with ethyl ether (3x200 mLs), the combined portions dried over magnesium sulfate and the ether taken off under reduced pressure on a rotary evaporator. The residue was then fractionally distilled with a Yigreux condenser and the fraction at 75-85°/40 mm collected. This portion (35 g) consisted of 60% ct-(chloromethyl ) acryloni tri le ( 6 ) and 40% of cisand trans6 chloro-a-methacryloni trile (7). The percentages were obtained from the integration in the proton NMR (Fig. 4).

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23 N 2 gas in H 2 0 out E^O $> / I pyrex glass beads o o o heating coils at 250°C o s o I porcelain burro saddles quartz tube y // Hoskins Electric Furnace FD303A at 500°C N 2 gas out passed through traps in dry ice/ isopropanol and liq. N collecting flask immersed in dry ice/ isopropanol Fig. 3: Apparatus for the pyrolysis of chloroacetone cyanohydrin acetate.

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24 CO Fig. 4: Proton spectrum of the pyrolysis products with the integration (in CDCL

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25 • O O Lit b.p . 00 of cis-g-chloroa -methacrylonitrile 57.5-58720 mm, trans-g-chloro-d-methacryloni trile 47-48740 mm, a -(chloromethyl ) acrylonitrile 61.5-62.5718 mm. * H NMR (CDCI 3 -TMS) 5 ( 6 ): 4.160 (m,2H,J
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26 DMSO (10 mLs) so that the temperature did not rise appreciably. Stirring was continued for 12 hrs. Water (10 mLs) was then added and the ether was extracted with pentane (3x75 mLs). The pentane extracts were combined and dried over magnesium sulfate. The pentane was removed under reduced pressure on a rotary evaporator. The ether was purified by preparative high pressure liquid chromatography (Fig. 5). Compound (8) (0.94 g, 24% yield) was recovered. NMR (benzene d 6 -TMS) <5; 3.492 (t,2H), 3.988 (m,2H), 5.150 (q.lH), 5.243 (m,2H), 5.370 (m,lH), 7.036-7.367 (m,5H). Note: The coupling constants in all of the above multiplets are < 1 Hz. 13 C NMR (CDC1 3 -TMS, int ref CDC1 3 ) 5: 143.33, 138.21, 131.34, 128.42, 127.98, 126.03, 120.33, 117.02, 115.11, 72.61, 69.96. IR (NaCl ) : 3080 (m), 3060 (w), 2925 (m), 2860 (m), 2230 (m), 1750 (w,br), 1630 (m), 1610 (w), 1575 (w), 1495 (m), 1445 (m), 1410 (m), 1305 (w), 1120 (s), 1090 (s), 1025 (m), 950 (s), 915 (s), 850 (w), 780 (s), 710 (s). Chemical analysis: found (calculated): % C 77.92 (78.35), % H 6.46 (6.58), % N 6.73 (7.03). Bromoacetone (9) The procedure used here was one followed by Levene. 34 A three necked, 2L, round bottomed flask was fitted with a mechanical stirrer, a reflux condenser and a dropping funnel. To this was added water (800 mLs), acetone (250 mLs) and glacial acetic acid (186 mLs). With stirring, the mixture was heated to about 65° C on an oil bath. Through the dropping funnel, bromine (177 mis, 3.65 mole) was

PAGE 37

2-phenylallyl 2 Â’ -cyanoallyl ether flow rate 5 mL/min of hexane. time 55 mins. -+ 0 Fig. 5: HPLC chromatograph. Separation of 2-phenylallyl 2'cyanoallyl ether.

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28 added dropwise, the dropping being regulated by the disappearance of color from the preceding drop. After addition was complete, it was diluted with cold water (400 mLs) cooled in an ice-water mixture and neutralized with solid sodium carbonate (~ 500 g). The oil which separated out was collected and the aqueous layer extracted with ethyl ether (2x400 mLs). The extracts together with the oil was dried over sodium sulfate. The ether was removed by distillation (since bromoacetone is a bad lachrymator, care should be taken accordingly) and not on a rotary evaporator. The residue containing compound (cpd)(9) as well as 1,1-di bromoacetone was distilled and bromoacetone (200 g, 402 yield) was recovered at 86-87760 mm. lit b.p . 34 40-42713 mm X H NMR (CDCI 3 -TMS) : 3.90 (s,2H), 2.40 (s,3H). 13 C NMR (CDC1 3 -TMS, int ref CDC1 3 ): 26.98, 34.82, 199.68. l-Bromo-2,2-dimethoxy Propane ( 10 ) The procedure of Jacobson et al . 35 was used for this synthesis. To a 250 mL, round bottomed flask fitted with a drying tube was added 95 mLs of 952 bromoacetone (< 0.5 mole) (52 of 1,1di bromoacetone), trimethyl orthoformate (60 mLs, 0.55 mole), methanol (25 mLs) and concentrated sulfuric acid (10 drops). After stirring for 2 hrs, the mixture was basified with triethylamine (2 mLs) and then attached to a water pump to remove most of the unreacted methyl formate. The resulting reaction mixture was added to an ice cold solution of sodium hydroxide (20 g) in methanol (200 mLs) destroying the unketalized 1,1-dibromoacetone. This mixture was then partitioned between pentane (300 mLs) and water (200 mLs). The

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29 aqueous layer was extracted with pentane (2x50 mLs) and the three pentane layers combined, washed with water (50 mLs) and dried over potassium carbonate. Removal of the pentane by distillation at atmospheric pressure and distillation under vacuo of residue gave 75 g (0.41 mole > 80% yield) of l-bromo-2,2-dimethoxypropane boiling at 83° C/80 mm. lit b.p. 35 156° C/760 mm. X H NMR (CDC1 3 -TMS) 6: 1.45 (s,3H), 3.20 (s,6H), 3.35 (s,2H). 13 C NMR (CDC1 3 -TMS, int ref CDC1 3 ) 6: 20.81, 34.55, 48.69, 99.76. IR (NaCl): 2950 (s,br), 2840 (m), 1460 (m), 1425 (m), 1380 (m), 1270 (m), 1250 (m), 1215 (m), 1170 (m), 1165 (m), 1110 (s), 1075 (s), 1045 (s), 925 (w), 880 (m), 830 (m), 745 (m), 675 (m). Diisopropylethylammonium p-toluenesulfate (11) The procedure of Jacobson et al. 35 was followed. To a 100 mL round bottomed flask was added p-toluenesulfonic acid monohydrate (3.80 g, 0.02 mole) in anhydrous methanol (10 mLs). To this was added diisopropylethylamine (2.80 g, 0.022 mole). The resulting solution was concentrated in vacuo, yielding an oil which crystallized on standing. The solid was crushed and the last traces of solvent removed by subjecting it to vacuo (0.01 mm). Five and five-tenth grams (92% yield) of (11) was obtained of m.p. 85-86° C (lit. m.p. 35 87-88.5° C) X H NMR ( CDC1 3 -TMS ) : 1.37 (m,15H), 2.35 (s,3H), 2. 8-3. 3 (m,2H), 3. 3-3. 9 (m,2H), 7.17 (d,2H), 7.82 (d,2H), 9.18 (br.S.lH). 13 C NMR (CDC1 3 -TMS, int ref CDC1 3 ) : 12.09, 16.86, 18.23, 20.96, 42.40, 53.97, 125.59, 128.27, 139.19, 143.04.

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3-Bromo-3-methoxypropane (12) Method A . The method followed by Hoffman and Greenwood^ was 30 used initially but this method proved laborious. A three necked, 500 mL, round bottomed flask was fitted with a thermometer, a mechanical stirrer and a dropping funnel and to it was added N-bromosuccinimide (50 g, 0.281 mole) in carbon tetrachloride (150 mLs). The flask was heated in an oil bath so that the temperature of the mixture was about 55° C. Heating was stopped and 2-methoxypropane (20 mLs) was added. The 2-methoxypropane was initially dried over CaCl 2 and distilled. The addition, with vigorous stirring, was done so that the temperature inside the flask was maintained. After addition was complete, the reaction mixture was cooled to ca. 10° C by immersion in an ice-water mixture. The suspension was filtered to remove the precipitated succinimide and concentrated at the water pump for 15 mins by immersion of the flask in warm water. This removed unreacted 2-methoxypropene, methanol, methyl acetate and some CC1 4 . The remaining solution was washed with potassium hydroxide (2x300 mLs of IN) and then ice cold water (2x100 mLs). Base destroys l-bromo-2methoxy-2-succinimidopropane and bromoacetone. Alkaline conditions also discourages the hydrolysis of any bromoketal to bromoacetone and methanol and suppresses the addition of water to enol ethers. Washing with water neutralizes the solution. The organic layer was dried over CaCl 2 and stirred over Na^O^. The solution so prepared contains mainly CC1 4 (50%), 2-methoxyally bromide (30-35%) and 1bromo-2-methoxypropene (13) (~ 14%). The percentages were determined by analytical gas chromatography . The carbon tetrachloride was

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31 removed by distillation leaving a yellow residue containing about 55 % 2 -methoxypropene and 28% l-bromo2 -methoxypropene with an unidentifiable residue. Method B . The procedure here was that followed by Jacobson et al. This method provided a more stoichiometrically clean product with minimal exposure of the unstable 2 -methoxyallyl bromide to room temperature and light. A distillation apparatus with a 100 mL, round bottomed flask containing l-bromo-2,2-dimethoxypropene (50 g, 0.2732 mole) and di isopropylethylammoni urn p-toluene sulfonate (1 g) was fitted with a 12 inch, 15 mm diameter vigreux column with heating coils and a short-path distillation assembly. The flask was heated at 150-190° C in an oil bath while distilling of the methanol at the rate of 1 drop/2 seconds. This rate is used so as to keep the complete time of reaction to less than an hour and a half. Complete removal of the methanol was shown by a rise in the head temperature to > 75° C. The fraction collected between temperatures of 85-130° C had the highest percentage (67%) of 2-methoxyallyl bromide. The total fraction (> 85° C) had the following percentages as calculated from the investigation of the proton NMR (Fig. 6 ): % 2-methoxyallyl bromide: 45 % l-bromo-2-methoxy propene (13): 15 % l-bromo-2,2-dimethoxypropane/starting material): 40.5 NMR (CDCI 3 -TMS) 5 (12): 4.3 (d,lH), 4.15 (d,lH), 3.9 (s,2H), 3.65 (s,3H); (13): 5.2 (s.br.lH), 3.55 (s,3H), 1.95 (s,3H).

PAGE 42

OCH 32 Fig. 6: Proton (60 MHz) spectrum in COCK.

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33 13 C NMR (CDCI3-TMS, int ref CDCI3) 6 (12): 31.63, 55.41, 85.29, 159.03; (13): 18.47, 55.02, 77.58, 157.17. IR (NaCI): 3000 (m), 2950 (m), 1725 (s), 1420 (m), 1390 (m), 1360 (s), 1275 (m), 1240 (m), 1215 (sh,m), 1150 (s), 1005 (w), 700 (w), 660 (w,br). 2-Carboethoxyallyl Alcohol (14) The procedure of Rosenthal et al. 37 was used. Caution : Nickel carbonyl used here is very toxic. Appropriate handling measures were taken. A 2L, five necked, round bottomed flask was equipped with a mechanical stirrer, a thermometer, a dropping funnel, a gas inlet which almost touches the bottom, and a dry ice-cooled condenser. In it was placed 95 % ethanol (700 mLs) and the flask was cooled in a dry ice/isopropanol bath. Through the inlet nickel carbonyl was passed with nitrogen as a carrier until the amount of Ni ( CO >4 added (measured by weight difference of the laboratory bottle) was approximately 86 g (0.50 mole). Then was added hydroquinone (10 g) and acetic acid (120 g, 2 mole), and the flask was heated with an oil bath to 55° C with stirring. Through the dropping funnel was added initially 2 g of propargyl alcohol (112 g, 2 mole total) and the color darkened and the internal temperature rose (ca. 2 mins). At this point the heating mantle was removed and the remainder of the propargyl alcohol added dropwise such that the refluxing was under control. The temperature at the end of the addition was 75-80° C. The solution was allowed to stir for 30 mins and then concentrated sulfuric acid (28 mLs, 0.5 mole) was added slowly with stirring via the dropping funnel. Green nickel sulfate hexa hydrate

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34 precipitated. The contents were filtered at a water pump through a bromine trap, into a 2 L, round bottomed flask. Concentrated sulfuric acid (10 mLs) was added and the solution was refluxed for 12 hrs, the condensate being passed through a soxhlet-extractor containing anhydrous magnesium sulfate. The reaction solution was then cooled and sodium hydroxide (106 mLs, 5 N) was added to neutralize the acid. An equal volume of water was added and the solution was extracted with chloroform (4x250 mLs). The combined extracts were dried and the chloroform removed under reduced pressure on a rotary evaporator. The liquid residue was distilled to give cpd (14) (93.6 g, 36 % yield) b.p. 55-57° C/0.7 mm. lit b.p.^ 72.5° C/1.5 mm. l H NMR (CDC1 3 -TMS) 5: 1.3 (t,3H), 2.7 (s,lH), 4.25 (q,2H), 4.3 (s,2H ) , 5.8 (s.br.lH), 6.25 (s.br.lH). 13 C NMR (CDCI3-TMS, int ref CDC1 3 ) 6: 13.89, 60.58, 61.55, 124.81, 139.58, 166.09. IR (NaCl ) : 3440 (s,br), 2980 (s), 2930 (m), 2900 (m), 2870 (w), 1705 (s), 1635 (m), 1445 (m), 1380 (s,br), 1305 (s,br), 1270 (s), 1220 (m), 1170 (s,br), 1095 (m), 1055 (s), 1035 (s,sh), 945 (m), 850 (w), 810 (m). 2-Methoxyal lyl 2'-Carboethoxya11yl Ether (15) The procedure used was similar to the one followed for the synthesis of compound (8). In a flame dried, three necked, 100 mL, round bottomed flask, fitted with a dropping funnel and through which a flow of nitrogen was maintained, was placed 0.8107 g of 60% sodium hydride (0.4864 g, 0.0203 mole) in a mineral oil dispersion. The

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35 mineral oil was removed in the manner described in the synthesis of compound (8). Then dry DMSO (25 mLs) was added. To this was added 2-carboethoxyallyl alcohol (2.634 g, 0.0203 mole) in dry DMSO (10 mLs) very carefully, or else the quick reaction leads to excess foam formation. After a deep red/orange color was observed (2 hours), 5.1 g of 60% 2-methoxyal lyl bromide (3.06 g, 0.0203 mole) in dry DMSO (10 mLs) was added dropwise through the dropping funnel. Stirring was continued at room temperature for 12 hrs, water (10 mLs) was added, and the ether extracted with pentane (3x75 mLs). The combined pentane extracts were dried over sodium sulfate and the pentane removed under reduced pressure on a rotary evaporator. The ether (15) (1.01 g, 24.6% yield) was obtained by fractional distillation and was the fraction distilled at 60° C/0.07 mm. X H NMR (CDCI3-TMS) 6: 1.2 (t,3H), 3.5 (q,2H), 3.55 (s,3H), 4.15 (s,2H), 4.15 (m,2H), 4.55 (s,2H), 5.90 (s.br.lH), 6.24 (s,br,lH). 13 C NMR (CDCI3-TMS, int ref CDC1 3 ) 5: 15.11, 55.02, 64.28, 66.28, 68.57, 83.92, 125.93, 137.29, 158.15, 165.36. IR (NaCl ) : 2960 (m), 2870 (m,sh), 1715 (s), 1665 (m), 1635 (m), 1450 (m), 1380 (m), 1305 (m), 1255 (m), 1220 (m), 1155 (m), 1100 (s), 950 (m), 880 (m), 820 (m), 740 (w), 680 (m). Elemental analysis: not done since monomer was unstable, but elemental analysis of polymer was done.

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36 Synthesis of Model Compounds 2-Carobethoxyallyl 2 ‘-Phenyl propyl Ether (16) The procedure followed here was similar to the one used for the synthesis of compound (15). In a flame-dried, three necked, 100 mL, round bottomed flask fitted with a dropping funnel and through which a flow of nitrogen was kept was placed 0.8187 g of 60% sodium hydride (0.4912 g, 0.02047 mole) in a mineral oil dispersion. The mineral oil was removed in a manner similar to that used for the synthesis of compound (15). Then dry DMS0 (25 mLs) was added and through the dropping funnel 2-phenyl propyl alcohol (2.78 g, 0.02047 moles) in dry DMS0 (10 mLs) was carefully added dropwise. The resulting solution was stirred magnetically at room temperature for 4 hrs. The alkoxide solution was then transferred to the dropping funnel and added to 2carboethoxyallyl bromide (3.95 g, 0.02047 moles) in dry DMS0 (10 mLs) dropwise such that there was no appreciable rise in temperature. The reaction mixture was allowed to stir for 12 hrs. Water (10 mLs) was added to destroy the unreacted sodium hydride and the ether was extracted with pentane (3x75 mLs). The combined pentane extracts were dried over magnesium sulfate and removed under reduced pressure on a rotary evaporator. The ether (16) (2.03, 40% yield) was recovered by preparative high pressure liquid chromatography (Fig. 7) after distillation at 118° C/0.7 mm. NMR (CDCI3-TMS) 6: 0.936 (t,3H,J=7.21 Hz), 1.221 (d,3H), 3.320 (d,2H,J=3.79 Hz), 3.212-3.407 (m,lH), 3.967 (q,2H0, 4.151 ( s,br,2H ) , 5.7291 (q,lH,J
PAGE 47

absorbance 37 5 time 15mins 0 Fig. 7: HPLC chromatograph. Separation of 2-phenyl propyl 2'Carboethoxyallyl ether.

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38 13 C NMR (benzene-d 6 , int ref benzene-d 6 ) 5; 14.11, 18.39, 40.37, 60.41, 69.37, 76.88, 124.54, 127.71, 128.54, 138.38, 144.67, 165.63. IR (NaCl): 3030 (m), 2980 (s), 2940 (m), 2900 (m), 2870 (m), 1720 (s), 1640 (m), 1605 (w), 1495 (m), 1455 (m), 1380 (m), 1305 (s), 1270 (s), 1175 (s), 1105 (s), 1025 (m), 950 (m), 860 (w), 820 (w), 760 (m), 700 (s). Elemental analysis: found (calculated) % C 72.80 (72.58); % H 7.84 (8.06). 2-Phenyl propyl 2 , -Cyanoa11yl Ether (17) The procedure followed was similar to that used for the synthesis of compound (16). In a flame dried, three necked, 100 mL, round bottomed flask fitted with a dropping funnel, and through which a flow of nitrogen was maintained, was placed 1.1034 g of 60% sodium hydride (0.6621 g, 0.02759 moles) in a mineral oil dispersion. The mineral oil was removed in the manner described in the synthesis of compound (16). To this was then added dry DMS0 (25 mLs) and then 2phenylpropyl alcohol (3.752 g, 0.02759 moles) in dry DMS0 (10 mLs) dropwise through the dropping funnel such that excessive foaming was avoided. The reaction mixture was stirred magnetically for 4 hrs and then transferred to the addition funnel. Then 4.67 g of 60% 2cyanoallyl chloride (2.8 g, 0.02759 moles) (other 40% being cis and trans-6-chloro-a-methacrylonitrile) in dry DMS0 (10 mLs) was placed in the flask and the alkoxide added dropwise such that the temperature did not rise appreciably. Stirring was continued for 4 hrs at the end of which the unreacted sodium hydride was destroyed

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39 with water (10 mLs) and the ether (17) extracted with pentane (3x75 mLs). The pentane extracts were combined and dried over magnesium sulfate and the pentane removed under reduced pressure on a rotary evaporator. The ether (17) (2.49 g, 45? yield) was purified by preparative high pressure liquid chromatography. : H NMR (C0C1 3 -TMS) 5: 1.30 (d,3H), 3.10 (p,lH), 3.55 (d,2H), 4.10 (s,2H), 5.90 (s,lH), 6.0 (s,lH), 7.30 (s,5H). 13 C NMR (CDC1 3 -TMS, int ref CDC1 3 ) 6: 18.03, 39.91, 70.23, 76.76, 117.11, 120.47, 126.52, 127.25, 128.37, 131.00, 143.77. IR (NaCl): 3030 (m), 2965 (m), 2930 (m,sh), 2870 (m), 2225 (m), 1640 (w), 1605 (m), 1495 (m), 1450 (s), 1410 (w), 1390 (w), 1375 (w), 1110 (s), 1025 (w), 1015 (w), 950 (m), 660 (m), 700 (s). Chemical analysis: found (calculated): % C 77.22 (77.61); % H 7.21 (7.46) * N 7.12 (6.97). g-Methoxypr op ionic Acid (18) The procedure followed here was that used by Leggetter and Brown^ and Reeve and Saddle^ who followed the method of Fuson and Wojcik 40 for the preparation of ethoxyacetic acid. In a three necked, 1000 mL, round bottomed flask fitted with a condenser and a dropping funnel was placed methanol (300 mLs). Through the condenser was added metallic sodium (0.652 g atoms) cut into bits, such that the solution refluxed gently. Then 2-chloropropionic acid (46.9 g, 0.326 moles) in methanol (40 mLs) was added through the dropping funnel such that the mixture refluxed gently. After the acid was added, the solution was heated for 30 mins so that refluxing

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40 continued. The excess alcohol was then removed by distillation initially and finally by passing steam into the residue. The aqueous solution was cooled and concentrated hydrochloric acid (30.4 mLs) was added. The precipitated sodium chloride was removed by filtration and washed with ethyl ether (2x25 mLs). The original filtrate was saturated with dry sodium sulfate and was then extracted with the ether which was used for washing the precipitate together with additional (2x25 mLs) ether. The combined ether extracts were dried over sodium sulfate and removed by distillation at atmospheric pressure. The acid (18) (26.9 g, 80% yield) was recovered by distillation under reduced pressure 95-96° C/12 mm. lit b.p . 38 108110730 mm L H NMR (CDCI 3 -TMS) 5: 1.50 (d,3H), 3.45 (s,3H), 4.0 (q,lH), 10.85 (s,lH). 13 C NMR (CDCI 3 -TMS, int ref CDCI 3 ) 6 : 17.93, 57.60, 75.83, 178.37. Methyl «-Methoxy propionate (19) The procedure used was that used by Fuson and Wojcik 40 for the synthesis of ethyl ethoxyacetate. In a three necked, 250 mL, round bottomed flask fitted for a gas inlet and an outlet to a sodium hydroxide solution (5N) was placed a-methoxy propionic acid (23 g, 0.2233 moles) and methanol (50 mLs). The solution was stirred with a magnetic stirrer bar and hydrogen chloride gas was passed into the solution via the inlet, which dipped into the solution, for 5 hrs. The flask was cooled with an ice-water mixture since heat is evolved. It was then allowed to stand for 24 hrs to ensure

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41 completion of the reaction at room temperature. The solution was cooled, and a saturated solution of sodium carbonate added slowly to avoid excessive foaming until the mixture was faintly alkaline to litmus. The ester (19) was extracted with ethyl ether (4x100 mLs) and the extracts combined and dried over anhydrous potassium carbonate. The ether was then distilled at atmospheric pressure and the ester (19) (16.2 g, 62% yield) recovered at 140-142° C/760 mm. lit b.p. 39 142° C/760 mm. L H NMR (CDCI3-TMS ) 5: 1.45 (d,3H ) , 3.40 (s,3H), 3.78 (s,3H), 3.85 (m,lH). 13 C NMR (CDC1 3-TMS , int ref CDC1 3 ) 5: 18.32, 51.85, 57.60, 76.32, 173.50. 2-Methoxy Propanol (20) The method employed here was that used by Reeve and Saddle 39 and adapted from the method of Fickett, Garner and Lucas 4 * for the reduction of ot-chloropropionyl chloride and Moffett's 42 method for the reduction of a-(l-pyrrol idyl )propionate. In a three necked, 500 mL, round bottomed flask fitted with a reflux condenser, mechanical stirrer with a mercury seal and dropping funnel was placed lithium aluminum hydride (9.1742 g, 0.2412 moles) and dry ethyl ether (200 mLs). The mixture was refluxed for 3 hrs to effect solution. To this was added methyl a-methoxypropionate (46.75 g, 0.3962 mole) in dry ethyl ether (100 mLs), at first a few drops until a white precipitate appeared and after cooling the solution down to 0° C with an ice-water mixture, the remainder. The addition was completed in 20 mins and stirring was continued for 30 mins. The excess

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42 LiAlH 4 was decomposed by adding methyl acetate (21.5 mLs) slowly with stirring. This was followed by the addition of hydrochloric acid (258 mLs, 6 N ) . The aqueous layer was separated, made strongly alkaline with sodium hydroxide (430 mLs, 6 N) and the alcohol extracted with ethyl ether (2x250 mLs). The original ether layer together with the extracts were combined and dried over anhydrous potassium carbonate. The ethyl ether was removed by distillation at atmospheric pressure and the alcohol (20) (37.4 g, 58% yield) recovered by distillation of the residue at 133-135° C/760 mm. lit b.p . 39 135° C/760 mm. : H NMR (CDC1 3 -TMS) 6 : 1.117 (d,3H), 2.621 (s,lH), 3.388 (s,3H), 3.494 (d,2H) , 3.49 (m,lH). 13 C NMR (CDCI 3 -TMS, int ref CDC1 3 ) 6 : 15.11, 56.24, 65.94, 77.39. IR (NaCl ) : 3400 (m,br), 2970 (m), 2930 (m,br), 2820 (m), 1630 (w,br ) , 1450 (m), 1370 (m), 1350 (m), 1235 (m), 1190 (m), 1140 (s), 1080 (s), 1040 (s.sh), 980 (m), 890 (m), 825 (w), 800 (m). 2-Methoxypropyl 2‘ -Carboethoxyallyl Ether (21) The procedure followed was similar to that followed for the synthesis of compound (17). In a flame dried, three necked, 100 mL, round bottomed flask, fitted with a dropping funnel and through which a flow of nitrogen was maintained, was placed 0.7047 g of 60% sodium hydride (0.4228 g; 0.0176 moles) in a mineral oil dispersion. The mineral oil was removed in a manner described in the procedure for the synthesis of compound (17). Dry DMS0 (25 mLs) was added and stirred with a magnetic stirrer bar. To this was carefully added

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43 dropwise 2-methoxypropanol (1.58 g, 0.0176 moles) in dry DMSO (10 mLs). Stirring was continued for 4 hrs. The alkoxide solution was then transferred to the dropping funnel and in the flask was placed 2-carboethoxyallyl bromide (3.4 g, 0.0176 moles) in dry DMSO (10 mLs). The alkoxide solution was added dropwise such that the temperature did not change appreciably. Stirring was continued for 12 hrs. Water (10 mLs) was added to destroy the unreacted NaH. The ether (21) was then extracted with pentane (3x75 mLs) and the combined extracts dried over magnesium sulfate. The pentane was then removed under reduced pressure on a rotary evaporator and the ether (21) (1.78, 50% ) was recovered by distillation at 55° C/0.06 mm. NMR (CDC1 3 -TMS) 5: 1.159 (d,3H), 1.304 (t,3H), 3.397 (s,3H), 3.478 (d,2H0, 3.353-3.489 (m,lM), 4.234 (s,2H0, 4.226 (q,2H), 5.885 (q, 1H , J<1 Hz), 6.298 (m,lH,J
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44 Miscellaneous Reactions 2-Chloro-2-propeny1 Acetate‘S (22) 2,3-Dichloropropene (16.679 g, 0.1503 moles), sodium acetate (15.428 g, 0.188 mole), glacial acetic acid (8 mLs) and pyridine (0.5 mLs) were put into a tube and sealed. The tube was heated in an oil bath at 140-150° C for 12 hrs. It was then opened after cooling and the contents of the tube extracted with ether (3x100 mLs). The combined extracts of ether were then washed with dil. sulfuric acid (100 mLs, 10%) and then a saturated solution of sodium bicarbonate (100 mLs). The extracts were dried overnight over magnesium sulfate. The ether removed under reduced pressure on a rotary evaporator and the ester (22) distilled at 142-147° C. lit b.p . 43 143-145° C) (11.1 g, 55% yield). X H NMR (CDCI 3 -TMS) 6 : 2.126 (s,3H), 4.651 (s,2H), 5.412 (s,lH), 5.441 (s,lH). 13 C NMR (CDCI 3 -TMS, int ref CDC1 3 ) 6 : 20.52, 65.84, 114.72, 135.83, 169.89. 2-Chloro-2-propenol (23) 43 2-Chloro-2-propenylacetate ( 22 ) (28.4 g, 0.21 moles) and methanol (35.5 mLs) containing 1% HC1 was refluxed in a 100 mL round bottomed flask for twelve hours. The methanol was distilled off. The solution was then poured into water (100 mLs) and sodium bicarbonate (1.1 g) added to neutralize the acid. The alcohol was extracted with ether (3x100 mLs) and the combined ether extracts dried over magnesium sulfate. The ether was removed under reduced

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45 pressure on a rotary evaporator and the alcohol (23) distilled at 135-137° C (lit b.p. 43 130° C) (15.2 g, 78% yield) NMR (CDC1 3 -TMS ) 5: 3.25 (s,lH, exch. with D 2 0), 4.15 (s,2H), 5.35 (s,lH), 5.50 (s,lH). 13 C NMR (CDC1 3 -TMS, int ref CDC1 3 ) 6: 65.5, 111.9, 140.6. 2-Chloroallyl Ether (24) The procedure followed was similar to that followed for the synthesis of compound (21). In a flame dried, three necked, 100 ml, round bottomed flask fitted with a dropping funnel through which a flow of nitrogen was maintained, was placed 0.8107 g of 60% sodium hydride (0.4864 g, 0.02027 moles) in a mineral oil dispersion. The mineral oil was removed in a manner described in the procedure for the synthesis of compound (8). Dry DMS0 (25 mLs) was added and stirred with a magnetic stirrer bar. To this was added 2-chloroallyl alcohol (23) (2.249 g, 0.0243 moles) in DMS0 (10 mLs) carefully dropwise. Stirring was continued for 4 hrs. The alkoxide solution was then transferred to the dropping funnel and in the flask was placed 2,3-dichloropropene (2.70 g, 0.024 moles) in DMS0 (10 mLs). The alkoxide solution was added dropwise such that the temperature did not change appreciably. Stirring was continued for 12 hrs. Water (10 mLs) was added and the ether (24) was extracted with pentane (3x75 mLs) and the combined extracts dried over magnesium sulfate. The pentane was removed under reduced pressure on a rotary evaporator and the ether (24) (1.2 g, 36% yield) recovered by preparative high pressure liquid chromatography .

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46 2 H NMR (CDC1 3 -TMS) 6: 4.12 (s,4H), 5.42 (s,2H), 5.52 (m,2H). 13 C NMR (CDC1 3 -TMS, int ref CDC1 3 ) 6: 72.42, 113.80, 137.48. IR (NaCl): 2860 (w), 1635 (m), 1440 (w), 1385 (w), 1365 (w), 1255 (w), 1270 (w), 1180 (m), 1090 (s), 1035 (w), 890 (s), 720 (m), 640 (m). Elemental analysis: found (calculated): % C 43.51 (43.11); % Cl 41.92 (42.51); % H 4.85 (4.80). Ethy1-a-(bis-2-chloroanyl )-ma!onate (25) The method of Hill and Fischer^ was used. In a three necked, 250 mL, round bottomed flask, fitted with a mechanical stirrer, a dropping funnel and a condenser was placed ethanol (75 mLs). To it was added sodium (4.2 g, 0.1826 gr. atom) slowly to keep the mixture refluxing gently. After the sodium was dissolved diethylmalonate (29 g, 0.183 mole) was added dropwise through the dropping funnel. Stirring was continued for an hour and then 2,3-dichloropropene (44.4 g, 0.4 mole) was added and stirring continued for 12 hrs at room temperature. The sodium chloride which precipitated was filtered off and the ethanol removed under reduced pressure on a rotary evaporator. Water (40 mLs) was added and compound (24) extracted with ether (4x50 mLs). The combined ether extracts were dried over magnesium sulfate. The ether was removed under reduced pressure on a rotary evaporator and compound (24) (34.4 g, 61% yield) distilled at 107° C/0.75 mm. 2 H NMR (CDC1 3 -TMS) 6: 1.266 (t,6H), 3.16 (s,4H), 4.22 (q,4H), 5.343 (br,s,4H).

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47 13 C NMR (CDCI3-TMS, int ref CDC1 3 ) 5: 13.74, 40.52, 55.31, 61.79, 117.74, 136.90, 169.50. Synthesis of Polymers Polymerization of 2-Chloroallyl 2‘-Phenylallyl Ether 2-Chloroallyl 2 ' -Phenylallyl ether (1) (0.926 g, 0.0044 moles) with benzene (1.389 g) and 2,2'-Azobisisobutyronitrile (AIBN) (0.046 g, 5 % w/w of monomer) were divided equally and put into two polymerization tubes and taken through five freeze-thaw cycles on a mercury diffusion vacuum line for degassing, and sealed. These were then immersed, with shaking, in a water bath at 40° C and an oil bath at 60° C, respectively. The tubes were opened after 4 days and poured into methanol (2x100 mLs). There was no precipitation. On evaporation of the methanol and benzene, the monomer (1) was recovered. The proton NMR did not show any new peaks and the integration ratios were maintained as in the monomer. Polymerization of 2-Carboethoxyallyl 2' -Phenylallyl Ether 2-Carboethylallyl 2' -Phenylallyl ether (3) (1.036 g, 0.0042 moles), benzene (1.554 g) and AIBN (0.0518 g, 5 % w/w of monomer) were divided equally and put into two polymerization tubes and taken through five freeze-thaw cycles on a mercury-diffusion vacuum line. These were then immersed, with shaking, in an oil bath at 60° C and a water bath at 40° C. After 4 days, the tubes were opened and the polymer precipitated into methanol (2x100 mLs). The yields were as follows:

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48 40° C polmerization: 0.292 (56%) 60° C polymerization: 0.441 g (85%) The polymers were soluble in DMSO, benzene, dimethylformamide. acetone, chloroform. 40° C polymerization sample: X H NMR (CDCI 3 -TMS) 6 : 0.95, 1.24, 2.1, 3.0, 4.1, 7.1 (Fig. 20). 13 C NMR (CDC1 3 -TMS, int ref CDC1 3 ) 6 : 13.35-14.10, 26.34-28.58, 40.30, 41.62, 44.71, 51.17, 60.72, 72.66, 126.03-128.32, 140.41144.99, 173.55-174.96 (Fig. 21). IR (KBr ) : 2980 (m), 2850 (m), 1730 (s), 1630 (w), 1600 (w), 1580 (w), 1495 (m), 1470 (m), 1445 (m), 1380 (m), 1245 (m), 1200 (m), 1110 (s), 1025 (m), 965 (w), 890 (w), 850 (w), 760 (m), 695 (m). 60° C polymerization: NMR (CDCI 3 -TMS) 6 : 0.95, 1.24, 1.625, 2.1, 3.0, 4.1, 7.1 (Fig. 15 of Discussion and Results). 13 C NMR (C0C1 3 -TMS, int ref CDCI 3 ) 6 : 13.35-14.10, 30.16, 40.60, 41.72, 44.84, 50.20, 60.72, 72.37, 126.03-128.37, 140.65143.97, 173.69. IR (KBr) same as for polymer formed at 40° C. VPO (benzil standard): 6550. Elemental analysis: found (calculated): % C 71.07 (73.17); % H 7.33 (7.32). Polymerization of 2-Cyanoallyl 2 1 -Phenylal lyl Ether at 40% 2-Cyanoal lyl 2 ' -Phenylal lyl ether ( 8 ) (1.09 g, 0.0055 mole), benzene (1.635 g) and AIBN (0.0545, 5% w/w of monomer) were divided equally and placed in two polymerization tubes and taken through five

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49 freezethaw cycles on a mercury diffusion vacuum line for degassing, and sealed. They were then immersed with shaking, in an oil bath at 60° C and a water bath at 40° C, respectively. The tube in the 60° C bath developed a white precipitate within 30 mins and was removed after 2 hrs and the polymer was precipitated into methanol (100 mLs). The tube at 40° C developed a precipitate in about 2 hrs and the polymer was precipitated into methanol (100 mLs) after 6 hrs. The polymers in both cases were insoluble in DMS0, benzene dimethylformamide, acetone, and chloroform. The percentage conversions in the two cases were as follows: 40° C polymerization 0.32 g (59?); 60° C polymerization 0.37 g (68%). IR (similar for both cases except for relative intensities) (KBr): 3040 (m), 3020 (m), 2910 (m), 2850 (m), 2225 (w), 1625 (w), 1600 (w), 1580 (w), 1490 (m), 1465 (m), 1445 (m), 1380 (m), 1240 (m), 1095 (s), 960 (m), 885 (w), 835 (w), 760 (m), 695 (s). Elemental analysis: found (calculated): % C 75.24 (78.35); % H 6.46 (6.58), % N 6.73 (7.03). Polymerization of 2-Cyanoallyl 2‘ -Phenylallyl Ether at 10% 2-Cyanoallyl 2 ' -Phenylal lyl ether (8) (1.08 g, 0.0054 moles), benzene (9.81 g) and AIBN (0.0545 g, 5% w/w of monomer) were divided equally into three polymer tubes and taken through five freeze-thaw cycles on a mercury diffusion vacuum line for degassing and sealed. They were then immersed, with shaking, in a water bath at R.T. for 5 days, a water bath at 40° C for 8 hrs and a water bath at 60° C for 1 hr. The conversion was kept low in all three cases. The polymers formed in the three cases were precipitated in methanol (3x100 mLs).

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50 The percent yields were as follows: polymerization at R.T.: 0.092 g (26%) polymerization at 40° C: 0.078 g (22%) polymerization at 60° C: 0.05 g (14%) The polymers were soluble in DMS0, dimethyl formamide, acetone and chloroform. The IR spectra were similar to the polymers formed in the previous experiment done at 40% monomer concentration. Polymer sample formed at R.T.: l H NMR (CDCI3-TMS) 5: 1.2574, 1.5638, 3.0627 (br), 4.1204, 4.4428, 5.3620, 5.5240, 6.0263, 7.33. Polymer sample formed at 40° C: X H NMR (CDCI3-TMS) 6: 1.258, 1.724, 2.315 (br), 3.126 (br), 3.917, 4.120, 4.442, 5.350, 5.576, 6.020, 7.334. Polymer sample formed at 60° C: : H NMR (CDCI3-TMS) 6: 1.257, 1.547, 1.725, 2.317, 3.100, 3.924, 4.133, 4.40, 5.366, 5.54, 6.023, 7.334. Polymerization of 2-Carboethoxyallyl 2‘ -Methoxyallyl Ether 2-Carboethoxyallyl 2 ' -Methoxyal lyl ether (15) (0.553 g, 0.0028 moles), benzene (0.8295 g) and AIBN (0.0277 g, 5% w/w of monomers) were placed in a polymerization tube and taken through five freezethaw cycles on a mercury diffusion vacuum line for degassing and sealed. This was then immersed, with shaking, in a water bath at 40° for 2 days. The polymer was precipitated in methanol (100 mLs). A similar procedure was followed for 0.475 g (0.0024 moles) of cpd

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51 (15), benzene (0.7125 g) and AIBN (0.0238 g, 5% w/w of monomer). The water bath was however at 60° C. The percentage yields were as follows: polymer formed at 40° C: 0.45 g (81%) polymer formed at 60° C: 0.39 g (82%) Both polymer samples were soluble in benzene, chloroform, acetone, DMS0 and DMF. Sample formed at 40° C: : H NMR (CDCI3-TMS) 6: 1.152, 1.349 (sh), 1.862, 2.261, 3.222, 3.557, 4.081, 4.265. 13 C NMR (CDCI3-TMS, int ref CDC1 3 ) 6: 14.96, 20.27, 27.19, 42.30 (br), 481.69, 49.51, 54.73, 65.74, 83.04, 99.47, 173.65. IR (KBr ) : 2970 (m), 2940 (m), 2870 (m), 1725 (s), 1670 (w), 1635 (w), 1445 (w), 1375 (m), 1300 (w), 1230 (w), 1100 (s), 845 (w), 810 (w), 745 (w). Elemental analysis: found (calculated): % C 57.36 (59.96); % H 7.88 (8.06). Sample polymerized at 60° C: X H NMR (CDCI3-TMS) 6: 1.133, 1.340, 1.873, 2.171, 3.218, 3.560, 4.081, 4.250. 13 C NMR (CDCI3-TMS, int ref CDC1 3 ) 6: 15.01, 20.37, 27.19, 48.25, 49.17, 54.78, 66.28, 83.04, 99.47, 173.65. IR (KBr): same as 40°C polymerization sample.

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52 Attempted Polymerization of 2-Chloroallyl Ether 2-Chloroal lyl ether (0.98 g, 0.0059 moles), benzene (1.47 g) and AIBN (0.049 g, 5 % of monomer) were placed in a polymer tube. It was taken through five freeze-thaw cycles on a mercury diffusion vacuum line and sealed. It was then immersed in a water bath at 60° C for 4 days. The contents were then poured into methanol (100 mLs) but no precipitate was obtained. A viscous liquid was obtained after removing the methanol but was not identified.

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CHAPTER III RESULTS AND DISCUSSION NMR Analyses The assignments of unsaturated carbons have been rationalized using the resonance structures as shown in Figure 8. 45 As shown in the top resonance structure with an electron releasing group, a negative charge in one of the contributing resonance structure would shift the carbon 6 to the methoxy group to a lower 6 value and, along the same arguments, the carbon a to the methoxy group to a higher 6 value. Similarly an electron withdrawing group would lower electron density on the carbon b to the electron with drawing group as shown in the bottom resonance structure of the above mentioned figure. This analysis has been used in conclusions regarding "charge transfer" or a biased electron delocalization in related structures. A similar analysis could be drawn up for assigning hydrogens in the proton NMR. Synthesis of Monomers The Williamson reaction 469 was the base reaction in the synthesis of the four monomers. The reaction is depicted in general terms below. 53

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54 + Fig. 8: Information regarding C 13 NMR chemical shifts of substituted alkenes.

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55 base RX + R 1 OH ROR' solvent base RX or R 1 OH * R'O" R 1 OR (S N 1) Hence for each ether the following combination of reactants could be used. (RX.R'OH) or (R'X.ROH) for the same ether ROR* For the monomers synthesized the ease of synthesis of the halide and the corresponding alcohol dictated the combination used. For the allylic ethers prepared, whenever the unsaturated point had an electron-wi thdrawing group attached in the halide, the alkoxide in DMSO was added to the halide in DMSO and whenever the unsaturation point had an electron donating group attached in the halide, it (in a DMSO solution) was added to the alkoxide. This was due to the possible attack of the alkoxide as shown. giving side reactions thereby

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56 2-Phenyl ally! 2 1 -Chloroal lyl Ether (1) (Scheme 3) The combination used here for the Williamson reaction was 2-phenylallyl alcohol^ and 2-chloroallyl chloride due to the availability of both reagents. The 2-phenylallyl alkoxide formed by sodium hydride was added to 2-chloroallyl chloride. The product, 2-phenylallyl 2* -chloroallyl ether (1), was isolated by high pressure liquid chromatography since an attempt at fractional distillation did not give a very efficient separation from the unreacted 2-phenylallyl alcohol. The 2-phenylallyl 2'-chloroallyl ether structure was confirmed via proton NMR and carbon-13 NMR (as shown in Fig. 9), IR and elemental analysis. The assignments were confirmed by an INEPT^ spectrum which showed negative peaks at 6 = 72.077, 113.058 and 114.722 ppm. The assignments for carbon 1 and carbon 3 were done on the basis of electron density at the double bond itself and on the analysis discussed at the beginning of this chapter. The infrared spectra showed peaks at 1635 and 1600 cm -1 corresponding to the C=C stretch of the a-phenyl allyl and 2chloroallyl moiety respectively. The proton assignments were based on general assignment principles as well as integration ratios. As can be seen, the two sets of unsaturated carbons do not differ widely as regards electron density as can be concluded from Figure 9 and the initial analysis. i

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57 "S 0 Cl l.c. separation NaH < DMSO oh: cpd.(,3) 20 % yield l.c. separation ^ CO^C^H^. \ C„H OH cpd.QI | ^ H , reflux Scheme 3: Synthesis of compounds (1) and (3).

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58 Fig. 9: Proton (100 MHz) spectrum and noise decoupled C 13 spectrum of compound (1) in CDC1 3 .

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59 2-Carboethoxyallyl 2'-Phenyla11y1 Ether (3) (Scheme 3) The combination used in the synthesis was 2phenylallyl alcohol and 2-carboethoxyallyl bromide (2). The 2carboethoxyallyl bromide (2) was synthesized via the acid catalyzed structure of (2) was confirmed by C 13 NMR, proton NMR and IR. The C 13 NMR and proton NMR assignments are listed in Table 1. Here again 2-phenylallyl alkoxide in DMSO was added to the 2-carboethoxyallyl high pressure liquid chromatography since attempts to isolate the compound (3) via distillation under reduced pressure (upto 0.5 mm) seemed to polymerize it. The identity of the monomer was confirmed via carbon-13and proton NMR spectra which are shown in Figure 10. The carbon assignments were confirmed by an INEPT spectrum showing negative peaks at 5 = 69.04, 73.28, 114.46 and 125.33 ppm and •positive peaks at 6 = 14.61 and 60.95 ppm. The proton NMR spectrum showed four different peaks assigned as shown. The two sets of carbons do differ to a greater extent than in compound (1) as can be seen from the carbon spectra. The C=C stretch for the 2-phenylallyl and the 2-carboethoxyallyl moiety occur at 1635 and 1600 cm -1 in the IR spectra. 2-Phenylallyl 2 1 -Cyanoal lyl Ether (8) (Scheme 4) The mechanism of the first step would be esterification as reported 32 from a-(bromomethyl )acrylic acid. The *31 bromide as described. The monomer was isolated via preparative o HSQ, 3 Cl

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60 Table 1: Carbon-13 and proton NMR assignments for compound (2) 4 5 / C0 2 CH 2 CH 3 Br 4 5 6 co 2 ch 2 ch 3 Br proton 6: 1.26-1.40 5 carbon 6: 13.99 6 (CDC1 3 ) 4.16-4.38 4 (CDC1 3 ) 61.11 5 4.19 3 68.41 3 5.96 1 125.01 1 6.32 2 137.58 2 167.75 4

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61 Fig. 10: Proton (100 MHz) spectrum (in CDC1 ) and C 13 noise decoupled 25 MHz spectrum (in benzene-d 6 ) of compound (3).

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62 cpd.C8) 2b% yield l.c. separation CN cpd. C6) Cl 500° C NC H N 2 '% cis & trans Cl cpd. CT) 0 X 0 NC ci cpd. C5) 0 0 OH 28% yield Cl Scheme 4: Synthesis of compound (8).

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63 The identity of the chi oroace tone cyanohydrin (4) was confirmed by carbon-13 and proton NMR and IR spectra and the assignments for the protons and carbons shown in Table 2. The chi oroace tone cyanohdrin acetate (5) was confirmed by carbon-13 and proton NMR spectra and the assignments for the protons and carbons shown in Table 3. Compound (4) showed the CN stretch in the IR at 2250 cm *. 2-Cyanoallyl chloride ( 6 ) was confirmed by carbon-13 and proton NMR and IR. The assignments for the protons and carbons are shown in Table 4. In the proton NMR and H 2 occur at the same chemical shift. They occur at
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64 Table 2: Proton and carbon-13 NMR assignments for compound (4), ^ Cl Cl proton 6: 1.708 1 carbon 5 : 24.80 1 (CDC1 3 ) 3.681 2 (CDClo) 50.05 2 4.309 3 68.72 3 119.50 C=N Table 3: Proton and carbon-13 NMR assignments for compound (5). 0 0 1 1 o4s 1 4 I J2 Js. 2 "Vi CN 1 Cl Cl proton 5 : 1.85 1 carbon 5 : 20.61 1 (CDCI3) 2.15 3 (CDCI3) 22.76 4 3.90 2 46.83 3 70.62 2 116.38 CN 168.38 5

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65 Table 4: Proton and carbon-13 NMR assignments for compound (6). proton 6: 4.160 3 ( CDC1 3 ) 6.116 1,2 carbon 6: 43.23 ( CDC1 3 ) 113.26 115.65 133.29 Table 5: Proton and carbon-13 NMR assignments for compound (7). proton 6: cis 2.018 1 trans 2.034 (CDC1 3 ) 6.667 2 6.926 C-13 5: cis 18.42 1+ NC^ 1 2 ^C1 3 trans 15.45 (CDC1 3 ) 116.23 4 116.23 119.79 2 119.79 131.78 1 135.14 H M GO

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66 Fig. 11: Proton spectrum (100 MHz) (in benzene cL) and C 13 noise decoupled spectrum (25 MHz) (in CDC1 3 ) Of compound (8).

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67 Fig. 12: 25 MHz decoupled and multiplicity determination C 13 spectra for compound (8).

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68 greater extent than even compound (3). The infrared spectrum shows the C^N stretch at 2230 cm *. 2-Carboethoxyal lyl 2' -Methoxyallyl ether (15) (Scheme 5) The combination used here for the Williamson reaction was 2-carboethoxyallyl alcohol (14) and 2-methoxallyl bromide (12). The syntheses of the synthons^ of the other combination were not reported. 2-Carboethoxyallyl alcohol was prepared via the method of Rosenthal et al. 37 4H-ChC-CH 2 -0H + Ni(C0) 4 + 2CH 3 C0 2 H + 55°, C 2 H 5 0H 4CH 2 =C-CH 2 0H + Ni (CH 3 C0 2 ) 2 + 2[H] co 2 h ch 2 =c-ch 2 oh + c 2 h 5 oh co 2 h h 2 so 4 -h 2 o C°2 C 2 H 5 ch 2 =c-ch 2 oh The identity of the ethyl -o-( hydroxymethyl )acrylate (14) was confirmed via C 13 NMR, proton NMR and IR. The assignments for the carbons and protons are listed in Table 6. The first method for the synthesis of 2-methoxyallyl bromide via bromination using Nbromosuccinimide of Greenwood and Hoffman 3 ^ was successful but the method of Jacobson et al. 35 was preferred. The drawback of the method of Greenwood et al. was that one obtained a carbon tetrachloride solution of the 2-methoxyallyl bromide contaminated with products resulting from the addition of succinimide to the enol

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69 OMe OMe cpd. Cl 5 ) 25% yield C 0 2 C 2 H 5 OH = . NiCCO), \ ~ OH. CH 3 C0 2 H, H 2 0, 55° C 0 II 'COOH c 2 h 5 oh H OH OMe C 0 2 C 2 H 5 OH cpd . (11+ ) V C • >N HOTs 150°19Q°C .OMe MeO Br cpd. Cl2) b5% H Br 15% cis & cpd. ( 13 ) Scheme 5: Synthesis of compound (15). trans

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70 Table 6: Carbon-13 and proton NMR assignments for compound (14). 2 1 h ? co 2 ch 2 ch 3 V ^ 3 OH u 456 proton 5: 1.3 1 (CDC1 3 ) 2.7 4 (deuterium exchange) 4.25 2 4.3 3 5.8 5 6.25 6 carbon 6: 13.89 6 (CDCU) 60.58 5 (or 3) 61.55 3 (or 5) 124.88 1 139.58 2 166.09 4 Table 7: Carbon-13 and proton NMR assignments for compound (9). 0 Br proton 6: 2.40 1 (CDClo) 3.90 2 Br carbon 5: 26.98 1 (CDC1 3 ) 34.82 3 199.68 2

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71 Table 8: Carbon-13 and proton NMR assignments for compound (11). 2^1 T 1 0"h + K — (t I \ proton 6: (CDC1 3 ) 1.37 1,2, 3, 4, 5 carbon
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72 ether double bond. It also resulted in only 10-20% conversion to the desired 2-methoxyal lyl chloride. The l-bromo-2,2-dimethoxypropane (10) was prepared from bromoacetone using the method described by n c Jacobson et al. Bromoacetone was synthesized from acetone and the identity was confirmed by carbon-13 NMR, proton NMR, and IR. The assignments for the carbons and protons are listed in Table 7. The catalyst used here was reported to be the most efficient*^ and was synthesized as per the method reported by Jacobson et al.^ jhe structure was confirmed by carbon-13 NMR and proton NMR. The assignments of these are listed in Table 8. l-Bromo-2,2-dimethoxy propane (10) was confirmed by carbon-13 NMR, proton NMR and IR. The assignments for the carbons and protons are listed in Table 9. The fraction collected between 85° C and 130° C had the highest percentage of 2-methoxyal lyl bromide.^ This would seem true since 1bromo-2, 2-dime thoxy propane (10), the other major constituent, has a boiling point of 156° C. The proton NMR assignments for (12) and (13) are listed in Figure 6 and the carbon-13 NMR spectrum and the assignments in Figure 13. The mixture could be used directly in the subsequent reaction for the synthesis of (14) since again the allylic bromine in (12) would be more easily displaced than the allylic hydrogen in l-bromo-2-methoxypropene (13) and the bromine in (10) by 2carboethoxyal lyl alkoxide. 2-Methoxyallyl 2‘-carboethoxyallyl ether (14) was prepared using the Williamson reaction and identified using C 13 NMR, proton NMR and IR. The spectra are shown in Figures 14 and 15. Figure 14 also shows the off-resonance decoupled C 13 spectrum. The structure was also confirmed by an INEPT spectrum.

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73 Table 9: 2 proton 6 (CDC1 3 ) Carbon-13 and proton NMR assignments for compound (10). OMe, 3 OMe, OMe„ 1 OMe„ Br 1.45 2 3.20 1 3.35 3 carbon 5: 20.61 (CDC1 3 ) 34.55 48.69 99.76 h ro oj

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74 7, a O' O' rH nn h O m Fig. 13: Carbon-13 (25 MHz) spectrum of the pyrolysis of l-bromo-2, 2-dime thoxypropane

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75 H 5 H 6 8 COOCH^CH^ Fig. 14: Proton spectrum (60 MHz) in CDC1 3 (15).

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76 Noise and off-resonance decoupled C 13 spectra in CDC1-, (15). J Fig. 15:

PAGE 87

77 Synthesis of Model Compounds The model compounds were synthesized mainly to see if there was any charge transfer occurring in the free state of the monomer. Hence compounds were synthesized having structures similar to the monomers prepared. The monomer, 2-chloroallyl 2'-phenylallyl ether, was not pursued since it was not expected to show any "charge transfer" interaction due to its non-polymerizability. The two 2sets of carbons are comparable as per the carbon-13 NMR spectra. This would be expected since the chlorine group is electron releasing by resonance and electron withdrawing by induction, and field effects which contribution predominates would determine whether the chlorine group acts as an electron donating or an electron withdrawing group. It was decided therefore only to synthesize model compounds for compounds (3), (8) and (15). The model compounds would have an unsaturation point only attached to the electron withdrawing group since if the unsaturation point was attached to the electron releasing group chemical shifts in the proton and carbon-13 NMR spectra would be extremely small. 2-Carboethoxyallyl 2 1 -Phenyl propyl Ether (16) (Scheme 6) This was prepared by the Williamson reaction using 2-phenyl propanol and 2-carboethoxyal lyl bromide (2), with sodium hydride as the base. The identity of the 2-carboethoxyal lyl 2'phenyl propyl ether (16) was confirmed by C 13 NMR, proton NMR, IR and elemental analysis. The C 13 NMR and proton NMR assignments are listed in Table 10.

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78 C0 2 C 2 H 5 cpd. (l6) bO% yield CN cpd.Cl7) yield Scheme 6: Synthesis of compounds (16) and (17).

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79 Table 10: Carbon-13 and proton NMR assignments for compound (16). 7 8 7 8 9 co 2 ch 2 ch 3 0 proton 6: (CDC1 3 ) 0.936 8 carbon 5: 14.11 9 1.221 5 (benzene d°) 18.39 6 3.320 4 40.37 8 3.212-3.407 6 60.41 4 3.967 7 69.37 3 4.151 3 76.87 5 5.7291 1 124.54 1 6.280 2 127.71 Cp 7.117-7.128 HP 128.54 Cp 138.38 2 144.67 Cp 165.53 7

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80 An attempt to isolate (16) via distillation proved unsuccessful to purify it totally and preparative high pressure liquid chromatography had to be used. 2-Cyanoallyl 2 '-Phenyl propyl Ether (17) (Scheme 6) The Williamson reaction was utilized for this synthesis. The 40:60 mixture of 8-chloro-a-methacrylonitrile (7) and a-(chloromethyl )acryloni trile (6) was used directly and (17) isolated via preparative high pressure liquid chromatography. The compound (17) was isolated and identified via C 13 NMR, proton NMR, IR and elemental analysis. The C 13 NMR and proton NMR spectra are shown in Figure 16. 2-Carboethoxyal lyl 2 1 -Methoxypropyl Ether (21) (Scheme 7) The Williamson reaction was used here and the reaction was carried out by adding 2-carboethoxyallyl bromide (2) in DMSO to 2-methoxyprop-oxide in DMSO. 2-Methoxypropanol was synthesized using standard reduction procedures from methyl-2methoxypropionate with lithium aluminum hydride. 2-Methoxypropanol was identified by C 13 NMR, proton NMR and IR. The assignments for the C 13 NMR and proton NMR spectra are listed in Table 11. The methyl -2-methoxypropionate (19) was obtained via LiAlH 4 +ch 3 -c-ch 2 oh + ch 3 oh 0CH 3 esterification of 2-methoxypropionic acid (18). The carbon-13 NMR

PAGE 91

81 Fig. 16: Proton (100 MHz) NMR spectrum (in CDC1.J and carbon-13 (25 MHz) NMR spectrum (in CDCl^) of compound (17).

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Cl J 1. MeO Na OE 2. H OMe LiAlH, cpd. C20) OH 1. NaH, DMSO 2 . , C0 2 C 2 H 5 OMe Br OMe OH' cpd. (j.8T CH OH, HClCg). OMe 0 cpd. (21) , 5Q£ yield C0 2 C 2 H 5 Scheme 7: Synthesis of compound (21).

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83 Table 11: Proton and carbon-13 NMR assignments for compound (20). proton <$: (CDC1 3 ) 1.117 2.621 3.388 3.494 3.49 1 5 3 4 2 (D 2 O exchange) C-13 (CDC1 3 ) 15.11 56.24 65.94 77.39 1 3 4 2 Table 12: Proton and carbon-13 NMR assignments for compound (19), 5 OMe 3.40 3.78 3.85 1 5 4 2 carbon 6 : 18.32 51.85 57.60 76.32 173.50 H LO OJ CO

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84 Table 13: Proton and carbon-13 NMR assignments for compound (18). 3 OMe proton 6: 1.50 1 carbon <5: 17.93 3.45 3 57.60 4.0 2 75.83 10.85 5 178.37 H fO M

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85 and proton NMR assignments used for the identification of (18) and (19) are listed in Tables 12 and 13, respectively. The 2-methoxypropionic acid (18) was obtained via a substitution of the chlorine in 2-chloropropionic acid. 4( ^ C1CH-C0 2 H + 2CH 3 0Na » CH 3 0CH-C0 2 Na + NaCl + CH OH CH 3 CH 3 CH 3 0CH-C0 2 Na + HC1 CH 3 0-CH-C0 2 H + NaCl ch 3 ch 3 CH 3 0-CH-C0 2 H + CH 3 0H — >CH 3 0-CH-C0 2 CH 3 + H 2 0 ch 3 ch 3 2-Carboethoxyallyl 2' -methoxypropyl ether (21) was purified via distillation. The identity was confirmed via carbon-13 NMR, proton NMR, IR and elemental analysis. The carbon-13 NMR spectrum and the INEPT spectrum with the assignments are shown in Figure 17 and the proton NMR assignments are listed in Table 14. Comparison of Spectra The carbon-13 chemical shifts of the unsaturated carbons of interest in compounds (3), (8) and (15) and their respective models (16), (17) and (21) are listed in Tables 15, 16 and 17. The protons for the models have decreased in chemical shift and the carbons have decreased (C^ to which the protons are attached < C 3 ) and increased (C 2 > C^) in chemical shifts with respect to the monomers. This is

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86 , p COOCH CH __/ 7 3 6 5 OCH„ I (_ 160 lUO 120 100 80 So Uo 20 -PPM W i CK,CH-* + Fig. 17: 25 MHz decoupled and multiplicity determination sequence C 13 spectra (21).

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87 Table 14: Proton NMR assignments for compound (21). 4 5 co 2 ch 2 ch 3 proton 6: 1.159 (CDC1 3 ) 1.304 3.397 3.478 3.353-3.489 4.234 4.226 5.885 6.298 9 5 7 6 8 3 4 1 2

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88 consistent in all three pairs. Assuming no intermolecular interaction due to the dilute conditions under which the NMR spectra were obtained, one could conclude that intramolecular interaction amounting to "charge transfer" could be taking place. Referring back to Section A and Figure 8, if there had been no "charge transfer," relative to the molecule with charge transfer the double bond with the electron donating group would be more electron rich which could be looked upon as another very weak electron donating group attached to the unsaturation. This would cause to increase and C2 to decrease relative to the molecule having "charge transfer" if the weak electron donating group were attached to Cj.. A similar analysis could be drawn for the double bond with the electron withdrawing group which would cause C 3 to decrease and C 4 to increase. This latter case is, indeed, what is seen in the case of the monomers and their model compounds. A similar analysis could be drawn for the hydrogens attached to in Tables 15, 16 and 17. They would decrease in chemical shift as woul d C 1Q . However, certain deviations may be expected anyway since factors other than "charge transfer" would come into effect because the hydrogens would be susceptible to steric interactions. The magnitude of the shift in the carbon-13 NMR would be expected to be small as could be derived from an experiment done by mixing 2,4,6-trimethoxystyrene 5 ^ with fumaroni tri le. The scheme for preparation used for the synthesis of 2,4,6-trimethoxystyrene is shown in Figure 19. The proton and carbon-13 NMR chemical shifts of two separate compounds and a mixture in a 1:1 molar ratio are shown

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89 Table 15: Comparative proton and carbon chemical shifts for compounds (3) and (16). H3 Eh CO„C„H r \3 V 2 2 5 R.T. benzene-d^ cdcl 3 HI 6.284 6.302 H2 5.802 5.856 Cl 124.83 125.59 C2 138.23 137.34 deer. incr. 0 R.T. benzene-d® cdcl 3 H3 6.280 5.238 H4 5.729 5.754 C3 124.54 125.15 • C4 138.38 137.43 '

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90 Table 16: Comparative proton and carbon chemical shifts for compounds (8) and (17). benzene-d® COCL3 5.243 5.979 130.19 131.39 120.79 120.23 deer. incr. 0 I » R.T. benzene-d^ CDCL3 H3 5.242 5.955 H4 5.170 5.869 C3 129.80 131.00 C4 121.03 120.47

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91 Table 17: Comparative proton and carbon chemical shifts for compounds (15) and (21). OMe R.T. benzene-d^ cdcl 3 HI 6.366 6.346 H2 5.841 5.909 Cl 125.03 125.93 — i C2 138.23 137.29 — H3 \3 4/ C0 2 C 2 H 5 deer. incr. R.T. benzene-d® cdcl 3 H3 6.327 6.298 H4 5.850 5.885 C3 124.49 125.30C4 138.48 137.34-

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92 N.M.R D', A' relatively weak compared to D,A 0 no complex Cl increase in p • p • m « C2 decrease in p.p.m. C3 decrease in p.p.a. C4 increase in p.p.m. Fig. 18: Analysis for explanation of observed shifts.

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93 compound supplied by Dr. S. Mallakhpour. Fig. 19: Synthesis scheme used for 2,4,6-trimethoxystyrene.

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94 in Tables 18 and 19. The shift of the fumaroni trile protons and carbons are effectively in the same range as the shifts in the monomer and model compounds discussed. The shifts in the case of the non-aromatic double bond in 2,4,6-trimethoxystyrene would, as expected, not be very great due to a resonance interaction with the aromatic ring. The chemical shifts in the case of fumaroni trile would be a decrease on mixing of the components, to a lower due to loss of electron density as is seen by R.B. Seymour et al . 26 The magnitude of the difference in chemical shift is greater in the case of ( 8 ) and (17) than in (3) and (16) in Table 20 which would be expected since CN is a stronger electron withdrawing group (keeping the electron donating group, phenyl the same) than carboethoxy. A similar magnitude difference is seen in the case of (15) and (21) and (3) and (16) in Table 21 where methoxy is a stronger electron donating group than phenyl and carboethoxy is kept the same. The differences mentioned above are more pronounced in benzene-d® 2 ^ than in CDC^ where the actual conditions of polymerization (with respect to solvent) are kept constant. This might be expected since benzene is a less polar solvent than CDCI 3 . Benzene could itself act as an electron donor towards "charge transfer" but the intramolecular complex formed could have a more negative free energy of formation due to both enthalpy as well as entropy factors. The enthalpy factor could be due to the styrene moiety being a better electron donor and the entropy factor could be due to the molecules not being immobilized in the case of

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95 Table 18: Comparative carbon chemical shifts for fumaroni trile and 2,4,6-trimethoxystyrene separate and mixed in a 1:1 molar ratio. C2 C 13 NMR in benzene-d^ (ppm) separate at R.T. 1:1 at R.T. Cl under the benzene peaks (~ 128) C2 116.01 116.06 C3 160.22 160.17 C4 160.75 160.75 C5 91.16 91.11 C6 109.09 109.04 C7 117.77 117.57 C8 114.06 114.06

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96 Table 19: Comparative proton chemical shifts for fumaroni trile and 2,4,6-trimethoxystyrene separate and mixed in a 1:1 molar ratio. hi Proton NMR in benzene-d® (ppm) separate at R.T. 1:1 at R.T. H3 7.593 7.560 7.471 7.439 7.413 7.380 7.291 7.259 HI 6.509 6.485 6.477 6.454 6.327 6.305 6.295 6.273 H2 5.642 5.625 5.610 5.593 5.521 5.504 5.489 5.472 Hf 4.565 4.349

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97 Table 20: »C chemical shift di fferences with acceptors different ( const) difference C 1 & c 3 C 2 & c 4 4> d^ CDC1 3 * d 6 CDC1 3 CN 0.39 0.39 -0.24 -0.24 C0 2 Et 0.29 0.44 -0.15 -0.10 1 1 Table 21: C chemical shift differences with donors different (carboethoxy const) difference C 1 & C 3 C 2 & c 4 -eo. Ol CDC1 3 d 6 CDC1 0.29 0.44 -0.15 -0.10 och 3 0.54 0.63 -0.24 -0.05

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98 intramolecular "charge transfer." Benzene however has been quoted to be a nondonor solvent. ^ Referring to Figure 18 and the model compounds if the group 1 were considered a stronger electron releasing group than group 2, the relative effect on the chemical shifts would be that C3 would decrease and C 4 increase in ppm. This would imply that group 3 is a stronger electron releasing group than group 4 making Cg appear at a lower ppm than Cg, which is contradictory to what is observed. group 3 group 4 An attempt to investigate the UV spectra with change in temperature led to a decrease in UV intensity with increase in temperature as is shown in Figure 20. This is quite similar to data observed by Butler and Olson^ and does not prove, individually, the existence of an interaction.

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99 Fig. 20: UV of compound (15) (cone = 10 ^ M) in t-butyl alcohol at different temperatures.

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100 Polymer Synthesis and Characterization Poly (2-chlorallyl 2‘ -phenylallyl ether) The attempted polymerization of monomer (1) did not afford even oligomers. The monomer was recovered from the attempted polymerization. Poly (2-carboethoxyallyl 2'-phenylallyl ether) Poly(2-carboethoxyallyl 2'-phenylallyl ether) was formed at 40° C and 60° C. The polymers formed at the two temperatures were characterized by NMR, IR, elemental analysis and GPC. The number average molecular weight of the polymer formed at 60° C was determined by Vapor Pressure Osmometry to be 6550. The number average molecular weight of the polymer formed at 40° C seemed to be in the same range as per the GPC curve (Fig. 21). The GPC curve using dimethylformamide (DMF) indicates that the polymer has a very broad molecular weight distribution. The solubility of the polymer in solvents such as benzene, chloroform, acetone, dimethyl formamide and dimethyl sulfoxide indicates that the polymer is linear and, hence from the expected structure, cyclic. The proton NMR and C 13 NMR spectra are shown in Figures 22 and 23. The carbon spectra are nearly identical but the proton NMR spectra with the help of spectra of methyl -4-phenyl butyrate^ 9 and methyl -5-phenyl valerate ^ seem to mediate a fi ve-membered ring predominance at 40° C changing to a six-membered predominance at 60° C.

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101 13 15 17 19 21 23 25 counts (.94nls/min) Fig. 21: GPC curves for polymers (in DMF) formed at different temperatures.

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102 Fig. 22: Proton NMR spectra for polymers (in CDC1 o ) formed at 40° C and 60° C.

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I Fig. 23: Carbon-13 NMR spectra for polymers formed at 40° C and 60° C.

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104 Poly ( 2-cyanoal lyl -2 * -phenylal lyl Ether) The polymer formed at 40% monomer concentration was extremely insoluble and hence could not be analyzed with respect to NMR spectroscopy. Polymer formed at 10% monomer concentration was soluble in chloroform, DMF, acetone and DMSO and GPC curves (Fig. 24) showed these to be bimodal. The area under the curve from counts 17 to 23 corresponded to the branched polymer and the area under the curve from counts 23 to 26 corresponded to the linear polymer. The latter portion decreased relative to the former at higher temperature. At higher concentration the monomer led to cross! inked polymer. The elemental analysis would not change depending on the degree of branching or crosslinking. Poly (2-methoxyal lyl 2 l -carboethoxya11yl ether) The polymer formed was soluble in benzene, chloroform, acetone DMF and DMSO. Characterization was done using IR, NMR (C 13 and proton), elemental analysis and GPC. The GPC curves again showed a bimodal distribution indicating a mixture of branched and linear polymer. The NMR data, hence, were not interpreted. Conclusion on Polymerization of Monomers For polymers of 2-carboethoxyallyl 2‘-methoxyallyl ether and 2cyanoallyl 2* -phenylallyl ether, no definite conclusions could be drawn regarding “charge transfer." At lower temperatures a complex could be formed. However, at higher temperatures as the complex tends to break up, reactivity ratios would tend to play a dominant part. However this does not rule out, at lower temperatures, kinetic

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105 13 15 -17 19 21 22 23 24 25 26 27 23 29 30 counts ( . 94mls/min) t 1 1 1 1 1 1 1 1 1 1 1 t 1 1 1 1 i » I r ... 12 14 16 18 20 22 23 24 25 26 27 28 29 30 counts ( . 94mls/min) Fig. 24: GPC curves for polymers (in DMF) formed at R.T. and 40° C

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106 control of ring formation and intermoleculear propagation leading to a linear cyclopolymer with five-membered rings as per the mechanism of Butler or six-membered rings as per the mechanism of Butler and Matsumoto 66 and Butler et al. 67 Unsaturation remaining in the polymers corresponding to the a-methoxy vinyl ether and styryl moieties leads one to conclude that these two moieties could perhaps lead to crosslinking or branching due to the relative stability of their radicals at higher temperatures. The facile homopolymerization CQ of a-methyl acryloni trile and methyl methacrylate would have to be taken into account. For 2-chloroal lyl 2'-phenylallyl ether, one could perhaps assume that no "charge transfer" is taking place between the 2 unsaturation units. The a-methyl vinyl chloride moiety does not polymerize in a cyclo-fashion as can be seen from the attempted polymerization of 2-chloroal lyl ether. From the polymers of 2-carboethoxyal lyl 2' -phenylallyl ether Scheme 8 is proposed. Initial attack of the initiator perhaps occurs at the point of unsaturation having the donor group. This would be the more reactive of the double bonds. The first equilibrium has been shown to exist but it may be largely lying to the right due to lack of observation of any other peaks in the NMR spectra. At 60° C, however, the stability of the benzyl radical and the methoxyvinyl radical may be a factor since equilibrium II (Scheme 8) would play an important role due to the break up of the "charge transfer" complex 26 and the consequent lower contribution of the other pathway. Thus

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107 polymer with 5-niembered a rings M * polymer with 6-membered rings c ro ssl inked /branched polymer Scheme 8: Possible paths for polymerizations of monomers.

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108 with a highly reactive acceptor substituted vinyl radical (relative to donor substituted vinyl radical) intermolecular reaction could occur over ring closure as is indicated by the polymerization rates. Thus the proportion of branched polymer increases at higher temperatures in the case of poly (2-cyanoallyl 2-phenyallyl ether) and poly(2-methoxyal lyl 2'-carboethoxyallyl ether). This would leave the substituted benzyl and the substituted a-methoxy vinyl unsaturation which is seen in the case of the branched polymers in both the carbon and proton NMR spectra. Frontier Molecular Orbital Analysis For the monomers studied, an analysis would involve considering each molecule as two separate entities. The entities would be substituted vinyl groups, the substituents being electron withdrawing (A) and electron donating (D) or conjugating (C). The related energy levels of frontier orbitals of ethylene and some monosubsti tuted ethylenes are shown in Figure 25 for comparison. Here the size of the circle is roughly in proportion to the coefficient on the vinyl carbon in the frontier orbital; the shaded and unshaded ones are of opposite signs of the coefficient in the molecular orbital representation. "Charge transfer" complexes are predicted to have favored interactions. Maximum overlap between the highest occupied molecular orbital (HOMO) of the donor and the lowest unoccupied molecular

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109 Fig. 25: Frontier orbital energies and coefficients of ethylene and monosubsti tuted ethyl enes.

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no orbital (LUMO) of the acceptor would lead to the maximum amount of charge-transfer stabilization. In the system studied subsequently, the LUMO of the acceptor, Nmethylmaleimide, and the HOMO of the donor, methyl vinyl ether, are represented below with the area of the circle being proportional to HOMO -0.4901 eigenvalue the coefficient of the p£ orbital, the atomic orbital of the atom mainly contributing to the molecular orbital. Maximum overlap could therefore be obtained with the stereochemistry of the complex as proposed by Butler and 01 son. 25 This is indeed seen in the next chapter when a high energy of stabilization is obtained from calculations. Also polymers obtained from these monomers support this structure. For the system studied, in order to determine "charge transfer" via frontier orbitals, the system could be looked at as shown in Figure 26. These combinations as can be seen from Figure 25 would be the combinations that would give the minimum energy difference and the maximum overlap. Thus "charge transfer" would be maximized. The energy levels and the coefficients would vary with substituent. This

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Ill Fig. 26: Representations of the systems studied.

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interaction is seen experimentally as discussed under Section D of this chapter. Thus one could expect a structure such as and the expected geometry may be visualized as With no interaction existing, the singly occupied molecular orbital ( SOMO ) of the vinyl group with the acceptor substituent interacting with the HOMO of the other vinyl species (having the C or D substituent) would lead to a six-membered radical. The vinyl group having the acceptor substituent would have to be the one forming the radical species initially since it has a relatively low energy SOMO. This would be more sensitive to the polarization of the HOMO of the other vinyl group which is raised in energy due to the C or D substituent leading to a six-membered ring. This is indeed what is observed at higher temperatures in the absence of "charge transfer" complexa tion.

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113 However, in the presence of complexation, a concerted addition of the complex to the chain end would lead to five-membered ring formation thus: The next complex could add to the radical end. This would explain the five-membered ring predominance at 40° C and the six-membered ring proportion increasing upon polymerization at 60° C.

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CHAPTER 4 THEORETICAL CALCULATIONS Introduction OC Butler and 01son tJ have, on the basis of stereochemistry observed, cited the complex (XIV) in the copolymerization of Nsubstituted maleimides and vinyl ethers. I R The stereochemical results were rationalized by invoking the attack of the radical chain end on the side of the complex that is syn to the vinyl ether as shown: The mechanism cited was thus a concerted addition of the complex to the chain end. The next complex could add to either side of the vinyl ether radical, thus explaining the random selective stereochemi stry between the vinyl ether methine carbon and the methines of adjacent succinimide units observed in the copolymers. 114

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115 It was intended that theoretical molecular-orbital calculations be carried out on complex XIV. The intermolecular interaction in charge-transfer complexes (a form of molecular association) has been treated most frequently by means of perturbation theory. 54 However a molecular orbital treatment considering the complex as a single molecule seemed to be more suitable for giving quantitative predictions. As yet, the results of some molecular-orbital (MO) calculations using several semi -empirical all valence electron methods have not been very successful. Extended Huckel Theory (EHT) calculations on some calculations of this type failed to find any stable arrangement. 55 Complete Neglect of Differential Overlap/2 (CNDO/2) 5 ^ calculations on the Tetracyanoethylene (TCNE)-benzene complex are reported. 55 The CNDO/2 method overestimates the stabilization energy considerably and the minima are at too short distances of the complex components. The basic purpose behind such a calculation, however, is the elucidation of those factors which dictate the observed relative intermolecular geometric characteristic of the majority of both charge-transfer and charge-resonance complexes. The PCILO 50,51 (perturbative configuration interaction using localized orbitals) method in the field of charge-transfer interaction has been applied to calculate intermolecular energies in the cis-2-bulene-l i thium (I) 5 ^ complex and complexes of thiazoles with tetracyanoethylene 58 (TONE). Again in these cases, the too short distances of the complex components and the slight overestimation of the stabilization energy given by the PCILO method

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116 may be caused by using the CNDO parameterization. This effect is intensified by the so-called "basis-extension" effect. 58,62 program PCILO calculates the electronic ground state energy and the one particle density matrix. Essentially it looks at the molecule as an assembly of two center, two electron molecules (chemical bonds) in interaction, the interaction being treated by perturbation theory in an anti symmetrized basis. The method relies on four fundamental steps: (1) Building up the bonding and anti bonding orbitals. (2) The antibonding orbitals are used for the construction of Slater determinants' corresponding to excited configurations. (3) The bonding orbitals are used to construct a Slater determinant which is the zero-th order wave function for the molecule. (4) In the basis of all these determinants the molecular Hamiltonian is represented by a configuration interaction matrix. The eigen-value and eigen vector are calculated by a Rayleigh-Schrodinger perturbation series. The program in its present form applies the zero differential overlap (ZDO) simplification in order to force the starting set of bonding orbitals to be orthogonal. The application of CNDO/2 approximations for the molecular integrals further simplifies the calculations.

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117 Table 22: Comparison of CNDO and PCILO determinations with experimental data, AE-kcal/mole, R-A°. Charge-Transfer PCILO CNDO/2 Experimental Comples R -^E R -ae R benzenete tr a cy a n oe thy 1 e n e (TCNE) Configuration 1 22.5 2.20 125 1.75 3.35 2.54 3. 2-3. 5 Configuration 2 23.3 2.20 143 1.75 direne-TCNE Configuration 1 5.7 2.50 5.5 5.32 3. 2-3. 5 Configuration 2 3.5 2.75 hydrofurinonequinone 5.6 2.60 2.9 2.4 5.2 3.33 2.4 2.60 ethylene-fluorine 27.7 1.60 37 1.46 ethylene-chlorine 8.7 2.25 62 2.26 2-3 3.0

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118 Calculation Details The ZINDO program, a geometry optimization analytical gradient INDO program , 63 was used to initially optimize the geometries of Nmethylmaleimide and methyl vinyl ether. The input was done via the Quantum Chemistry Interactive Program Utility (QUIPU). 6 ^ After a ball and stick geometry optimizer on the initial geometry sketched in, it took 46 cycles of ZINDO for the N-methylmaleimide and 106cycles for the methyl vinyl ether for the optimization to take place. The final optimized geometry of N-methylmaleimide and methyl vinyl ether are listed in Tables 23 and 24 respectively and the zaxes views are shown in Figure 27 corresponding to the tables. Similarly structures C 2 and C 3 0 were optimized using ZINDO utilizing 158 and 170 cycles of ZINDO respectively. The geometries likewise are listed in Tables 26 and 27 and the z-axis views in Figure 28 corresponding to the tables. For each of the structures obtained a CND0/2 calculation was also done. The final analytical gradients for each of the four structures is shown in Tables 28-31. The CND0/2 density matrices and the gross charge density are listed in the Appendix.

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zzcooirinooicDC 119 Table 23: Parameters of methyl vinyl ether. # 1 2 3 4 5 6 7 8 9 10 X Y Z -2.155475 -1.118756 -0.011722 -0.231796 1.350768 -0.021649 -1.837222 -0.074178 -0.022282 -0.564335 0.303948 -0.013968 1.709325 0.889606 -0.650592 -2.660554 0.641938 -0.042616 0.445465 -0.625126 -0.005711 1.685946 -0.016889 -0.025861 2.006073 0.246262 0.995184 2.406381 -0.741222 -0.440396 bond distance (Angstroms) atom # C -H 1.092035 ( 31) C -H 1.098396 ( 42) C -C 1.327889 ( 43) H -C 1.091380 ( 63) 0 -C 1.372204 ( 74) C -H 1.101167 ( 85) C -0 1.381721 ( 87) H -C 1.101936 ( 98) H -C 1.102508 (108) bond angles atom # ANGLE H -C -H 114.077 ( 136) ANGLE H -C -C 123.482 ( 134) ANGLE H -C -C 122.440 ( 634) ANGLE 0 -C -H 114.994 ( 742) ANGLE 0 -C -C 120.841 ( 743) ANGLE H -C -C 124.163 ( 243) ANGLE C -0 -C 111.256 ( 478) ANGLE H -C -H 108.279 (1085) ANGLE H -C -0 107.634 (1087) ANGLE H -C -H 108.388 (1089) ANGLE H -C -0 112.937 ( 587) ANGLE H -C -H 108.840 ( 589) ANGLE 0 -C -H 110.636 ( 789)

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120 Table 24: Parameters of N-methylmaleimide. # X Y Z H 1 2.468957 -1.316618 0.026650 H 2 2.422603 1.401612 0.024827 C 3 1.607880 -0.644828 0.016713 c 4 1.585969 0.699810 0.015605 0 5 -0.209097 -2.320781 -0.006374 c 6 0.225542 -1.119139 0.005417 N 7 -0.632975 -0.011410 0.012919 C 8 0.188179 1.124291 0.002032 0 9 -0.292639 2.308335 -0.014892 C 10 -2.049829 -0.010518 0.015301 H 11 -2.429451 0.911421 0.480609 H 12 -2.441137 -0.870347 0.579238 H 13 -2.456109 -0.064028 -1.007527 bond < li stance (Angstroms) atom # C -H 1.092179 ( 31) C -H 1.092047 ( 42) C -C 1.344817 ( 43) C -C 1.461491 ( 63) C -0 1.277886 ( 65) N -C 1.401489 ( 76) C -C 1.460885 ( 84) C -N 1.401510 ( 87) 0 -C 1.278058 ( 98) C -N 1.416856 (107) H -C 1.100271 (11-10) H -C 1.100206 (12-10) H -C 1.101864 (13-10) bond i angles atom # ANGLE H -C -C 123.103 ( 136) ANGLE H -C -C 128.893 ( 134) ANGLE C -C -C 108.004 ( 634) ANGLE C -C -H 123.119 ( 842) ANGLE C -C -C 107.826 ( 843) ANGLE H -C -C 129.056 ( 243) ANGLE C -C -0 128.825 ( 365) ANGLE C -C -N 108.835 ( 367) ANGLE 0 -c -N 122.339 ( 567) ANGLE C -N -C 127.813 (1076) ANGLE C -N -C 125.832 (1078) ANGLE C -N -C 106.352 ( 678) ANGLE C -C -N 108.970 ( 487) ANGLE C -C -0 128.997 ( 489) ANGLE N -C -0 122.033 ( 789) ANGLE H -C -N 111.539 (13-107) ANGLE H -C -H 107.861 (13-1012) ANGLE H -C -H 107.821 ( 13-1011) ANGLE N -C -H 110.857 ( 7-1012) ANGLE N -C -H 110.259 ( 7-10-: 11) ANGLE H -C -H 108.383 (12-1011)

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121 Fig. 27: Z-axis view of ZINDO geometry optimized molecules

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122 Table 25: Coordinates of C 2 and C 3 . c 2 # X Y Z H 1 -0.047261 -0.173410 2.052074 H 2 -0.155125 -1.668463 1.095092 H 3 -1.232495 1.749109 -0.552373 H 4 2.184063 -2.056608 1.116932 C 5 0.390623 -0.718163 1.202615 H 6 -0.670409 -0.700898 -0.625612 C 7 -0.272027 1.401415 -0.173834 C 8 1.867711 -1.036828 1.378780 C 9 0.075794 -0.010309 -0.192795 0 10 0.994258 3.482943 0.381848 C 11 0.777943 2.210983 0.205857 C 12 1.616201 -0.002367 0.367804 0 13 1.279182 -0.285027 -0.957784 0 14 2.467187 -0.511035 2.515959 N 15 1.844923 1.355599 0.658698 C 16 2.996969 -1.546737 3.264033 H 17 2.287192 -2.379177 3.385536 H 18 3.121724 2.421299 1.901999 C 19 2.150495 1.782710 1.005145 H 20 3.814882 0.929178 1.212002 H 21 3.925987 -1.922564 2.808128 H 22 3.232079 -1.134969 4.258494 H 23 3.598419 2.368683 0.186215 C 3 # X Y Z H 1 -1.386499 5.210777 -0.833059 H 2 -5.968158 4.880950 -0.881623 H 3 -3.822517 4.492895 1.324146 0 4 -3.394825 5.110639 -0.589539 C 5 -2.150468 5.398664 -0.061567 H 6 -2.111048 6.464612 0.215709 H 7 -6.172678 5.173616 0.832432 C 8 -5.654066 4.501787 0.129825 C 9 -4.160453 4.338033 0.281423 H 10 -1.905240 4.796018 0.826672 H 11 -5.765467 2.879046 1.509824 C 12 -5.744148 3.032752 0.411025 C 13 -4.327551 2.894143 -0.110248 H 14 -4.333150 2.847267 -1.218958 0 15 -7.459940 1.469682 -0.575175 C 16 -6.316233 1.781691 -0.101071 C 17 -4.054110 1.501000 0.261834 0 18 -3.019094 0.884686 0.684292 N 19 -5.277694 0.841652 0.034649 H 20 -6.522173 -0.807283 -0.140700 C 21 -5.455671 -0.564204 -0.023341 H 22 -4.908936 -1.002344 -0.873406 H 23 -5.089802 -1.045983 0.896849

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123 Table 26: Bond angles and bond distances (A) of bond angles atom # ANGLE H -C -H 107.788 ( 251) ANGLE H -C -C 108.165 ( 258) ANGLE H -C -c 101.515 ( 259) ANGLE H -C -c 113.628 ( 158) ANGLE H -C -c 112.147 ( 159) ANGLE C -C -c 112.685 ( 859) ANGLE H -C -c 125.828 ( 37-11) ANGLE H -C -c 121.081 ( 379) ANGLE C -C -c 112.839 (1179) ANGLE C -C -c 113.183 (1285) ANGLE C -c -H 122.608 (1284) ANGLE C -c -0 111.778 (128-14) ANGLE C -c -H 116.495 ( 584) ANGLE C -c -0 115.759 ( 58-14) ANGLE H -c -0 114.960 ( 48-14) ANGLE H -c -C 101.448 ( 695) ANGLE H -c -C 116.765 ( 697) ANGLE H -c -C 140.492 ( 69-12) ANGLE C -c -C 117.799 ( 597) ANGLE C -c -C 118.830 ( 59-12) ANGLE C -c -c 102.452 ( 79-12) ANGLE N -c -c 107.609 (15-117) ANGLE N -c -0 115.742 (15-11-10) ANGLE C -c -0 136.632 ( 7-11-10) ANGLE C -c -N 120.641 ( 8-12-15) ANGLE C -c -0 123.525 ( 8-12-13) ANGLE C -c -c 113.145 ( 8-129) ANGLE N -c -0 115.508 (15-12-13) ANGLE N -c -c 103.183 (15-129) ANGLE 0 -c -c 123.526 (13-129) ANGLE C -0 -c 108.947 (16-148) ANGLE C -N -c 119.418 (19-15-12) ANGLE C -N -c 125.326 (19-15-11) ANGLE C -N -c 113.438 (12-15-11) ANGLE H -C -H 108.741 (21-16-22) ANGLE H -C -0 110.785 (21-16-14) ANGLE H -C -H 109.370 (21-16-17) ANGLE H -c -0 106.863 (22-16-14) ANGLE H -c -H 108.701 (22-16-17) ANGLE 0 -c -H 112.274 (14-16-17) ANGLE H -c -N 110.679 (23-19-15) ANGLE H -c -H 107.904 (23-19-18) ANGLE H -c -H 107.846 (23-19-20) ANGLE N -c -H 110.480 (15-19-18) ANGLE N -c -H 111.608 (15-19-20) ANGLE H -c -H 108.192 (18-19-20)

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124 Table 26-continued . bond distance (Angstroms) c -H 1.101123 c -H 1.100036 c -H 1.089349 c -C 1.521305 c -H 1.099361 c -H 1.105017 c -C 1.596040 c -C 1.454064 c -C 1.392192 c -0 1.296855 c -C 1.458142 c -C 1.639265 0 -C 1.396661 0 -C 1.388887 N -C 1.407482 N -C 1.427047 C -0 1.383099 H -c 1.100683 C -N 1.416675 C -H 1.101350 H -C 1.101234 H -C 1.100986 H -C 1.101718 H -C 1.102110 atom # ( 52) ( 51) ( 73) ( 85) ( 84) ( 96) ( 95) ( 97) (117) ( 11 10 ) ( 12 8 ) (129) (13-12) (148) (15-12) (15-11) (16-14) (17-16) (19-15) (19-18) (20-19) (21-16) (22-16) (23-19)

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125 Table 27: Bond angles and bond distances of C3. bond angles atom # ANGLE C -0 -c 111.809 ( 549) ANGLE H -C -H 108.487 (1051) ANGLE H -C -0 113.244 (1054) ANGLE H -C -H 108.569 (1056) ANGLE H -C -0 108.738 ( 154) ANGLE H -C -H 108.437 ( 156) ANGLE 0 -C -H 109.261 ( 456) ANGLE C -C -H 114.950 (1282) ANGLE C -C -H 116.733 (1287) ANGLE C -C -C 93.767 (1289) ANGLE H -C -H 106.617 ( 287) ANGLE H -C -C 113.829 ( 289) ANGLE H -C -C 117.881 ( 789) ANGLE H -c -C 112.419 ( 398) ANGLE H -c -C 114.401 ( 39-13) ANGLE H -c -0 110.082 ( 394) ANGLE C -c -C 91.824 ( 89-13) ANGLE C -c -0 114.872 ( 894) ANGLE C -c -0 115.476 (1394) ANGLE C -c -H 108.831 ( 8-12-11) ANGLE C -c -C 142.517 ( 8-12-16) ANGLE C -c -C 91.780 ( 8-12-13) ANGLE H -c -C 102.703 (11-12-16) ANGLE H -c -C 110.231 (11-12-13) ANGLE C -c -C 99.574 (16-12-13) ANGLE C -c -C 100.005 (17-13-12) ANGLE C -c -H 102.365 (17-13-14) ANGLE C -c -C 145.470 (17-139) ANGLE C -c -H 110.043 (12-13-14) ANGLE C -c -C 94.215 (12-139) ANGLE H -c -C 107.519 (14-139) ANGLE C -c -0 133.392 (12-16-15) ANGLE C -c -N 104.362 (12-16-19) ANGLE 0 -c -N 122.245 (15-16-19) ANGLE C -c -0 133.887 (13-17-18) ANGLE C -c -N 103.983 (13-17-19) ANGLE 0 -c -N 122.125 (18-17-19) ANGLE C -N -C 124.441 (21-19-16) ANGLE C -N -C 125.429 (21-19-17) ANGLE C -N -C 110.118 (16-19-17) ANGLE H -c -N 110.965 (23-21-19) ANGLE H -c -H 108.334 (23-21-20) ANGLE H -c -H 107.813 (23-21-22) ANGLE N -c -H 110.184 (19-21-20) ANGLE N -c -H 111.317 (19-21-22) ANGLE H -c -H 108.116 (20-21-22)

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Table 27-continued bond distance (Angstroms) atom # C -H 1.101885 ( 51) C -0 1.382077 ( 54) H -C 1.102126 ( 65) C -H 1.100536 ( 82) C -H 1.101802 ( 87) C -H 1.107030 ( 93) C -C 1.510102 ( 98) C -0 1.393492 ( 94) H -c 1.101039 (105) C -C 1.498417 (128) C -H 1.109702 (12-11) C -C 1.515812 (13-12) C -c 1.505363 (139) H -C 1.109715 (14-13) C -C 1.467882 (16-12) C -0 1.276813 (16-15) C -C 1.467672 (17-12) 0 -C 1.276547 (18-17) N -C 1.407358 (19-16) N -C 1.408372 (18-17) C -N 1.418263 (21-19) C -H 1.100131 (21-20) H -c 1.101588 (22-21) H -C 1.101236 (23-21)

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127 Table 28: Energy gradient values of last cycle and summary of geometry optimization of cycles 95-106 for methyl vinyl ether. Energy = -43.187676 Geometry 9 Atom:Energy Gradient ( A. U . ) X Y z 1 0.000278 -0.000202 0.000308 2 -0.000347 0.000150 -0.000405 3 -0.000528 -0.000195 -0.000057 4 -0.000160 0.000598 -0.000042 5 0.000066 0.000220 0.000546 6 -0.000297 -0.000184 -0.000551 7 0.000128 0.000634 0.000734 8 0.000394 -0.000059 0.000110 9 0.000743 -0.000637 0.000170 10 -0.000277 -0.000326 0.000813 Optimization Summary for Number 9 Geometry All Gradients Lt 0, .00100 Geometry Converged Hurray Summary of Geometry Optimization Cycle Opt Type Energy Convergence Rms Grad 0 1 -43.187571 0.000000 0.000647 1 1 -43.187574 0.000000 0.000534 2 -1 -43.187578 0.000000 0.000524 3 1 -43.187581 0.000000 0.000464 4 1 -43.187583 0.000000 0.000631 5 1 -43.187620 0.000002 0.003397 6 -1 -43.187639 0.000001 0.002533 7 1 -43.187655 0.000000 0.001952 8 -1 -43.187674 0.000001 0.000455 9 1 -43.187676 0.000000 0.000407

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128 Table 29: Energy gradient values of last cycle and summary of geometry optimization of cycles 38-46 for N-me thy 1 ma 1 e i mi de . Energy = -84.993218 Geometry 8 AtomrEnergy Gradient (A.U.) X 1 -0.000471 2 -0.000523 3 0.000059 4 -0.000423 5 0.000885 6 0.000704 7 -0.000320 8 0.000444 9 0.000475 10 -0.000382 11 0.000404 12 -0.000370 13 -0.000482 Optimization Summary for Number 8 Y Z 0.000608 0.000130 -0.000326 0.000183 -0.000553 0.000034 0.000438 0.000050 0.000037 -0.000009 -0.000009 -0.000120 -0.000157 -0.000458 -0.000123 -0.000123 -0.000739 -0.000029 0.000629 0.000243 -0.000651 -0.000337 0.000584 -0.000086 0.000262 0.000522 Geometry All Gradients Lt 0.00100 Geometry Converged Hurray Summary of Geometry Optimization Cycle Opt Type Energy 0 1 -84.992995 1 1 -84.993015 2 1 -84.993036 3 1 -84.993106 4 -1 -84.993184 5 1 -84.993194 6 1 -84.993202 7 1 -84.993211 8 1 -84.993218 Convergence Rms Grad 0.000002 0.001404 0.000004 0.001140 0.000001 0.000949 0.000012 0.004004 0.000001 0.000919 0.000001 0.000680 0.000000 0.000503 0.000003 0.001092 0.000000 0.000414

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129 Table 30: Energy gradient values of last cycle and summary of geometry optimization of cycles 155-158 for C 2 . Energy = -128.683929 Geometry 2 Atom:Energy Gradient (A.U.) X Y Z 1 -0.000163 -0.000748 0.000142 2 -0.000680 -0.000241 -0.000154 3 0.000683 0.000471 -0.000026 4 -0.000316 -0.000689 0.000135 5 -0.000195 -0.000470 -0.000105 6 0.000179 0.000761 -0.000786 7 0.000133 0.000149 0.000479 8 -0.000310 -0.000575 -0.000033 9 0.000121 0.000207 0.000041 10 0.000922 -0.000324 0.000459 11 0.000533 0.000573 0.000613 12 0.000025 -0.000463 0.000244 13 0.000132 0.000014 0.000011 14 -0.000013 -0.000178 -0.000360 15 -0.000177 -0.000487 0.000479 16 0.000229 0.000280 0.000130 17 0.000538 0.000012 -0.000126 18 -0.000631 0.000052 -0.000342 19 -0.000204 -0.000011 -0.000274 20 0.000039 0.000133 -0.000561 21 0.000603 0.000639 0.000625 22 -0.000449 0.000762 0.000076 23 -0.000998 0.000132 -0.000616 Optimization Summary for Number 2 Geometry All Gradients Lt 0.00100 Geometry Converged Hurray Summary of Geometry Optimization Cycle Opt Type Energy Convergence Rms Grad 0 1 -128.683915 0.000004 0.000457 1 -1 -128.683923 0.000001 0.000433 2 1 -128.683929 0.000000 0.000427

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130 Table 31: Energy gradient values of last cycle and summary of geometry optimization of cycles 167-170 for C3. Energy = -128.645698 Geometry 3 Atom:Energy Gradient (A.U.) X Y Z 1 0.000120 -0.000153 0.000238 2 -0.000211 -0.000160 -0.000006 3 0.000778 0.000266 -0.000302 4 0.000075 -0.000196 -0.000158 5 -0.000072 0.000232 -0.000022 6 0.000077 0.000379 -0.000535 7 0.000071 -0.000167 0.000391 8 -0.000033 0.000040 0.000063 9 -0.000017 -0.000059 -0.000041 10 -0.000983 0.000623 0.000497 11 0.000459 -0.000204 0.000090 12 0.000105 0.000079 0.000112 13 0.000008 0.000105 0.000004 14 0.000007 0.000050 -0.000011 15 0.000381 0.000020 -0.000049 16 0.000117 -0.000054 -0.000379 17 0.000328 -0.000321 0.000890 18 -0.000480 -0.000304 -0.000205 19 0.000142 -0.000027 -0.000424 20 -0.000264 0.000202 -0.000041 21 -0.000169 -0.000157 -0.000066 22 -0.000268 -0.000237 -0.000086 23 -0.000172 0.000042 0.000043 Optimization Summary for Number 3 Geometry All Gradients Lt 0.00100 Geometry Converged Hurray Summary of Geometry Optimization Cycle Opt Type Energy Convergence Rms Grad 0 1 -128.645688 0.000001 0.000352 1 -1 -128.645692 0.000000 0.000309 2 -1 -128.645695 0.000000 0.000297 3 1 -128.645698 0.000000 0.000290

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C21 131 \ O M £ £ as a l/N f— f— m C\J -3 -3VO CM CO m cm I I 3 3 03 £ -3 < 7 \ cm cn rH 00 in vo CM CO m cm •H r-l I I N It CM O CM VO 3 <4 Fig. 28: Z-axis view of ZINDO geometry optimized molecules

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132 CNDO/2 calculations treating the complex as a single moiety were also done at various distances between the components. Methyl vinyl ether (ZINDO optimized structure) in plane z = distance, was made to approach N-methylmaleimide (ZINDO optimized structure) in plane z = 0, along the z-axis, i.e., along parallel planes with bond 3-4 of methyl vinyl ether (Fig. 27) directly over bond 3-6 of Nmethylmaleimide (Fig. 27). A view along this axis (2) is shown along with the potential diagram in Figure 29. The intermolecular interaction energy aE is obtained from the difference aE compl “ E c (r) E c ( -> where E c (r) is the energy of the system with distance y between subsystems A and B and The energy of stabilization ( -A E com p-| ex ) seemed to be maximum at an o intermolecular distance of 1.75 A. The energy of stabilization is calculated to be 75 kcal mole. The calculation done in the PCILO frame work 65 gave the energies depicted in Table 33. The energy of stabilization is again calculated from AE , . = E (r) E («) compl* c c E c (») here is taken as E c (7.0). The sum of the energies of the separated molecules was not taken as the reference since in the program, lone pairs were to be replaced by fictitious atoms having a

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133 Table 32: CNDO energy and difference in energy corresponding to various distances between molecules N-methylmaleimide and methyl vinyl ether. d ( A ) -E (au) -AE(au) -AE(kcal/mo1e) 7.0 131.9373 1.87xl0“ 5 0.0117 6.0 131.9373 3.06xl0" 5 0.0192 4.0 131.9374 1.383xl0~ 4 0.0868 3.5 131.9380 7.6xl0" 4 0.4817 3.0 131.9418 4.544xl0' 3 2.8516 2.5 131.9601 2.286xl0“ 2 14.3447 2.0 132.0218 8.46xl0~ 2 53.0649 1.75 132.0573 1. 201xl0 -1 75.3415 1.50 12.8622 -119.075 -74718.4 1.25 19.6092 -112.3281 -70484.77

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134 OJ O 2 ® Q O + I o LU II Qe o o LU < O CT> C\l CD E 0 ) vs. distance.

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135 zero nuclear charge and the number of lone pairs in the complex (9) are not the same as the sum of the lone pairs in the separated components (7). A plot of the fourth order corrected energy versus distance is shown in Figure 30. The energy of stabilization was maximum at an intermolecular distance of 4.2 A for the fourth order corrected plot. The energy of stabilization was calculated to be 395 kcal/mole. The coordinates for the complex with the moieties at a distance o of 7.0 A are listed in Table 34. Before the energies were calculated, care was taken that the bond polarities were adjusted such that the polarization energy is miminized and hence converges. This is done in the supplied program by recalculation. The 'del* parameters in case the 'POLO' subroutine does not cause the polarization energy to converge within the twenty cycles, for which the program is adjusted. Discussion The ZINDO optimization of C2 would give a higher energy of stabilization than is calculated by the CNDO method since this would involve minimization of the steric and other electronic factors (rehybridization, etc.) that effect the conformation corresponding to the minima in Figure 29. The ZINDO optimized structure would not be the same as the actual structure and hence the data would have to be judged qualitatively rather than quantitatively. As one can see from the formal charges of the carbons involved “charge transfer" has

PAGE 146

Vinyl methyl ether approaches N^methyl) maleimide along the z-axls. PC1L0 was used to calculate the energies (fourth order). 136 (“) vs. distance.

PAGE 147

137 Table 33: PCILO energy and difference in energy corresponding to various distances between molecules N-methylmaleimide and methyl vinyl ether. distance Order total after AE compl* zero + 1st 2nd corr 3rd corr 4th corr 4th order 7.0 -81567.61 -856.855 -519.087 -425.392 -83368.94 0 6.5 -81567.73 -856.631 -518.600 -424.666 -83367.62 +1.319 5.0 -81457.03 -1208.349 -774.369 -111.611 -83551.36 -182.42 4.5 -81541.06 -1148.428 -728.849 -288.748 -83707.08 -338.14 4.0 -81536.49 -1132.748 -740.938 -321.718 -83731.88 -362.94 3.5 -81567.03 -972.601 -517.099 -316.887 -83373.62 -4.674 3.0 -81649.63 -813.138 -345.600 -262.518 -83070.89 +298.05 2.5 -81772.13 -691.085 -203.728 -175.179 -82842.12 +526.82 2.0 -82002.43 -606.165 -133.117 -114.558 -82856.27 +512.67 1.5 -81991.07 -636.631 -69.434 -133.997 -82831.13 +537.81 N -methyl maleimide -54732.72 -381.715 -71.673 -47.561 -55233.16 Methyl vinyl ether -26155.52 -622.636 -46.575 -1204.213 -27935.80

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133 Table 34: Coordinates of t|je complex (E r *) with the moieties distance of 7.0 A. # X Y Z C 1 0.000000 0.000000 0.000000 C 2 -0.415600 -1.278900 -0.011600 0 3 2.627000 0.995600 0.000000 C 4 1.461500 0.000000 0.000000 N 5 1.914000 -1.326400 0.003500 C 6 0.768800 -2.134000 -0.020800 0 7 0.839500 -3.409900 -0.044400 C 8 3.253800 -1.787200 0.013600 H 9 -0.602500 0.910800 7.000000 H 10 1.944700 -0.908800 6.887200 C 11 0.000000 0.000000 7.000000 C 12 1.327900 0.000000 7.000000 H 13 3.670200 0.075800 7.652500 H 14 -0.585400 -0.921100 7.002200 0 15 2.031400 1.178100 7.014700 C 16 3.393500 0.947900 7.039700 H 17 3.781700 0.802900 6.018700 H 18 3.875300 1.840700 7.471400 H 19 3.663300 -1.862600 -1.006600 H 20 3.898600 -1.104100 0.586400 H 21 3.310100 -2.785000 0.473700 H 22 -1.434800 -1.671200 -0.012400 H 23 -0.596500 0.914800 0.010500 X 24 1.901400 1.928100 0.000100 X 25 3.250700 0.842200 -0.000100 X 26 0.002500 -3.956900 -0.059400 X 27 1.731800 -3.861300 -0.047700 X 28 1.895400 -1.330100 1.003300 X 29 1.774300 1.700900 7.827400 X 30 1.804700 1.703200 6.194400 X 31 -0.415600 -1.278900 0.988400 X 32 2.262700 0.995600 1.000000

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139 taken place. The PCILO program takes into account fourth order energy correction which is not the same as previously used 5 ^*^® (only went to third order). Again the data would have to be judged qualitatively. o The distance of 4.2 A seems to be large for charge-transfer complexes and the energy of stabilization also particularly large. Once again this would be an effect of numerous assumptions, approximations and estimations. The fact one should consider here would be that the total energy of the complex is approximately the same as calculated by the CNDO/2 and the PCILO program (132.0573 au or 82864.64 kcal/mole via CNDO/2 and 83731 kcal/mole via PCILO). However, one should remember that the PCILO method depends on the CNDO parameterization. Conclusions Qualitatively one can say: (a) One could have theoretically (PCILO and CNDO/2) predicted a "charge transfer" intermediate for the two reacting monomers. (b) Of the possible intermediates (C 2 and C 3 ) C 2 is more stable as predicted experimentally and hence is the intermediate.

PAGE 150

APPENDIX CNDO/2 DENSITY MATRICES AND GROSS CHARGE DENSITIES FOR N-METHYLMALEIMIDE, METHYL VINYL ETHER, C 2 AND C 3 , RESPECTIVELY

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N-Methylmaleimide N -O 0 O o N00 O 0 0-0 oooo — n© — sno MONO OOOO non o o on « ©no o K-n o « ® n ('90 n — no N®S» — N*. o o — — o oooo oon© n © 0 o NONO OOOO 0013 0020 0091 0007 0112 0085 0037 0026 K n o o n N o o 0 o o o 0 1 0 1 oooo 1 1 oooo 1 1 -oo o 1 1 1 oooo 1 1 1 0000 1 oooo 1 1 • • • • 0000 1 1 • • • • 0000 1 1 1 • o • o • o 10 • 0004 N >0 o o ©ON® ONN® OOOO 0009 ©O0© OOOO ooos oooo -NO « ONN « ooo © OOO N S90 OOO0 ooos oooo ©no© -ONS oooooo — -© ©NO oooo OOON — ON© o — — — ooo — oooo NNOO 00-0 oooo oooo 0 © o o 0 N o 0 N N o 0 1 o OOoO 1 oooo 1 ooo d t oooo 1 1 booo i i i 0000 1 1 0000 1 oooo 1 1 1 • o • o • 0 1 0 4 o © n ©n — N0O N 0 0 KO0O £^ 0 nn« o Notn o OOO o nsnn coon 9^n es«® »©— — 0 0 on o — OtftOO Ooo MO OOOO ntfto oooo noNO oooo 9SSO — NOO — — o oooo oooo oooo o o o o o o o o 0000 1 i T oo—o 1 1 000 o 1 1 T , 9000 Till oooo 1 1 1 oooo • • • • 0000 1 1 1 t • • t oooo • o t 0 1 • 0 1 e 0 n©o® ©K0O noo o <0 (ON O N CM C KOKO OAIOO OOOO 09*00 SN O — O-o OOOO — NOO NN-O oooo n*nn ooo oooo N«SS sn© o 0-0 NOO 00-0 oooo -0-0 n©oo oooo © o o N — o n o o 0 1 o OOOO 1 OOOO 1 000,5 obob 1 l l oooo ??°? • • • • 0000 1 1 • • • • ©OoO • 0 1 • o • o K so o o 0 in s«n«o 00*0 no*o 9M« -0*KO nn^o OOOO -NO K -O MN^o OOO o ons0 MONO ONOO oooo ©OO©0NO n^ — o oooo OOOO 0 N 0 N O O n©oo oooo N © O oooo oooo -0ON ©©o N O O OOOO 0 n o o n N o o — n o o 0 1 o oooo — OOO OOO o 0000 1 1 0000 1 1 1 oooo i • • • • oooo 1 1 1 • • • • OOOO • o • 0 1 • 0 1 © c CO o to o o o oonn oooo ooos oooo -0 — 0 OSOfi OOOO OOOO oZ°Z ooo o O O o sno# ns-o oooo* OOON ©00 OMS O O O — OOONO®S © — — 0 ooos oooo — ©ON o n n N OOOO OOON non OON® oooo oooo 0 o o © — o © N N o o 0 1 oooo oooo 1 000 o 1 1 0000 1 1 1 oooo • T i i oooo 1 • • • • oooo 1 1 • • • • oooo 1 1 • o • o • 0 1 n c CO c n o ©©0 coco nNo OOOO non* COO N ®s#o Oioo ©-*© KlNIt © -0—0 OOO Q 00-0 ms^m -9no MNOO nON -NMnoNo oooo noon nnno O0O oooo N©n© no-o N n n o OOOO ©0©©o Oooo oooo n © o o N o o o n o o o 0 1 0 1 00-0 1 OOOO 1 OOOo 0000 1 1 1 0000 1 1 • • • • oooo 1 • • • • OOOO 1 • • • • 0000 1 1 1 • o • 0 1 • 0 1 to 0 0 -©O -0©O s»«o n — nn 0 on o 00*0®O©0 0 — K O 0-0 ON — 0 ® ©0N N^SS O0N© 0 o c N O ®no 00*00 0O0O OMOO OO-o ooo 0 NOO O oooo — N — O OOOO o--o oooo n®oo OOOO — o o o o o o 0 1 oooo OOOO 1 1 oo o o 0000 1 II 1 oooo 1 OOOO 1 | • • • • 0000 1 • • • • 0000 1 1 1 • o • 0 1 • o to N 0 • o o Q O • 0 1 N -® c --0O n*©o OOOO • • • • — ooo 1 nn® 0*0 K©0 no«o • • • • oooo 1 0O0K N O O o O 0 o o ooo o • • • • oo o o 1 1 — ®nn 0crsin Nnoo n^ — o • • • • oooo N N N — 0 00*0 — o oooo • • • • 0000 1 1 1 N-00 NS-O ONOO OOOO • • • • 0000 1 1 1 N © — — 0© M NNno oooo • • • • oooo — ©«M ©© o N O O oooo • • • • OOOO 1 1 N 0 o o • 0 1 0 — o o • o 0 N o o 0 1 ® c CM «o o • 4 N >0 o ©0*0 0 O ONHO O OOo OOOM 0 N© C N — o 0©0© O® on — o onN 0 OO Oo ©C©0 o--o ©cn© Oooo ©an cun n — <0 0 0O OOOO N-0© S0SO NN— O OOOO — —00 NO — — no oooo OSND 00—0 — N Oo OOOO N © o o 0 o 0 n o o 0 1 o 0000 1 1 1 1 oooo 00 Oo 1 I 1 1 Oooo oooo 1 0000 1 1 0000 1 1 1 • • • • 0000 1 1 • 0 1 • o • o c N — <0 © c c c o ccno K 00 c 90 (*<0*0 NO00 <©0 Ofltno oooo M9 0« 0-2. --no oooo O' 00 • ©o NN-O oooo ©sn n^ — — 0 00O oooo MSO© -NOO 0CNO oooo ©©*> ©oo onNO oooo n©©n 0-00 — NOO oooo 0 o © N o o N N o o o 0 1 oooo 1 0000 1 1 1 00 o o 1 l t i 0000 1 1 1 oooo l i OOOO 1 0000 1 1 1 • • • • 0000 1 1 1 • o • 0 1 • o 0 (ft VIXWN o.Q.0. 0 a.aa 0*>N a. a a lltXSN a.a.0. (AX VN a. aa IAX>N a do. 0XNN 0.0.0. 0X>N 0.0.0. 0 0 0 z r UUUU u^uu O OO Cj uuuu 2722 <->UuU oooo uuuu r z z N nnmn 0000 COCO ssss 0 0 0© ©©©© oooo m N n — — — — — — — — N n+cc M)90 -Mn« c 0 S« 9*0— N n ©© S#90 0 NNNfg n n n n nnnn n n n 141

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34 35 36 37 1 1 M s 0*0 003 0*0151 -0* 0079 0*0022 2 2 M s 0*0003 -0*0092 0* 01 46 0*0035 3 3 C s -0* 0 002 -0.0067 0*0018 -0*0026 4 3 c PX 0*0000 0*0114 -0* 00 76 0.0020 5 3 c PV -0*000 1 0*0093 -0* 0087 -0*0003 6 3 c PZ -0*0 083 0*0104 0* 01 18 -0*0229 7 4 c s -0*0002 0*0035 -0. 0073 -0*0031 0 4 c PX 0*0000 -0.0099 0*0120 0*0031 9 4 c PY 0*0001 0*0095 -0* 0084 -0*0006 10 4 c PZ -0*0080 0*0095 0*0125 -0*0226 1 1 5 0 s -0*0026 0*0037 0*0023 0*0008 12 5 0 PX 0*0050 0*0096 -0* 01 49 0*0021 13 5 0 PY -0*0028 -0*006 0 0*0070 -0.000 1 14 5 0 PZ -0.0171 0*01 95 0*0289 -0*0444 15 6 c s -0*0005 0 *0511 -0*0254 0*0069 16 6 c PX 0*0005 -0*0541 0*0249 -0*0073 1 7 6 c P Y 0.001 1 0*052 0 -0. 0325 0*0062 1 0 6 c PZ —0 *0 04 0 -0*0229 -0*0232 0*0460 19 7 M s -0*0030 -0*0072 -0* 0072 -0*0044 20 7 N PX 0*0045 -0*0002 0*0021 0*0030 21 7 N PY 0*0001 -0*0402 0.0377 0*0026 22 7 N PZ 0* 1 944 -0*0540 -0* 0662 0*1209 23 8 C s -0*0008 -0*0283 0*0492 0*0114 24 8 c PX 0*0009 0*0256 -0* 04 99 -0*0117 25 6 c PV -0.001 1 0*0382 -0. 0518 -0* 0112 2 6 8 c PZ -0*0025 -0 *0185 -0.0274 0*0464 27 9 0 s -0.0031 0*0031 0* 0044 0*0011 2 8 9 0 PX 0*0059 -0*0189 0* 0081 0* 0031 29 9 0 PY 0*0034 -0 .0077 0* 0046 0*0006 30 9 3 PZ -0*0161 0*0251 0* 0229 -0.0431 31 1 0 c s 0*0007 0*4 982 0*4990 0*4996 3 2 1 0 c PX -0*0007 -0.2803 -0*2872 -0 *2 928 33 1 0 c PY 0*0 0 04 0*7209 -0.6730 -0*0426 34 1 0 c PZ 0*9835 0*3637 0*4401 -0*7970 35 11 H s 0*3637 0*9972 -0. 0257 -0*0363 36 12 H s 0*4401 -0*0257 0*9995 -0.038 1 37 13 M s -0*7970 -0*0363 -0* 0381 1*0110 TOTAL EMEWCV 97 . 720107730 *. 1 2 3 A 5 6 7 0 9 10 I 1 12 13 H C C o c N c 0 c H H H BINDING Energy* 0*9626 0*9624 •0240 *•02*9 6.2990 3.6781 3.1707 3.6788 6.3004 3.890 1 0.9972 0.999 8 1.0110 0. 4607420199 A.U. COMPONENTS densities S.P » .0 total X « .39198 0.76180 0.00000 2.1 8378 r 0.04018 0.02339 0. 00000 0.06388 — "MW J J 01 POLE MOMENT. 2 . 18718 OEBYES Z 0.10612 -0.00364 0. 00000 0. 10248

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Methyl vinyl Ether N 9*N© Nn©9 N O fNHIAKNO • O O — — O — HNNO «o o ooeo oooo t • •••• • • • • o e oooo oooo I I I I « k« 9 ® N 9 ©nn© * o (W NN-O ©©*• * N n N©© N*Nn N — — o o OOON OOO — O OONfl ON 99 o NO o oooo oooo o o OOO — WN — N o • • • # • • • • • • • • • • • 1 • # • # • e o o Oooo OOOO o o oooo OOOO — o N 9 ON 9 N*® O © o — — N — NNOO N © n — 0«(w* NOOO N o O-NN © one N n ®N * ID-NO *® OO N N 090 0 — — oo o n o N -N-O 0090 o o N n N O oooo O o • • • • • • • • • • • • • • • • • • • • • • 0 1 O 0000 1 1 oooo o o 0000 1 1 0000 1 1 0 1 0 1 N « oooo — NOO n OOON -©09 N © ® ® N©C O o® o N nn 9— ©O © 9 ON o NOO — ® noo N ONOO nNno O O O N * *NO 0900 O o nn*o oooo o o • • • • • • • • • • • t • • • • • « • • • • o O 0000 1 1 1 1 0000 1 0 1 0 1 °?°? oooo 1 o o * n NoO — NN N 90® N n ®9 © N o * 9 on** N N O w N ON ON ® n *w n o N NO jt N ® © n — O — NO NIDOO o © o ® n®— o oooo o o Nnno oooo o o • fl • • • • • • • • • • • • • • • • • • • • o O OOOO — ooo o o ooo o oooo o o I o n -M# —090 O — o O — No + 0+0 n 0O O OOOO 0-00 — — O O OOO— 0009 O O • • • • • • • • • • • • o o ooo— oooo o o III I II 9 e ®N*n OON9 N N N N OONN © N N n O o® O --©o ©ON O o n N O 0090 — N — O o © t • • • • • • • • • • • • 1 • 0000 1 OOOO 1 o o N — ®NNN NOO© o M « n * o — no©N N * N *9 — 0 — ©— — N N O 0900 ©NO O O • • • • • • • • • • • • 9 1 0 1 0000 1 1 oooo 1 1 1 o 0 1 N N ® ©© — *®9© 9 o N 9 Nnoo ONON N « — **-o 9N ©O © O oooo n* — o O © • • • • • • • • • • • • O 0 1 — ooo 1 1 1 OOOO 1 1 1 o o © ® n — ©n n©N* N © © © 9®N — 9 ©-© O * N* — -NOO ooo o © — o oooo ©NN o O o • • • • • • • • « • • • O — oooo OOOO o o — fl 9 — © ® * * GS«« 009 — N — o N«Oo OOOO OOO o • ••• •••• 0000 oooo 1 III o o IN! © O — © 9 *N9© 0900 N iv* n — — 09 nooo * oo o o o O IV* ooo— c (WO o Oooo oooo * • • • • • • •••• • O o Oooo oooo o lilt I © n oooo 9 o • • 0 o 1 I N^9© (W(V*(WO **« O ©NNO • • • • OOOO I I ©X>N a. a a. no© *ono oiwiwo oooo • • • • OOOO 0.0.0. T Z bUUU UUUU T Z oooo N ©X>N © © © © ©X>N © XNN © © ©X>N ©JON © © a.0. a. o. o. a 0.0.0. 0.0.0. 0.0.0. 0.0.0. noon UUUU z z T z UUUU UUUU T Z oooo UUUU T z NSNN ©Ooo 9 01 N nnnn ** © © NNNN ©o® ® 9 o n *©© NOOO N N n*©© N 090 N n*©© N ® 9 O N — — — N N N — — — — — — — N N

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TOTAL energy » -•21 70987040 1 2 3 4 5 6 7 6 9 XO # H C C H H O C H H BINDING ENERGY* 0.971 7 1*0 158 4.1 104 3.8280 1*0194 0.9 79 6 6 *1958 3.8483 1 *0174 1 *0134 -3.8077704854 A. COMPONENTS 0ENSIT1ES S.P P.0 total 01 POLE MOMENTS * 0.29894 0.33343 0 .00000 0.63237 Y 0.61829 1* 14493 0.00000 1 • 76322 FOMENT. 1.87340 0E8YE3 Z -0.01 152 -0. 01 680 0.00000 -0.02831

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147 h 1 2 3 4 9 * 7 0 9 to 11 1 ft H s 0.9301 0.0391 0.0601 0.0669 0.9010 0.3312 6.4291 0.6474 0.0280 0.0166 0.0007 a 2 N 9 0.0391 0.9942 0.0011 0.0006 o.ooao 0.4100 0.7136 0.1 102 0.1227 0.0290 0.0180 3 3 N 9 0.0001 0.0011 0.9710 0.0069 0. 0249 0.0032 0.0203 0.0403 0.0709 0.9991 0.7124 4 4 H 9 0.0660 0 . 0000 0 . 0069 0.9799 0.0069 0.0070 0.0274 0.0213 0.0000 0.0003 0. 0057 3 9 C 9 0.9010 0.4910 0 . 0249 0 . 0069 0.9982 0.1194 0.0299 0.0777 0.0241 0.0013 0.0194 4 9 C PX 0.3312 0.4166 0. 0032 0.0070 0.1154 0.9610 9.0940 0.0671 0.0247 0.0044 0.0196 7 9 c PV 0.4291 0.7130 0 . 0263 0.0274 0.0299 0.0940 1.0206 0.0046 0.0176 0.0044 0.0099 6 9 c PZ 0.6474 0.1102 0.04 03 0.0213 0.0777 0.0671 0.0046 1.0296 0.0404 0.0004 0.0192 9 * M 9 0.02 00 0.1227 0 . 0709 0.0000 0.0241 0.0247 0.0176 0.0404 1.0030 0.0000 0.0210 10 7 c 9 0.0166 0.0290 9. 5391 0.0003 0.0013 0.0044 6.0044 0.0004 0.0000 0.9835 0.0699 tl 7 c PX 0.0007 0.0100 0.7124 0.0057 0.0134 0.0196 0.0099 0 . 0 152 0.0210 0.0699 1.0300 i a 7 c PT 0.0371 0.0464 0.2402 0.0037 0. 0064 0. 0007 9.0082 0.0131 0.0213 0 .0883 0.0499 13 7 c PI 0.0063 0.0213 0.2023 0.0234 — 0. £937 0.0229 0.0236 0.0563 0.0046 9.0229 0.1981 1 4 O c 9 0.0216 0.021 1 0 . 00 80 0.5923 0 . 21 6 * 0.3679 0. 1013 0.0772 0.01 69 0.0152 0.0019 15 • c PX 0.01 SO 0.0271 0.0066 0.2204 0.3740 0.6196 0 . 2 J 07 0.2 002 0.0954 0.0030 0.0239 ft * 0 c PV 0 . 0104 0.0171 0. 0014 0.7512 0.0390 0 . 094 9 0.1491 0.0126 0.0210 0.0060 0 . 0083 IT 0 c PZ 0.0110 0.0221 0. 0010 0.1763 0.0106 0*0440 9.0352 0.1927 0.0960 0.0164 0.0196 1 * 9 c 9 0.0043 0.0330 0.0439 0.0130 0.1703 0.0917 0.1460 0.2856 0.4991 0.3033 0.0096 19 9 c PX 0.0029 0.0221 0 . 0224 0.0094 — 0.0399 0.0749 0.0923 0.0047 0.5364 0.1334 0. 1439 20 9 c PV 0.0231 0.0019 0.0209 0.0063 0.1936 0. 0749 0.0278 0.2577 0.9431 0.4309 0.1469 tl 9 c PZ — 0.0036 0.0316 0.0124 0.0429 0.3233 0.1920 0.3097 0.4 370 0.3040 0.0099 0.0577 22 10 0 9 0.0029 0.0032 0.0126 0.0023 0.0002 0.0009 0.0006 0.0 oot 0.0030 0.0060 0.0120 23 10 0 PX 0.0021 0.0094 0.0190 0.0040 0.0143 0.0009 0.0126 0.0149 0.0230 0.0894 0.0075 24 10 0 PY 0.0143 0.0072 0 . 0270 0.0142 0.0043 0.0007 0.01 04 0.0033 0.0277 0.0287 0.0246 29 10 0 PZ 0.0003 0.0049 0.0161 0.0094 0.0441 0.0064 0.0304 0.0504 0.0019 0.0109 0.1314 2 * ftl c s 0.0063 0.0049 0 . 0392 0.0006 0.0103 0.0006 0.0144 0.0142 0 . 0662 0.3673 0. 3701 27 11 c PX 0.0021 0.0007 0. 0002 0.0030 0 . 0160 0.0030 0.0163 0 . 0 156 0.0310 0.3861 0.1631 20 1 ft c PY 0.0100 0.0060 0.0200 0.0129 0.0100 • 0.0017 0.0170 0.0125 0.0303 ”0 .2 422 0.2781 29 11 c PZ 0.001 1 0.0097 0.0003 0.0106 0.0603 0.0146 0.0306 0.0621 0.0103 0.1366 0.3220 30 12 c 9 0.0244 0.01 73 0. 0262 0.0163 0.1243 0 . 1672 0.0777 0.0 661 0.0118 0.0012 0.0135 31 12 c PX 0.0401 0.1041 0.0920 0.0001 — 0 r 2320 0.1619 0.2331 0.2 666 0.0929 0.0207 0.0331 32 12 c PY 0.0323 0.0006 0 . 0130 0.0326 0.0924 0.1372 0.0276 0.0 787 0.0146 0.0213 0.0081 33 12 c PZ 0.0197 0.0062 0.0090 0.0192 0.1640 0.1664 0.1419 ” 0.001 7 0.0919 0.0131 0.0167 34 13 0 9 0.0261 0.0047 0.0194 0.0116 0.0069 0.0019 0.0132 0.0065 0.0196 0.0041 0 . 0294 33 13 0 PX 0.0940 0.0710 0 . 0310 0 . 0271 0 . 04 76 0.046 0 0.0302 0.0332 0.0496 0.0083 0. 0620 34 13 0 PV 0.0043 0.0020 0.0224 0.01 1 1 0. 0360 4. 0071 0.0073 0 . 021 3 0.0661 0.0364 0.0131 37 13 0 PZ 0 . 0*76 0.0204 0 . 0237 0.0476 0.0497 0.0207 0.0467 0.0663 0.0291 0.0010 0 . 017 * 30 14 0 9 0.0311 0.0240 0.0041 0.0190 0.0070 0.0046 0.0130 0.0188 0.0021 0.0000 0.0000 39 14 0 PX 0.0204 0.0240 0.0035 0.0344 0.0507 0.0737 0.0390 0.0350 0.0246 0.0010 0.0061 40 14 0 PV 0.0336 0.0177 O . 0020 0 . 1039 0.0023 0.0093 0.0119 0.0 209 0.0076 0.0011 0.0023 41 14 0 PZ 0.0999 0.0370 0 . 0063 0.0314 0 . 0169 0. 0243 0.0206 0.0137 0.0106 0.0000 0.0015 42 19 N s 0 . 016 * 0.0233 0 . 0007 0.0394 0.0096 0.0110 0.0143 0.0 01 5 0.0371 0.0246 0 . 0174 43 19 M PX 0.0060 0.0393 0 . 0699 0.0193 0 . 036 3 0.0080 0.0129 0.0303 0.0469 0.0197 0.0337 44 IS N PV 0.0460 0.0416 0.0390 0.0712 0. 006 0 0.0106 0.0014 0.0091 0.0396 0.0166 0.0103 40 19 N PZ 0.0109 0.0494 0.0349 0.0249 0.0441 0.0410 0.0041 0.0210 0.0147 0.0023 0. 0346 46 1* c s 0.0010 0.0017 0.0007 0.0276 0.0075 0.01 17 0.0049 0.0009 -0.0011 0.0008 0.0010 47 1 6 c PX 0.0039 0.0009 0.0002 0.0192 0.0012 0.0049 0.0067 0.0077 0. 0046 ” 0.0007 0.0017 40 16 c PY 0.0079 -0.0010 -0. 0017 0.042 9 0.0126 0.0174 0.0001 0.0 062 0.0009 0.0006 0.0005 49 16 c PZ 0.0047 0.0021 0. 0006 0.0036 0.01 44 0.0194 0.0012 0.0002 -0.0005 0.0 006 0.0006 50 17 H 9 0.0066 -0.0011 0.0009 0.0090 0.0060 0.0119 0.0033 0.0041 0.0010 0.0006 0.0006 91 to H 9 0.0090 0.0007 0.0002 0.0033 0.0002 0.0019 0.0027 0.0042 0.0044 0.0007 0.0060 S2 19 c 5 0.0019 0.0127 0.0167 0.0003 0.0147 0.0096 0.0113 0.0163 0.01 18 0.0260 0.0261 S3 19 c PX -0.0011 0.0192 0 . 0277 0.0026 0.0167 0.0063 0.0166 0.0224 0.0220 0.0399 O . 0337 54 19 c PV 0.0013 0.0119 0.0130 0.0009 0.0137 0.0064 0.0023 0.0 142 0.0102 0.0124 0.0178 SS 19 c PZ 0.0013 0.0061 0 . 0069 0.0019 0.0069 0.0071 0.0069 0.0079 0.0069 0.0103 ”0.0010 5* 20 H 9 0.0064 -0.0099 0.0176 0.0096 6.0094 0.0063 0.0626 0.0001 0.0076 0.0067 0.0060 97 21 H 9 0.0006 0. 0039 0.0006 0. 004 7 0.0000 0.0001 6.0019 — 0.0014 0.0010 0.0006 0.0002 90 22 H 9 0.0100 0.0034 0.0020 0.0204 0.0046 0.0062 0.0006 0.0002 0.0006 0.0010 0.0006 SO 23 n 9 0.0017 0.0169 0.0090 0.0110 0.0114 0.0666 0.6032 0.0000 0.0117 0.0013 0.0105

PAGE 158

148 12 13 14 ia 14 17 18 19 20 21 22 I 1 M S 0*0371 • 0.0063 0. 0216 4 * 01 SO 4*4144 • 4*0114 • 4*0063 0.0029 • 0. 0291 • 0.0036 — 0. 0025 2 2 H 9 • 0*0444 • 0*0213 0*0211 • 4.0271 4*4171 • 4*4221 4*4354 0*0221 0*0019 0.0516 0.0032 3 3 M 9 0*2482 • 0.2029 • 0*0080 0.0066 • 0 * 0014 0*0010 • 0*0635 • 4*0226 0*0209 • 0.0124 • 0.0126 4 4 H 9 0*0037 0*0294 " t .& S 23 0*2204 4 * 7512 • 4*1763 0*0130 9*0096 0 * 0 O £ 3 " 0 . 0429 -v 0*0023 9 9 C 9 0.0044 • 0.0937 0*2166 • 0*3740 0 * 0390 0*0106 / 0.1703 0.0395 936 0 .3233 j — 0. 0002 9 C RX 0.0087 0.0229 0 . 34 79 • 0*6196 0*0549 0*0496 j 0.091 7 0.0769 0.0749 • 0.1520 1 0.0005 9 c py • 0.0082 • 0.0236 0. 1013 0.2307 0 * 1491 4.0352 ^ 0.1668 0.0923 • 0.0276 0.3097 0. 0006 a 9 c RZ • 0*0191 0*0563 0*0772 • 0*2002 • 0*0126 0 * 1927 y 0.2856 • 4.0647 0.2577 4.4370 • 0.0001 9 4 M 9 0*0213 • 0*0046 0 * 0169 • 0*0954 0*0210 0*0568 ' 0.«91 • 0.9 364 • 0 . 5431 ^= 4.3046 0.0036 10 7 c S 0.0883 0.0220 0 * 01 52 O . 0030 0*0060 • 4.0164 0.3033 • 0.1 334 0.4309 4.0099 11 c RX 0.0494 0. 1981 • 0.0015 0.0239 0 . 008 3 • 0.0156 ( 0.0856 0.1 439 0.1489 0.0577 jo . 01 26 c 0.8823 • 0.0344 0 . 0206 0.0052 0 * 0093 0.0149 VO .6876 0.2 197 • 0.5796 -0 .0 049 • 0.0039 13 7 c RZ • 0.0344 1*4677 0.0256 • 0*0381 • 0*0146 . 4.0164 -<*,0055 6.6472 0.0401 0.3004 0.0051 14 8 c S • 0.0204 0*0256 0 . 9618 0*0729 0.0675 0.0037 0.0061 4.0 066 0.0163 0.0259 0. 0004 19 8 c RX 0.0092 • 4.0381 0. 0725 0.9933 0 . 0680 • 0.1302 0.0080 0.0243 0.0056 14 c 0.0093 • 0.0146 0. 0875 0.0680 0.9700 • 0.0324 • 0.0006 0.0133 0.0077 0.0262 0. 0020 IF a c RZ 0*0144 0*0164 0 * 0037 • 0* 1302 0*0324 0.9631 • 4.0023 4.0 233 • 0.0110 0.0128 0.0016 ia 9 c 9 • 0.4876 0.0055 0.0061 0.0080 -o.'oooo • 0.0023 4.9533 • 0 * 1 700 O.IISI 0.0690 0.0161 19 9 c RX 0.21 97 0.0472 0 . 0066 0.0243 0.0133 • 0.0233 4 . 1700 0.8205 0.0088 -0.0022 20 9 c py 0.5796 0.0401 0.0163 0.0056 0. 0077 •0. 01 1 0 0.1151 0.0088 1.0830 0.0176 0.0261 21 9 c RZ • 0.0049 0*3086 • 0.0259 0.0104 0*0262 0.0124 • 4.0694 4.0022 0.0176 0.8692 0.0030 22 10 0 9 0.0099 0.0091 • 0 . 0004 • 0.0007 • 0. 0020 0.0016 0.01 81 • 4.001 0 0.0261 0.0030 1.7706 23 1 0 0 RX 0.0399 0.1256 0. 0060 0 . 01 1 9 0. 0092 0.0181 • 0.0291 0.0 175 0.0379 0.0281 0.0755 24 1 0 0 PY 0.0084 0.0238 0 . 009 7 0.0119 0.0110 • 0.0223 0.0509 0.0 119 • 0.0490 0.0057 29 10 0 PZ 0.041 1 • 0.2803 0 . 0094 0.0028 0.0013 0.0031 • 4.0093 0.0 341 • 0.0019 0.0497 0.0490 24 11 c 9 0.3343 0.1582 0.0163 0.0130 0.0190 • 4.0244 0.0161 0.0093 0.0270 0.0062 0.2367 27 1 1 c • 0.3969 0.3191 0 . 0139 0.0212 0 * 024 0 4.0292 • 4.0092 • 0.0229 0.0137 0.0233 0.0604 28 1 1 c 0.076 T 0.1379 0 . 019 / • 0.0192 0 . 01 85 0 . 0349 • 4.0022 • 0.0234 • 0.0464 -4 .001 7 0.3834 29 II c RZ • 0 . 1 782 0.9106 0 . 0069 0.0009 0*0028 • 0.0064 • 4.0484 • 0.0317 0.0077 0.021 1 0* 0361 30 12 c 9 • 0.0404 0.0160 0*2662 0.0369 0*3198 • 0.3492 4.1362 0.2 083 0.0074 0.0356 0.0143 31 12 c 0.0873 0 . 11 76 0.3268 0*1986 • 0.2746 • 0.2586 • 0.3304 0.0498 0.2647 0.0030 32 12 c • 0.0199 0.0060 -0.2798 0.0426 0.2226 0.4076 • 4.0093 0.0021 0 . 06 55 0.0325 33 12 c RZ 0*0104 • 0.0594 0 * 2363 • 0.0393 0*3000 • 4. 1635 • 4.0744 • 0.1400 0.0069 0.0990 0.0031 34 13 0 9 • 0.0089 0.0430 • 0.0078 0.0004 0.0043 0.0177 4.1351 0.2935 • 0.0954 0.1779 0.0007 39 13 0 RX 0.0140 0.1920 0 . 0034 • 0*1314 0.0442 0 • 0745 • 0.2817 • 4.4533 0. 1073 0.4744 0.0006 34 13 0 PY 0.0441 0.0202 0 . 04 09 0.0207 0. 0363 -0 . 04 04 0.0267 0.1 190 0.0609 0.0827 37 13 0 RZ • 0.0044 0.0031 • 0.03 74 • 0.0093 0*0361 0.0458 4.1384 0.2847 • 0.0597 0.071 1 0.0012 34 14 0 9 0.0022 • 0.0015 0 * 1959 0 * 1632 0* 1557 0.3244 4.0160 0.0124 0.0127 0.0176 0.0008 39 14 0 RX 0.0024 0.0109 0.1966 0*0147 0*1326 • 0.3051 0.0188 0.0077 0.01 91 0.0216 14 0 0.0024 0.0068 0. 1790 • 0.1592 0*0026 0.2937 -0.01 13 • 0.0 496 0.0098 0.0 160 0.0009 41 14 0 RZ 0.0088 0.0008 • 0.3671 • 0*3117 • 0*2434 • 0.4490 • 0.0206 • 4.0207 0.0164 • 0.0220 0.001 1 42 19 N 9 0.0110 • 0.0280 • 0.0030 0*0063 • 0*0130 0.0075 • 4.0396 0.0230 • 0.0982 • 0.0096 0.0046 0.0127 0.0235 0 . 0004 0 * 0488 • 0 . 01 36 0.0311 0.0965 0.0 121 0.0116 0.0410 • 0.0129 19 0.0267 0.0080 0 . 01 70 0.0224 0 . 0130 • 0.0518 • 4.0280 4.0330 • 0.0127 0.0 154 0.0104 49 19 N PZ 0*0162 0.1079 • 0.0412 0*0488 0*0007 0.0094 4.0051 0.0060 0.0320 0.0757 0.0049 44 14 c 9 • 0.0005 •0.0015 0 . 0220 0*0315 0 * 0030 0.0451 • 4.0007 • 4.0 002 0.0008 0.0026 47 14 c RX 0.0006 0*0030 • 0.0252 0.0159 0.0233 • 4.0396 • 0.0009 0.0 006 • 0.0002 0.0009 48 1 4 c 0.0012 0.0009 0 . 01 84 0 . 0 08 1 0.0060 • 4.0002 4.0031 4.0031 0.0034 0.0067 0.0001 14 c RZ 0.0004 0.0018 0*0396 • 0*0470 0. 0432 • 4.0553 0.0016 0.0006 •0.0008 0.0015 0.0000 90 17 H 9 • 0.0013 0.0019 • 0. 0344 • 0*0103 • 0*0178 • 4*4244 0.0029 • 4.4419 0.0026 -0.0050 0*0000 91 ia H 9 0.0043 0.0206 0 * 0069 • 0*0021 0*0433 4*4446 4.0423 4.4449 • 0.0026 0.0065 0*0000 92 19 c 9 0.0119 0.0129 • 0.0038 • 0.0192 • 0.0093 0*0204 4* 020 0.0166 0.0066 0.0192 93 19 c RX • 0.0179 0.0147 0. 0001 0.0221 0.0097 • 4*0169 4.0316 4.0 172 • 0.01 19 0.0229 0.0043 94 19 c 0.002 6 0.0066 0.0009 0.0124 0. 0062 4*0153 4.0183 • 0.0099 • 0.0001 0.0129 0.0021 99 19 c RZ • 0*0039 • 0*0186 • 0.0002 0.0102 0.0007 0*0025 4.0081 4.0042 • 0.0019 0.0062 0.0007 94 28 M 9 • 0.0141 4 8 O • 0 1 0.0096 0*0084 0*0473 4*0404 4*4044 4.0051 0.0073 0.0043 0.0003 97 21 H 9 • 0*0004 0*0004 • 0.0192 • 4 * 00*1 4.0454 4*4401 4*4414 • 4.0413 0.0007 • 0.0025 •0.0001 90 22 H 9 0*0021 • 0*0014 0*0743 0*0417 4*41 24 4*4894 4*4487 y 0*0444 • 4.0047 0.0096 • 0.0001 99 23 H . 9 0*0089 0*0167 • 0*0072 4*0123 4 * 4414 4*4418 4*4432 0*4424 0.0462 • 0.0167 0.0006

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149 23 24 25 26 27 1 H 5 -0*0021 0*0145 0* 0005 0*0063 0* 0021 ! 2 N S “0*0054 -0*0072 “0*0045 0*0049 0*0007 1 3 H 5 0*0150 0*0270 0*0101 -0*0352 0* 0002 > 4 H 0 0*0040 “0*0142 0* 0094 -0*0006 -0 * 0030 ' 5 C S “0*0145 -0*0043 0*0441 -0*0103 0*0160 5 c PX 0*0009 0*0007 -0*0064 -0*0006 -0* 0030 5 c PY “0*0126 -0*0104 0*03 04 -0*0144 0.0183 > 5 c P2 0*0149 0*0033 -0*0504 0*0142 -0*0156 6 H S 0*0250 0*0277 0*0015 0*0662 -0.051 8 7 c S 0*0094 0*0207 0* 0185 0*3673 -0*3861 7 c PX 0*0075 0*0246 0* 1314 0*3781 -0* 1831 7 c PY 0* 03 95 0*0064 0*04 11 0* 334 3 -0*3569 7 c PZ 0*1256 0*0230 -0*2803 0*1582 -0*3151 8 c s “0*006 0 0*0097 -0*0094 0*0163 0*0135 8 c PX “0*01 19 0*0119 0* 0028 0*0130 0* 021 2 8 c PV •0*0092 0*0110 -0*001 3 0*0190 0* 0240 8 c PZ o* o i a i -0*0223 0* 0031 -0*0248 -0*0292 9 c 5 “0*0251 -0*0505 -0*00 53 0*0141 -0*0092 9 c PX 0*0175 0.0119 0*0341 0*0053 -0*0229 9 c PY •0*0379 -0*0490 -0* 0015 0*0270 0*0137 9 c PZ 0*0201 -0*0057 “0*0497 -0*0062 -0* 0233 to 0 s 0*0 755 0*4320 0* 04 50 0*2387 0*06 04 10 0 PX 1*8621 -0*1295 0. 0806 -0*0376 0* 30 7 7 1 0 0 PY -0.1295 1 .1 678 -0. 0684 -0*5445 -0* 151 0 10 0 PZ 0*0806 -0*0664 1*6735 -0*0396 -0* 1421 It c s -0*0376 -0*3445 -0*0396 1*0466 -0* 0831 11 c PX 0*3077 -0*1510 -0* 1421 -0*0831 0*6562 It c PY -0* 1 95o “0*6380 -0* 1201 0* 1080 0*0886 1 1 c PZ -0*1433 -0*1058 0* 5937 -0*0270 0*0315 12 c s 0*01 12 -0*0346 -0* 0003 0*0091 0*0204 12 c PX 0*0344 -0*0135 -0*0015 0*0094 -0* 0429 12 c PY 0*0099 -0*0622 0*0221 0*0127 0*0142 12 c PZ 0*0077 -0*0147 0* 0071 0*0005 -0*001 4 13 0 s 0*0089 -0 *0027 -0*0300 -0*0139 -0*0064 13 0 PX -0*0223 0*0074 0*0595 0*0199 0* 0200 13 0 PY 0*0 066 0*0088 -0* 0238 -0*0130 -0* 0076 13 0 PZ 0*0106 -0*0047 -0*0348 -0*0250 -0* 0160 14 0 s -0*0047 0*0042 0* 00J3 -0*0002 0*0042 14 0 PX 0*0055 -0*0069 “0*0031 -0*0053 -0. 0090 14 0 P V 0*0038 -0.0030 “0*0021 -0.001 0 -0*0034 14 0 PZ 0*0039 “0*0040 -0* 0038 0*0025 -0*0034 15 N s -0*1401 0*0788 -0*0700 0*2340 0*3785 15 H PX 0*0572 -0*0303 0*0799 -0*261 1 -0*2678 IS N pr -0*0701 0*024 1 -0* 01 33 0*2434 0* 3463 IS H PZ 0*1019 -0*0167 -0* 1268 -0*1093 -0*2452 1 6 c s 0*0001 0*0008 -0*0007 0*001 2 0*0006 16 c PX 0*0002 -0*0008 0* 0003 -0*001 4 -0.0012 1 6 c pr 0*0014 -0*0005 -0* 001 7 0*0007 -0*0006 16 c PZ “0*0010 0.0003 0* 0006 “0*0001 0*0009 1 7 H s 0*0001 0.0000 -0*0009 0*0009 0*0004 18 H s “0*0091 0*0027 0* 0252 -0*0050 0* 0038 19 c s 0*0092 0*0174 0*01 48 0*0103 -0*0027 19 c PX “0*0334 -0.0147 -0* 0221 -0*0163 -0* 0044 19 c PY -0*0103 0*0012 -0*0099 0*0031 0* 0339 19 c PZ 0*0003 -0*0036 -0. 0240 -0*0045 -0*0041 20 H s -0*0066 -0*0027 -0. 0045 0*0434 0* 0650 21 H s -0*0002 0*0007 -0*0005 0*0009 0* 0003 22 H s -0*0004 -0.0001 0* 0016 -0*0015 -0* 0002 23 H s 0*0187 0.001 3 -0*0253 “0*011 5 -0*0277 21 29 -o.oioo ••ooti 0060 O . M«r 0*0280 0*0083 0.0108 — O * 0903 0.01 40 “ 0*0388 0*0821 “ 0*0503 “ 0.0103 0*0129 0*0100 “ 0 * 0017 0 * 01 70 • 0*0125 30 0*0248 0*0173 0*0202 “ 0*0185 0*1243 0*1 672 0*0777 “ 0*0881 0*0401 “ 0*0325 33 0*0157 0*1041 • 0*0520 • 0*2520 0*1810 0*2351 0*2866 0*0006 0*0130 0*0320 0*0924 0.1372 0*0276 0*0787 0*1640 0* 1864 0* 1419 0*0110 0*0929 0*0146 “ 0*0515 “ 0*2422 “ 0.2781 • 0*0767 O . 1375 “ 0*1360 • 0*3220 “ 0*1782 0*5100 0*0012 “ 0*0135 • 0*0404 0*0160 0*0207 0 . 0 S 31 0*0349 0*0873 “0 *0213 0*0081 “ 0*0155 0*0060 • 0*0151 0*0167 0*0104 0*0594 0.0197 0*0069 0*2662 0*1176 0*2798 0*2363 0*0192 0*0009 0*0369 0*3268 0*0426 0*0393 0*0185 0*0028 0*3196 0* 1986 0*2226 0.3000 0*0349 0*0068 0*3452 0*2746 0*4076 0 * 1635 0*0022 0*0060 0*1 342 0.2584 0*0053 0.0780 0*0234 0.0317 0*2 083 O * J 304 0*0021 0. 1400 *.0*0464 0.0077 0*0074 0*0458 0*0655 0*0069 0 * 0017 0*0211 0*0356 0*2647 0*0325 0*0950 0*3834 0*0381 0*0143 0*0030 0*0212 0*0031 “ 0*1956 0*1433 0*0 112 0*0344 0*0099 0*0077 0*6380 0. 1056 0*0546 0*0135 0*0622 0*0147 0*1201 0*5937 0*0003 0*0015 0*0221 0 * 0071 0* 1088 0*0270 0*0091 0*0094 0 *0127 0*0005 0*0866 0*0313 0*0204 0 . 0429 0*0142 “ 0 * 0014 0*9392 0*0376 0*0057 0*0254 0*0067 0*01 10 0*0376 0*8031 0*0181 0*0127 0*0140 0*0111 0*0057 0*01 81 0.9777 0*2254 0*0470 0*0344 0 * 0254 0*0127 0*2254 0.7869 0*0742 0*0292 0*0087 0*0146 0*0470 0*0742 0*9830 0*0323 0*0110 0*0111 0*0344 0*0292 0*0323 0*8762 0 * 0099 0*0331 0*1 619 0*0383 0*0641 0*3135 0*0146 0.0773 0 * 1 501 0* 1970 0*0645 0*3214 0*0091 0*0325 0*0706 0*0312 0*0987 0* 1474 0*0160 0*0452 0*394 0 0*0940 0*1657 0*6106 • 0*0028 0*0075 0*0032 0*0004 0*2720 0*2913 0 * 1470 0* 1214 0*0010 0*0014 0*0000 0*0004 0*0030 0*0026 0*0009 0*0044 0* 1548 0*2170 0*1197 0*2211 0*0005 0 * 0003 0*0012 0*0005 0*0 105 0*0197 0*0280 0*0423 0*2612 0*0686 0*4 684 0*0 966 0*0 26 3 0*0245 0*0200 0*0228 0*0126 0*0644 0*0137 0*0435 0*0634 0*1808 0.1380 0*1368 0*01 34 0*01 95 0 * 0116 0*0044 0*0023 0 *0299 0*0326 0*0313 0*1590 0*021 1 0*0210 0.0151 0*0154 0*0010 0.0128 0*0052 0*0055 0.0050 0*0142 0*0931 0*0668 “ O * 1661 0* 1881 0*0193 0*0119 0 * 0158 0*0121 0*0103 0*0088 0*0057 0*0257 0*0538 0*0264 0*0610 0*0027 0*0015 0*0093 0. 0002 0*0023 0* 0342 0*0010 0*0011 0*0139 0*0072 0*0124 0*0142 0*0008 0*0228 0*0005 0*0016 0*0200 0*0009 0*0 157 0*0087 0*0034 0*0494 0.0000 0*0200 0*0301 0*0301 0.0447 0*0565 0*0205 0*0045 0*0075 0*0121 0*0172 0*0115 0*0 1 14 0*01 70 0*0002 0*0177 -< 0*0036 0*0066 0.0005 0*0050 0*0167 0*0035 0*0090 0*0310

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150 1 1 M 8 34 0.0261 33 -0.034 0 36 0. 0043 37 0.0676 30 -0.0311 39 0.0204 40 0.0336 4 1 0.0399 42 -0.0166 43 -0.0060 44 0.0460 2 2 H 8 “0.0047 -0.0710 0. 0020 -0.0204 0. 6240 -0.0240 -0.0177 -0.0370 0.0233 -0.0393 -0.0416 2 3 H 8 0.0194 -0.0310 0. 0224 0.0237 0.0041 -0.0038 -0.0020 -0.0063 0.0007 -0.0699 0.0330 4 4 H 8 -O.OIIO'* -0.0271 -O.OIII -0.0476 0.0190 -0. 0344 0.1039 0.0314 0.0394 -0.0133 -0.0712 3 8 C 8 0.0009 0.0476 0.0360 -0.0497 -0.0070 0.0307 -0.0023 -0.0 169 -0.0030 0.0363 0. 0060 4 3 C PX 0.0013 0.0460 0. 0071 0.0207 -0. 0046 0. 0737 0.0053 -0.0243 0.0110 0.0080 -0.0106 7 3 c PY 0.0132 0.0302 0.0073 -0.0467 -0.0130 -0.0356 -0.0113 0.0206 -0.0143 0.0123 -0.0014 • 8 c PZ 0.0068 -0.0332 -0.0213 0.0653 -0.0100 0.0330 0.0209 -0.0137 -0.0013 -0.0303 -0. 0091 9 6 H 8 >0.0196 0.0430 0.0661 0.0291 -0.0021 0.0240 0.0076 -0.0106 0.0371 -0.0469 -0.0336 1 0 7 c S 0.0041 -0.0003 -0. 0364 0.001 a 0. 0000 -O • 00 1 0 -0.001 1 0.0000 -0.0246 0.0157 0.0166 1 1 7 c PX -0.0234 0.0620 -0.0131 -0.0178 0. 0000 -0. 0061 -0.0023 0.0015 -0.0174 -0.0337 -0.0103 12 7 c PY -0.0069 0.0140 0.0441 -0.0044 0.0022 -0.0024 -0.0024 -0.0038 O.OIIO 0.0127 -0. 0267 13 7 c PZ 0.0430 -0. 1320 0. 0202 0.0031^ -0. 0013 0.0109 0.0060 -0.0000 -0.0200 0.0233 0.0060 14 0 c s “0.0070 0.0034 0. 04 09 -0.0374 0. 1935 -0. 1966 -0.1790 -0.3671 -0.0030 0.0004 0.0170 IS 0 c PX 0.0004 -0. 1314 0. 0207 -0.0053 0. 1632 -0.0147 -0.1332 -0.3117 -0.0063 “0.0466 0.0224 16 0 c PY 0.0043 -0.0442 0. 0363 -0.0361 0. 1337 -0. 1326 0.0026 -0.2434 -0.0130 -6.0136 0.0130 17 0 c PZ 0.0177 0.0748 -0.0404 0.0456 0.3244 -0.3051 -0.2937 -0.4400 o.oors 6.031 1 -0.0316 IS 9 c 8 0. 1 331 -0.261 7 0. 0267 *0.1300 0. 0140 -0. 0160 -0.0113 -0.0206 -0.0396 0.0363 -0.0260 19 9 c PX 0.2333 -0.4333 0.1190 0.2647 0.0124 -0.0077 -0.0096 -0.0207 0.0230 -0.0121 -0.0336 20 9 c PY “0.0534 0.1073 0. 06 03 -0.0537 -0.0127 0.0151 0.0090 0.0 168 -0.0502 0.0 1 16 -0.0127 21 9 c PZ -0.1779 0.4744 -0. 0627 -0.071 1 0.0176 -0.0216 -0.0160 -0.0220 -0.0066 0.0410 -0.0134 22 10 0 8 0.0007 -0.0006 -0.0038 0.0012 -0.0000 0.0010 0.0000 0.001 1 -0.0046 -0.0129 -0.0104 23 1 0 0 PX 0.0089 “0.0223 0. 0066 0.0106 “0.0047 0.0053 0.0030 0.0039 -0.1401 0.0572 -0.0701 24 10 0 PY -0.0027 0.0074 0.0068 -0.0047 0.0042 -0.0069 -0 . 003 0 -0.0040 0.0768 -6.0303 0.0241 2S 10 0 PZ -0.0300 0.0593 -0.0236 -0.0340 0.0033. -0.0031 -0.0021 -0.0036 -0.0700 0.0799 -0.0133 26 11 c 8 -0.0139 0.0199 -0. 0130 -0. 023 0 -0.0002 -0. 0033 -0.0010 0.0 023 0.2346 -6.2611 0.2434 27 1 1 c PX -0.0064 0.0200 -0.0076 -0.0160 0.0042 -0. 0090 -0.0034 -0.0034 0.3763 -0.2678 0.3483 20 11 c PY 0.0099 -0.0146 0. 0091 0.0160 -0.0026 0.0073 0.0032 0. 0 004 -0.2720 0.2913 -0. 1470 29 11 c PZ 0.0331 -0.077,3 0. 0323 0.0432 -0.0030 0. 0026 0.0009 0.0044 0. 1340 -6.2170 0.1197 30 12 c 8 / 0.16! 9 0.1301 ' ” 0.0 708 0.3940 -0.0163 -0.0197 -0.0200 0.0423 0.2612 -0.0666 -0.4664 31 12 c PX \ —0.0363 0.1970 -0. 0312 -0.0940 -0.0126 -0.0644 -0.0137 0.0433 0.0634 0.1806 -0.1380 32 12 c PY \-0.064t -0.0643 0.0967 -0.1637 ! 0.0023 0. 0299 0.0320 -0.0313 0.4190 -6.0923 -0.6133 33 12 c PZ “0.3 166—. ^0.3214 -0.1474 -0.6106/ -0. 0032 -0.0033 -0.0030 -0.0 142 0.0931 -0.0666 -0.1661 34 13 a s 1.7093 0.1341 ^o7iTT5" ^0.4543 0.0122 -0. 0060 -0.0032 -0.0233 -0.0013 -0.0017 0.0000 35 13 0 PX 0.1341 1 .4300 0.0360 0.0370 0.0137 0.0164 0.0006 -0.0339 0.0130 -0.0642 -0.0006 36 13 a PY -0.1 139 0.0560 1.9271 -0.1773 —0. 0006 -9.0063 -0.0000 0.0 02 3 -0.0399 0.0100 0.0781 37 13 0 PZ -0.4343 0.0370 -0. 1773 1.2078 0. 0347 -0.0107 -0.0107 -0.0303 0.0011 -6.0132 0.0037 30 14 0 8 0.0122 0.0137 -0.0006 0.0347 1.6096 9.0239 0.4370 0.1 191 -0.0199 “6.0006 0.0261 39 14 0 PX “0.0088 0.0164 -0. 0063 -0.0107 0. 0259 1 .7393 0.0434 -0.3213 0.0118 0.0046 -0.0287 40 14 0 PY -0.0032 0.0006 -0.0008 -0.0107 0.4370 0.0434 1.4399 -0.0077 0.0094 “0.0002 -0.0260 41 14 0 PZ -0.0233 -0.03S9 0.0023 -0.0363 0.1191 -0.3213 -0.0077 1.3010 0.0273 “0.0063 -0.0374 42 IS N 8 -0.0013 0.0130 -0.0399 0.001 1 -0.0199 0. 0110 0.0094 0.0273 1.2000 -0.0879 0.1236 43 IS N PX “0.001 7 -0.0642 0.0100 -0.0132 -0.0006 0.0040 -0.0002 -0.0063 -0.0679 1 .2 075 -0.0391 44 IS N PY 0.0000 -0.0006 0. 0761 0.0037 0.0281 -0.0287 -0.0260 -0.0 374 0. 1236 -0.0391 1. 0378 48 IS M PZ 0.0430 0.1143 0. 0322 0.0993 -0.0080 -0.0094 0.0012 0.0074 0.0972 -6 • 1 763 -0.0933 46 1 6 C s “0.001 0 -0.0047 0.'0022 -0.0079 0. 1929 0.1873 -0.3142 0.2237 0.0009 0.0001 0.0006 47 16 C PX 0.0023 0.0064 -0. 0019 0.0063 -0. 161 7 0.0337 0.2729 -0.1926 -0.0024 0.001 1 0.0003 40 16 c PY -0.0029 -0.0053 0. 0016 -0.0114 0.3166 0.2435 -0.3360 0.3374 0.0043 0.0002 -0.0046 49 16 c PZ 0.0030 0.0023 0.0002 0.0066 -0.2303 -9. 1924 0.3834 -0.1 062 -0.0037 -0.0006 0. 0034 SO 17 H 8 -0.0017 -0.0006 0.0011 -0.0052 0. 0271 0. 1000 0.0600 -0.0172 0.0000 -0.0003 -0.0014 81 10 H 8 -0.0060 -0.0160 -0.0146 -0.0171 -0.0047 0. 0020 0.0030 0.0040 -0.0300 0.0393 -0.0020 S2 19 C 8 0.0034 -0.0100 0.0061 0.0092 -0.0006 -0. 0012 0.0039 0.0006 0.2330 0.3903 0. 1220 33 19 c PX -0.0075 0.0134 -0.0173 -0.0160 -0.0136 -0.0120 -0.0074 0.0153 -0. 4620 “0.3333 -0.2196 S4 19 c PY -0.0043 0.0094 0. 0010 -0.0095 0.0031 0.0003 -0.0127 -0.001 1 -0. 1376 -0.2336 0.0796 ss 19 c PZ 0.0020 0.0121 0.0003 0.0060 -0. 0012 0.0001 0.01 10 0.0007 -0.1212 -0 • 1 998 -0.0603 56 20 H 8 0.0023 -0.0019 0.0130 0.0030 0.0017 0.0072 0.0077 -0.0 006 0.0153 “6.0283 0. 0376 S7 21 H 8 -0.0006 -0 .0023 0.0011 -0.0013 0. 0102 -6*1001 0.0213 0.0736 -0 • 0004 0.0000 0.0017 SO 22 H 8 0.0044 0.0067 “0. 0024 0.0131 -0.0300 0.0030 -0.0202 -0.0571 -0.0026 0.0009 0.0033 89 23 H 8 0.0037 0.0222 -0.0031 0.0108 0. 01 00 0.0040 0.0073 -0.0010 0.0004 -6.0237 -0.0222

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151 43 46 47 46 40 50 51 02 33 34 55 * 1 H 3 0*0103 0*0010 0*0039 0*0070 0*0047 0*6064 0*0090 0*0010 0*001 1 0*0013 0*0013 2 2 H 3 0*0434 0*0017 0 * 0000 0*0010 0*0081 0*0011 0*0007 0*0 127 0*0192 0*0110 0*0061 9 3 M 3 0*0349 0*0007 0*0002 0*0017 0*0000 0*0000 0*0002 0*0107 0*0277 0*0130 0*0069 4 4 H 3 0*0248 0*0276 0*0132 0*0423 0*0030 0*0000 0*0033 0*0003 0*0026 0*0009 0*0010 9 3 C 3 0*0441 0*0073 0 * 0012 0*0120 0*0144 0*0060 0*0002 0*0147 0*0107 0*0137 0*0089 * 3 C PX 0*0410 0*0117 0 * 0043 0*0174 0*0194 0*0115 0*0019 0*0090 0*0065 0*0064 0*0071 7 3 c PT 0*0041 0.0049 0 * 0067 0*0001 0 * 0012 0*0033 0*0027 0*0113 0*0166 0*0025 0*0089 • 3 c P 2 0*0210 0*0009 0*0077 0*0002 0*0002 0*0041 0*0042 0*0163 0*0224 0*0142 0*0079 9 0 H 3 0*0147 0*0011 0*0046 0*0000 0*0000 0*0910 0*0046 0*0110 0*0220 0*0102 0*0069 to 7 c 3 0*0023 0.0000 0*0007 0*0006 0*0006 0*0006 0*0007 0*0200 0*0390 0*0124 0*0103 11 7 c PJC 0*0340 0*001 0 0 * 0017 0 * OOO 3 0*0006 0*0006 0*0060 0*0 261 0*0337 0*0170 0*0010 12 7 c PY 0*0162 0*0005 0*0006 0*001 2 0 * 0004 9 * 0013 0*0043 0*0119 0*0179 0*0026 0*0039 12 7 c PZ 0*1079 0*0015 0*0030 0*0003 h Ji*oois 0*0010 0*0206 0*0123 0*0147 0*0066 0*0106 14 8 c 3 0*0412 0*0220 0*02 32 0*0184 0 * 0356 0 * 0344 0*0060 0*0030 0*0001 0*0005 0*0002 IS 0 c PX 0*0400 0*0315 0*0159 0*0081 0*0470 0*0183 0*0021 0*0192 0*0221 0*0124 0*01 02 1 4 0 c PY 0*0007 0*0030 0 * 02 33 0*0060 0 * 0432 0*0176 0*0033 0*0093 0*0037 0*0062 0*0007 17 0 c PZ 0*0096 0*0451 0*0396 0*0002 0 * 0333 0*0200 0*0006 0*0200 0*0160 0*0133 0*0023 IS 9 c 3 0*0051 0*0007 0 * 0005 0*0031 0 * 0014 0 * 0029 0*0023 0*0223 0*0316 0*0103 0*0081 IS S c PX 0*0060 0*0002 0*0006 0*0031 0*0006 0*0019 0*0040 0*0166 0*0172 0*0099 0*0042 20 S c PY 0*0320 0*0008 0.0002 0*0034 0.0000 0*0026 0*0020 0*0066 0*01 10 0*0001 — 0 * 001 9 21 0 c PZ 0*0737 0*0026 0*0003 0*0067 0*0013 0 * 0050 0*0009 0*0192 0*0229 0*0120 0*0082 22 10 0 3 0*0043 0*0002 0.0000 0*0001 0* 0000 0.0000 0*0000 0*0 101 0*0043 0*0021 0*0007 23 1 0 0 PX 0 * 1 01 9 0*0001 0 * 00 02 0*0014 0*0010 0*0001 0*0091 0*0092 0.0334 0*0103 0*0003 24 i 0 0 PY 0*0 167 0*0008 0 * 0000 0*0003 0*0003 0*0000 0*0027 0*0174 0.0147 0 *0012 — 0*0036 2 S 10 0 PZ 0*1260 0*0007 0*0003 0*0017 0*0006 0*0009 0*0232 0*0140 0*0221 0.0000 0*0240 24 11 c 3 0*1093 0*0012 0 * 0016 0*000 7 0* 0001 0*0009 0*0050 0*0103 0*0163 0 *0031 0*0049 27 1 1 c PX 0*2452 0*0006 0.0012 0*0000 0*0009 0*0004 0*0038 0*0027 0*0044 0*0330 0*0041 20 1 1 c PY 0*1 214 0*001 0 0 * 0014 0*0000 0 * 0004 0*0007 0*0057 0.0015 0*0093 0*0002 0*0023 2 S II c PZ 0*221 1 0*0005 0*0003 0*0012 0*0000 0*0010 0*0297 0*0072 0*0124 0*0142 0*0000 30 12 c 3 0*0966 0*0263 0 * 0243 0*0200 0*0220 0*0120 0*0530 0*0089 0*0137 0*0087 0 * 0034 31 12 c PX — 0 * 1 360 0*0134 0 * 01 95 0*0116 0*0044 0*0032 0*0264 0*0301 0*0447 0*0565 0*0205 32 12 c PY 0*1 390 0*0211 0 * 0210 0.0151 0 * 0134 0*0103 0*0610 0 * 011 5 0*01 14 0*0170 0*0002 33 12 c PZ 0*1 001 0*0193 0*01 19 0*0130 0*0121 0*0000 0*0027 0*0 036 0*0066 0*0009 0*0050 34 13 0 s 0*0450 0.0018 0 * 0025 0*0029 0.0030 0*0017 0*0060 0*0034 0*0075 0*0043 0*0020 3S 13 0 PX 0*1143 0*0047 0*0084 0.0033 0*0023 0*0006 0*0160 0*0 100 0*0134 0.0094 0*0121 36 1 3 0 PY 0*0322 0*0022 0 * 0019 0.0016 0*0002 0*001 1 0*0146 0*0061 0*0173 0 *0010 0 * 0003 37 13 0 PZ 0*0993 0*0079 0*0083 0*0114 0* 0006 0 * 0052 0 * 017 | 0*0002 0*0160 0*0003 0*0060 30 14 0 3 0*0000 0*1929 0*1617 0*3106 0*2303 0*0271 0*0047 0*0 086 0*0136 0*0051 0 * 0012 39 14 0 PX 0*0094 0*1573 0 . 0357 0*2453 0 * 1924 0*1000 0*0020 0*0012 0*0128 0*0003 0*0001 40 14 0 PY 0*0012 0*3142 0*2729 0*3360 0*3034 0 * 06 80 0*0036 0*0039 0*0074 0*0127 0*0110 41 14 0 PZ 0*0074 0*2237 0* 1926 0*3374 0*1062 0*0172 0*0046 0*0000 0*0159 0*0011 0*0007 42 13 H 3 0*0972 0*0009 0*0024 0*0043 0*0037 0 * oooo 0*0300 0*2538 0*4628 0*1576 0* 1212 43 1 5 H PX — 0*1 76 3 0*0001 0. 001 1 0*0002 0*0000 0*0003 0*0395 0*3 905 0*5533 0*2356 0* 1998 44 1 3 H PY 0*0953 0*0008 0 . 0003 0*0046 0*0034 0.0014 0*0020 0*1 228 0*2196 0*0798 0 * 0603 45 19 H PZ 1*7367 0*0031 0*0047 0*0033 0*0046 0*0023 0*1014 0*1060 0*1926 0.0668 0*1403 46 16 c s 0*0031 1*0340 0 * 039 7 0*0607 0*0560 0*5120 0*0016 0*0002 0 * 0003 0.0009 0 * 001 6 47 16 c PX 0*0047 0*0397 0* 9585 0*0307 0*0296 0*5622 0.0011 0*0 02 5 0*0039 0 .0034 0 * 0021 40 16 c PY 0*0633 0*06 0 7 0*0307 0*9180 0 * 0510 0*6277 0.0027 0*0023 0*0022 — 0 .0034 0*0029 49 1 6 c PZ — 0*0046 0*0366 -0* 0296 0*0310 0*9414 0*0756 0.0020 0*0017 0*0007 0.0015 • 0*0016 50 17 N 3 0*0023 0*3120 0*5622 0*6277 0 * 0756 1*0146 0.0003 0*0001 0*0001 0.0007 0*0003 31 10 H 3 0*1014 0*0016 0*0011 0*0027 0*0020 0*0003 0.9999 0*5001 0*0394 0.4904 0 * 6942 S2 19 c S 0*1 060 0*0002 0*0025 0*0023 0 * 001 7 0 * 0001 0 . 5001 1*0212 0*0680 0.0362 0*0182 33 1 9 c PX — 0 * 1 926 0.0003 0.00 39 0*0022 0*0007 0*0001 0.0394 0*0680 0*9147 0.01 14 0 * 0212 34 19 c PY — 0*0668 0.0009 0.0034 0*0034 0* 0015 0*0007 0.4904 0*0362 0*01 14 0.9663 0 * 0024 S3 19 c PZ 0*1403 0.0016 0.0021 0*0029 0*0016 0*0005 0.6942 0*0182 0*0212 0.0024 0*9826 36 20 H 3 0*0170 0*0037 0*0023 0*0000 0*0059 0*0003 0.0296 0*4933 0*5044 0.6750 0* 1391 37 21 H S 0*0003 0*3113 0*7090 0*2771 0*3706 0*0409 0.0002 0*0006 0*0007 0.0001 0*0001 50 22 H 3 0*0012 0*4987 0 * 1707 0*3209 0 * 7669 0*0370 -0.0000 0*0002 0*0023 0.0004 0*0003 59 23 M S 0*1203 0*0023 0*0030 0*0036 0*0031 0*0010 0*0430 0*4990 0*3329 0.4497 0*6412

PAGE 162

1 1 H 96 9 0.0044 97 0.0006 50 -0.0100 99 -0.001 7 2 2 H S -0.0069 0.0039 0. 00 34 0.0149 3 3 N 9 0.01 76 -0.0006 0.00 20 -0.0090 4 4 H S -0.0099 0.0047 0. 0204 0.0110 5 9 * 9 7 9 6 6 C C c c S 0.009* PX 0.0093 PY 0.0026 PZ -0.0001 0.0000 -0.0001 0.0019 -0.0014 -0.0043 -O. 0002 -0.0000 0.0002 -0.011 4 -0.0064 -0.0032 0.0008 9 4 M 9 -0.0076 -0.0016 0. 0004 0.0117 16 7 11 7 12 7 13 7 c c c c S -0.0047 PX -0.0000 PV -0.0141 PZ -0.0044 0.0004 0.0002 -0.0004 0.0004 -0.0010 0. 0000 0.0021 -0.0014 0.0013 0.0108 0.0009 -0.0167 14 6 c S 0.0096 -0.0192 0. 0743 -0.0072 19 6 16 6 17 6 c c c PX 0.0004 PY 0.0073 PZ -0.0000 -0.0041 0.0094 0.0001 0.0417 0.0126 0.0690 0.0123 0.0019 -0.0019 16 9 19 9 20 9 21 9 c c c c S -0.0004 PX 0.0091 PY -0.0073 PZ 0.0043 -0.001 0 -0.0013 0.0007 -6.0029 0.0097 0. 0046 -0.0047 0.0090 -0.0032 0.0020 0.0062 , -0.0167 . 22 16 23 10 24 10 29 10 o 0 0 0 S 0.0003 PX -0.0046 PY -0.0027 PZ -0.0049 -0.0001 -0 .0002 0.0007 -0.0009 -o.ooot -0.0004 -0. 0001 0.0016 -0.0006 \ 0.0107 0.0013 -0.0233 26 11 27 It 26 II 26 11 c c c c S 0.0434 PX 0.0490 PY -0.0342 PZ 0.0220 6.0009 0.0009 -0.0010 0.0009 -0.0013 -0. 0002 0.0011 -0.0016 -0.0119 -0.0277 0.0139 0.0200 36 12 31 12 32 12 33 12 c c c c 9 -0.0494 PX 0.0049 PY -0.0941 PZ -0.0147 0.0000 0.0079 -0.0074 0.0039 -0. 0200 -0.0121 0.0177 —0. 0096 0.0301 -0.0172 0.0203 0.0310 34 13 36 13 36 13 37 13 0 0 0 0 9 0.0023 PX -0.0019 PY 0.0130 PZ 0.0090 -0.0004 -0.0023 0.001 I -0.0013 0.0044 0. 0067 -0.0024 0.0131 0.0037 0.0222 -0.0031 0.0103 36 16 36 14 4# 14 41 14 0 0 0 o 9 0.0017 PX 0.0072 PY 0.0077 PZ -0.0004 0.0102 -0.1081 0.0213 0.0734 -0.0306 0.0098 -0. 02 82 -0.0971 0.0100 0.0049 0.0073 -0.0016 42 16 43 16 44 IS 46 16 M M N M 9 0.0193 PX -0.0283 PY 0.0376 PZ -0.0170 -0.0004 0.0000 0.001 7 -0.0003 -0. 0026 0. 0009 0.0033 0. 0012 0.0004 -0.0237 -0.0222 0.1203 44 16 47 14 46 14 46 16 C C c c 9 0.0097 PX -0.0023 PY 0.0080 PZ -0.0099 0.31 13 0.7090 -0.2771 -0.3706 0.4907 0.1787 0.32 09 0. 7669 -0.0023 0.0030 -0.0036 0.0031 66 17 H 9 0.0003 -0J0409 -0.0378 0.001 0 SI 16 H S -0.0240 0.0002 -0.0008 -0.0430 92 19 93 19 94 19 99 19 c c c c 9 0.4439 PX 0.9044 PY —0.6 730 PZ 0.1991 -0.0006 0.0007 .0.0001 0.0001 0. 0002 -0.0029 0. 0004 -0.0003 0.4990 0.3329 0.4497 -0.6412 96 20 N S 1.0292 0.0026 0.0009 -0.0321 97 21 H 9 0.0020 1 .0049 -0.0380 -0.0009 96 22 N 9 0.0009 -0.0300 0.9961 0.0067 SO 23 M 9 -0.0321 -0.0009 0. 0007 1*0041 a a 4 9 4 7 0 • It U ta 13 TOTAL ENEP6Y • B1NOIN6 ENER6V* 0.93a t 0.9942 0.9710 0.9799 3.9863 t .0030 4.3634 3.asaa 3.7261 4.4746 3.6492 3.6238 6.2742 6. 1900 9.2020 3.0927 1.0146 0.9999 3.0046 1 .0292 1.0069 0.9961 1.0041 •132.91 23921739 •10.0436362360 A.U. COMPONENTS densities pCo total 0 IP OLE MOMENTS X 1.01664 •0.20096 0.00000 0. 73966 Y •6.16306 •3.0961 2 0.00000 •12 . 0992 0 MOMENT* 12.46729 0C6YCS Z 2.00331 0. 39374 0.00000 3.19706 )

PAGE 163

153 ^3 1 2 3 4 3 6 7 6 9 10 1 1 1 1 M S 1.0118 • 0*0044 0 * 0173 0*0232 • 0*0361 0*0672 0*0719 0*3012 0*3767 • 0*1502 • 0*6085 2 2 H S • 0*0044 0*9762 0* 1029 0*0306 0*0262 0*0333 • 0*0432 0*0010 0.0094 • 0*0009 • 0*0061 3 3 H s 0*0173 0*1029 1 * 0220 0 * 0234 • 0 * 0273 • 0*0261 • 0*1032 • 0*0330 0*0317 0*0136 0*0236 4 4 O s • 0*0232 0*0306 0.02 34 1*6073 • 0*1463 0.1317 • 0*3916 0 . 1970 0*3833 0*0869 • 0* 1666 S 4 0 PX • 0*0561 0*0262 0. 0275 • 0* 1463 1*3340 • 0*2330 • 0*0362 0*3616 • 0*3699 • 0*1868 • 0*2928 6 4 0 PY 0*0372 0*0335 • 0 * 0261 0 * 1317 • 0*2330 1*7444 0*1833 0*0833 • 0*1561 0*1310 • 0*0333 7 4 0 PZ 0*0719 0*0432 • 0 * 1032 • 0*3910 • 0*0362 0*1693 1*3443 0*1669 • 0*3403 • 0*0764 0*0225 a 3 c s 0*5012 0*0010 0*0330 0* 1970 0*3616 0*0633 0* 1669 1*0 344 0*0720 0*0166 0*0234 9 3 c PX 0*5767 • 0*0094 0*0317 • 0*3633 • 0*5699 • 0* 1361 • 0*3403 0*0720 0*8906 0.0223 • 0*0300 10 5 c py 0 * 1 502 • 0*0009 0*0136 • 0*0669 0*1666 0*1310 0*0764 0*0 166 0*0223 0*9667 • 0*0029 1 1 3 c PZ 0*6065 0*0061 0 * 0236 • 0* 1660 • 0*2926 0* 0333 0*0225 0*0234 • 0*0300 • 0*0029 0*9390 12 6 H s 0*0396 0*0042 0*0164 • 0*0119 0*0341 • 0*1174 • 0.0463 0*3042 0*0101 0*6239 0*2092 13 7 H s 0*0037 • 0*0346 0*0750 0*0201 0*0231 -0*01 to 0.0188 0*0037 0*0088 0*0024 0*0049 14 a C 5 • 0*0124 0*4904 • 0*0069 • 0*0173 0*0392 • 0*0306 • 0*0024 0*0 238 • 0*0297 0*0177 • 0*0063 13 a C PX • 0*0240 • 0.2396 O * 01 61 0*0361 0 * 0532 0*0246 • 0*0249 0*0398 0*0464 0*0234 • 0*0163 14 a c PY • 0*0062 0*2263 0. 0058 0*0260 0*0153 0*0109 • 0*0290 0*0050 0.0072 0*0018 • 0*0084 17 a c PZ 0*0010 0*7834 0*0005 0*0166 0*0132 • 0*0177 • 0*0012 0*0029 0.0037 • 0*0024 0*0024 ia 9 c s 0*0470 0*0072 0 * 4948 0 * 164 6 • 0*2164 • 0*2333 0*2694 0*0 197 0.0408 • 0*0151 • 0*0061 19 9 c PX 0*0437 0*0122 0*2716 0*2262 • 0 * 1240 • 0*2663 0*3261 0*0318 • 0.0523 • 0*0440 O . OJ 2 J 20 9 c PY 0*0437 0.0056 0* 1281 0*2230 • 0*2450 • 0*1217 0*3205 0.0253 • 0*0314 • 0*0090 0.0134 21 9 c PZ • 0*0207 • 0*0105 0.7829 0*2639 0*2676 0*3010 • 0*2094 • 0*0 172 0.0147 0*0047 • 0*0023 22 to M s • 0*0391 0*0043 0*0007 0*0363 • 0*0143 0*0711 • 0*0762 0*3114 0* 1622 • 0*4769 0 * 6804 23 1 1 H s 0*0026 0*1166 0*0046 0*0060 • 0*0121 • 0*0139 0*0162 0*0013 0.0002 — O *0006 0*0010 24 12 c s 0*0074 • 0*0009 0 * 0032 0*0331 • 0*0232 • 0*0272 0*0440 0*0012 0*0013 0.0026 0*0035 23 12 c PX 0*0063 0*0139 0.01 12 0*0286 0 * 0118 0*0167 0*0371 0*0017 • 0 * 001 J 0*0041 0*0073 26 12 c PY 0*0039 0*0015 0*0065 0*0234 • 0*0128 • 0*0167 0 * 0300 0*0014 0*0006 • 0*0028 0*0052 27 12 c PZ • 0*0027 0*0069 0*0233 • 0*0002 0*0001 • 0*0004 0.0094 0*0002 0.0000 0*0004 • 0*0013 26 13 c s 0*0026 • 0*0022 • 0*0140 • 0*0043 0* 0270 0 * C 689 0*0273 0*0024 • 0*0112 0*0046 • 0*0031 29 13 c PX • 0*0070 0*0103 0 . 0269 0*0363 0*0089 0*0640 0*0336 0*0043 0 * 01 10 0*0003 0*0131 30 13 c PY • 0*00 1 6 0*0013 • 0 * 01 IS 0*0102 0*0203 0.0643 0*0122 0 . 0 C 70 • 0*0170 0*0031 0*0064 31 13 c PZ 0*0027 0*0230 0 * 0137 0*0234 0*0200 0*0232 0*0139 • 0*0038 0*0055 0*0026 0*0027 32 14 H 3 • 0*0026 0*0073 0 * 1134 • 0*0271 0*0241 0*0410 • 0*0423 0*0003 • 0*0066 0*0003 0*0035 33 1 5 O 5 0*0006 0*0026 0*0000 0*001 9 • 0.0015 0*0023 0*0024 0*0001 0*0004 •0 .0001 0*0004 J 4 IS PX 0.0001 0*0066 • 0*0035 0*0013 • 0*0011 • 0.0024 0 * 0020 0*0002 0*0001 • 0*0002 0.0003 33 1 5 0 PY 0*0015 0*0163 0 * 0045 0*0057 • 0*0043 • 0*0060 0*0073 0*0003 0*0011 0*0002 0*0016 36 IS o PZ 0*0040 • 0*0041 0*0136 0*0104 • 0 * 0063 • 0*0106 0*0127 • 0*0017 0*0031 0*0000 0*0025 37 16 c 5 • 0*0047 • 0*0342 0 * 00 31 • 0*0137 0*0146 0*0173 0*0184 0*0023 • 0*0048 • 0*0007 0*0030 36 1 6 c PX 0*0001 0*0147 0 * 0071 • 0 * 001 9 0 * 0014 0*0016 0*0026 0*0001 0*0001 0*0001 • 0*0008 39 16 c PY • 0.0047 • 0*0446 0*00 JS • 0.0144 0*0143 0*0154 • 0*0204 0*0020 • 0*0039 • 0*0004 0*0037 40 16 c PZ • 0*0045 0*0002 • 0*0091 0*0116 0*0113 0*0126 • 0*0129 0*0029 0*0049 • 0*0007 • 0*0022 41 17 c S • 0.0007 0*0069 • 0.0260 0*0094 • 0*0033 • 0*0269 0*0034 0*0003 0*0014 • 6*0009 0*0001 42 17 c PX 0.0014 • 0*0063 0 * 0029 • 0*0066 0*0061 0*0107 0*0062 0*0005 • 0*0018 • 0*0006 • 0*0006 43 17 c PY 0.0004 0*0071 • 0 * 0 J 94 0*0130 • 0 * 0069 0*0304 0. 0068 • 0.0002 0*0031 0*0013 0*0004 44 17 c PZ 0*0031 0*0066 • 0*0069 0*0062 0*0126 0*0017 0*0110 • 0.0010 0*0025 0*0014 0*0006 43 ia 0 5 0*0003 • 0*0002 0 * 0033 0 * 001 3 • 0*0006 • 0*0023 0.0013 • 0*0003 0.0003 0*0001 0*0001 46 ia Cl PX 0*0003 0.0044 0 * 0060 0*0007 • 0 * 0024 0*0032 0*0013 0.0001 0.0002 0*0006 • 0.0002 47 ia a PY 0*0002 • 0.0032 0 * 01 86 0.0033 0*0030 0*0042 • 0.0013 0.0000 • 0*0018 0*0005 0.0007 46 16 0 PZ • 0*0036 • 0*0121 0 * 00 76 • 0*0119 0*0121 0*0023 • 0.0123 0*0023 • 0*0038 0*0011 • 0.0023 49 l 9 N S • 0*0007 0*0004 0*0030 • 0*0052 • 0*0002 0*0163 0. 0027 0*0 006 0.0016 0*0009 0*0013 30 19 N PX 0.001 1 • 0*0007 • 0 * 00 32 0*0033 0*0016 0*0146 • 0*0041 0*0010 0.0020 0*0003 • 0*0013 SI 19 N PY • 0*0004 0*002 7 • 0 * 0006 • 0*0029 0*0003 0. 0060 0*0013 0*0003 0.001 1 0.0007 0*0008 32 19 N PZ 0*0003 0.0102 0*0126 • 0*0012 0*0023 • 0 * 0036 • 0*0004 0*0001 0.0003 O .0006 0*0003 S3 20 M 5 • 0 * 0(104 • 0*0016 0 * 0006 • 0*0021 0*0010 0*0032 • 0*0017 0.0003 • 0*0007 0.0002 • 0 * 0004 34 21 C 5 0*0000 0*0021 0*0011 0*0013 0*0002 • 0*0031 0 * 0000 0*0001 0 * 0004 • 0 . 000 J 0*0001 53 21 C PX 0*0000 0*0002 • 0.0010 0.0005 • 0*0002 0*0003 0*0003 0.0001 0*0001 -0*0001 a. oooi 36 21 c r»v 0.0000 • 0 .0034 -0. 0O| 1 0*0023 0*0002 • 0 * 0086 0*0003 0*0002 0.0009 • 0*0005 0.0003 57 21 c PZ 0.0000 0.0007 0*0006 0*0001 0*0002 0 * 0006 • 0 * 0003 •0*0001 0.0002 0 .0000 0.0001 56 22 H s 0*0002 •0.0008 0.00 22 0*0007 0*0002 • 0 * 0023 0*0006 0*0001 0.0002 0.0001 0.0002 39 23 M s 0*0001 0.0030 0 . 0027 0*0006 • 0*0009 • 6*0001 0*0067 • 6*0001 0.0002 0.0001 0.0000

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154 12 13 14 IS 16 t 1 H 9 >0.0396 0.0037 >0.0124 >••8249 >9* 6963 2 2 H S >0.0042 >0.0340 0. 4904 >9.2394 9« 2263 3 3 M 9 0.0164 >0.0790 -0.0069 -0.0181 >0.0099 4 4 0 S >0.01 19 0.0209 -0. 01 73 >0.0361 >0.0280 S 4 Q PX 0.0341 -0.0231 0.0392 0.0532 0.0133 6 4 U PY >0.1 174 >0.0118 >0.0306 >0.0246 0.0109 7 4 o PZ >0.0463 0.0188 >0. 0024 >0.0249 >0. 0290 8 9 c s 0.9042 >0.0037 0.02 38 0.0198 0.0090 9 9 c PX 0.0101 0.0088 -0.0297 -0.0464 -0.0072 10 5 c py 0.8239 0.0024 -0. 01 77 >0.0234 >0.0018 11 9 c PZ 0.2042 0.0049 >0. 0069 >0.0163 -0.0084 12 6 H s 1.0149 0.0037 -0.0020 >0.0066 >0.0021 13 7 H 9 0.0037 1.0030 0.4899 -0.3992 0.3097 14 8 c 9 >0.0020 0.4899 0.9869 >0.0389 0.0024 19 8 c PX >0.0066 -0.3992 -0. 0389 1.0394 0. 0689 16 8 c py >0.0021 0.9097 0. 0824 0. 0689 0.9783 17 8 c PZ 0.0010 0.9496 -0.01 09 0.0040 >0.0043 18 9 c s 0.0208 -0.0007 0.2406 0.4909 — 0.0494 19 9 c PX 0.0230 0.0232 -0.41d4 >0.6379 >0.0317 20 9 c py 0.0 109 -0.0363 0. 1319 0.2063 0. 1325 21 9 c PZ >0.0303 >0.0048 -0. 0399 >0.0839 >0.0099 22 10 H 9 >0.0399 -0.0020 0.0130 0.0290 0.0091 23 11 H S 0.0019 >0.0776 >0.0010 >0.0140 >••0103 24 12 c S 0.001 7 0.0043 0.2396 -0.1349 -0*4923 29 12 c PX 0.0009 0.0368 >0. 1 1 19 0.1227 0. 1 1 70 26 12 c py 0.0014 >0.0234 0.4090 >0. 1613 >0.6141 27 12 c PZ 0.0006 >0.0130 -0.0770 0.0950 0.1642 28 13 c 9 >0.0042 0.0746 0.0239 0.0297 >0.0398 29 13 c PX >0.0039 >0.0453 >0.0166 0.0168 0.1132 30 13 c py >0.0049 0.0583 0.0287 0.0881 -0.0397 31 13 c PZ -0.0004 0.0148 0.0127 >0.0090 >0. 0132 32 14 H 9 -0.0060 0.0289 >0.0271 >0.0101 0.0137 33 19 0 9 0.0002 0.0028 >0.007* 0.0009 0. 0077 34 19 u PX 0.0003 -O. 0028 >0.0185 0.0112 0.0274 39 19 o py 0.0009 >0.0086 >0. 0092 0.001 1 0.0020 36 19 o PZ 0.0009 0.0187 0. 0064 >0.0274 -0*0373 37 16 c 9 >0.0024 0.0269 0.0002 0.0334 0.0320 38 16 c PX >0.0003 0.0216 -0. 0013 -0.0045 0.0097 39 16 c PY -0.0021 0.0299 -0. 00 79 0.031 0 0.0343 40 16 c PZ -0.0019 -0.0119 0.0000 0.0361 0.0340 41 17 c s 0.0047 >0.0322 0. 04 44 0.0203 >0. 0392 42 1 7 c PX >0.0011 >0.0037 >0.0008 0.0147 0.0029 43 1 7 c py 0.0033 -0.0334 0. 0458 0.0213 >0.0230 44 17 c PZ -0.0003 0.0208 >0.0155 -0.0233 0.0141 49 18 0 s 0.0002 0.0044 -0.0029 -0.0026 0.0004 46 18 u PX >0.0001 -0.0005 0.0006 -0. 0006 0.0009 47 1 8 0 py >0.0012 0.0197 >0.0143 >0.0040 0.0034 48 18 0 PZ -0.0009 -0.0209 0. 0108 0.0123 -0.0031 49 19 N 9 -0.0018 >0.0114 0. 0316 >0.0120 >0.0462 90 19 H PX -0.0020 0.0110 >0.0271 0.0139 0.0493 91 19 H py -0.0009 -0.0085 0. 0300 >0.0129 -0. 0404 92 19 H PZ 0.0000 >0.001 1 0.0164 >0.0120 >0. 0320 93 20 H 9 >0.0008 0.0041 >0.0039 0.0026 0.0090 94 21 C 9 0.0006 0.0030 >0.0047 0.0049 0.0112 99 21 C PX 0.0001 0.0009 >0.0012 0.001 3 0.0043 96 21 c py 0.0011 0.0052 -0.0100 0.0073 0. 0200 97 21 c PZ 0.0001 0.0002 0.0002 0.0002 >0.0010 98 . 22 N 9 0.0002 >0.0034 0. 0084 >••0049 >••••44 99 23 H S 0.0002 >0.0023 0.0016 >0« 088 | >••0017 17 10 1 « 20 21 22 • : T ••04 70 0.0437 0.0437 > 0.0207 > 0.0391 -••7034 ••0072 0.0122 0.0096 0.0109 0.0043 0.0009 0*4940 0.2716 0.1281 0.7829 0.0007 0.0160 0. 1048 0.2262 0.2230 > 0.2639 0.0363 0.0132 > 0.2104 > 0. 1240 0.2490 0.2676 0.0145 0.0177 > 0*2333 0.2683 0 . 1217 0.3010 0.0711 > 0.0012 0*2694 0.3261 0.3205 > 0.2094 0.0762 > 0.0029 0.0197 0.0318 0.0293 > 0.0172 0.3114 0.0037 > 0.0400 > 0.0923 0.0314 > 0.0147 0.1622 > 0.0024 0.0191 > 0.0440 > 0.0090 0.0047 > 0.4769 0.0024 > 0.0061 0.0323 0.0154 0.0023 0.6004 0.0010 0.0200 0.0230 0.0109 > 0.0303 0.0393 0.9490 > 0.0007 0.0232 0.0363 > 0.0040 0.0020 > 0.0109 0.2406 > 0.4 184 0. 1319 > 0.0399 0.0130 0.0040 0.4909 0.6979 0.2063 > 0.0839 0.0250 0.0043 0.0494 > 0.031 7 0.1323 > 0.0099 0.0051 0.9066 0.0409 > 0.0807 0.0293 0.1343 0.0007 0.0400 0.9667 0.0 149 0.0300 0.0424 > 0.0424 > 0 . 0807 0.0149 0.9413 0.1097 0.0302 > 0.0211 0.0293 0.0300 0.1 097 0.9490 0.0283 > 0. 0363 0. 1943 0.0424 0.0302 0.0283 0.9331 0.0331 0.0007 > 0.0424 > 0.0211 > 0.0363 0.0331 1.0197 ••0049 > 0.0201 0.0034 0.0118 0.0019 0.0032 0.0000 0.0273 > 0.0563 > 0.0462 0.0064 > 0.0047 0.0242 0.0219 0.0346 > 0.1289 0.0147 0.0034 0 « 1464 0.0347 0.1 124 > 0.0039 0.0181 > 0.0023 0.1364 > 0.0130 > 0.0019 0.0129 0.0232 0.0007 > 0 « 0060 0.2436 0.0 570 > 0.4944 > 0.1223 0.0049 0.0169 0.2030 0.1 093 0.2379 > 0.0731 0.0131 > 0.0279 0.3777 0.0331 > 0.5518 > 0.1866 0.0007 0.0169 0.1120 0.0323 0.2267 0.0989 0.0003 0.0099 0.0024 0.0212 > 0.0074 > 0.0180 0.0092 > 0.0019 > 0.0034 0.0010 > 0.0006 0.0008 > 0.0005 > 0.0010 > 0.0044 0.0 009 > 0.0002 0.0009 > 0.0003 0.0088 > 0.0130 0.0017 0.0001 0.0036 > 0.0016 > 0.0090 > 0.0130 0.0 083 > 0.0023 0.0072 > 0.0034 0.0092 0.0481 0.0220 > 0.0293 > 0.0063 0.0052 0.0021 0.01 10 0.0078 > 0.0089 > 0.0013 0.0006 0.0070 0. 0493 > 0.0194 > 0.0103 > 0.0034 0.0049 0.0070 0.0238 > 0.0248 > 0.0079 > 0.0140 0.0043 0.0021 > 0.0017 > 0.0299 0 • 0393 0.0000 0.0019 > 0.0012 0.0007 0.0 104 0.0026 0.0014 0.0029 0.0024 > 0.0120 > 0.0249 0.0484 0.0120 > 0. 0024 0 * 01 13 > 0.0029 0.0224 0.0361 > 0.0084 0.0014 > 0.0003 0.0077 0.0 004 0.0069 0.0021 > 0.0004 > 0.0007 0.0170 0.0033 0.0274 0.0054 0.0006 > 0.0037 > 0.0070 0.0004 0.0009 0.0077 0.0009 0.0098 > 0.0063 0 . 0 IOI 0.0437 > 0.0034 0.0027 0.0094 0.0392 0.0033 > 0.0464 — O .0140 0.0022 > 0.0068 0. 0392 0.0 093 > 0.0335 > 0.0135 0.0026 0.0123 0.0271 0.0033 0.0322 > 0.0126 0.0013 0.0024 > 0.0132 > 0.0069 0.0282 0.0027 > 0.0009 0.0010 0.0094 0.0021 0.0136 0.0037 0.0009 > 0.0020 > 0.0037 > 0.0021 0.0122 0.0039 > 0.0004 0.0002 > 0.0020 0.0003 0.0012 0.0012 0.0000 0.0040 0.0122 0.0034 0.0226 0.0069 > 0.0009 0.0009 > 0.001 0 0.0000 0.0024 0.0015 0.0001 ••Mil > 0.0094 0.0020 0.0080 0.0417 > 0.0004 0.8000 0.0011 0.0009 > 0.0020 > 0.0003 > 0.0001

PAGE 165

155 23 24 23 20 27 29 29 30 31 32 33 1 1 N S 0.0020 0.0074 0.0043 9.0939 9.9027 9.9222 9.9979 0.0016 0.0027 9.0026 0.0006 2 2 H 3 0.1186 0.0009 ••9139 9.8913 0.8069 — 9 . 9422 9.9192 0.0019 0.0230 9.0073 0.0029 3 3 H S 0.0040 0.0032 0.0112 0.0005 0.0233 9.9149 0.0269 0*0119 0.0137 9.1134 0.0090 4 a 3 0.0000 0.0331 0 . 0288 0 . 0234 0.0002 9.0043 0.0363 0*0102 0.0234 9.9271 0.00 19 S 4 Pi 0.0121 0.0232 0.01 18 0.0120 0.0001 0.0270 0.0089 0.0203 0. 0200 0.0241 0. 0013 6 4 0 PV 0.0139 0.0272 0. 0187 0.0167 0.0004 0.0689 0.0640 0.0643 0.0252 0.0410 0. 0023 ? 4 0 PI 0.0102 0.0440 0.0371 0 . 0300 0.0094 0.0273 0.0336 0.0122 0.0139 9.9423 0.0024 • 3 c s 0.0015 0.0012 0.0017 0.0014 0.0002 9.0024 0.0043 0.0070 0.0058 0.0095 — 0.0001 9 3 c PX 0.0002 0.0013 0.0013 0.0006 0.0009 0.0112 0.0110 0.0170 0.0055 0.0066 0. 0004 10 5 c PY 0.0000 — 0.0028 0.0041 0.0028 0.0004 0.0048 0. 0003 0.0031 0.0026 0.0005 — 0.000 1 11 3 c P 2 0.0010 0.0053 0.00 73 0.0032 9.0018 6.0031 0.0131 0.0064 0.0027 0.9033 9.0004 12 0 H S 0.0013 0.0017 0.0003 0.0014 0.0006 9. 0042 0. 0033 0.0 049 0.0004 0.0060 0.0002 13 7 H S 0.0770 0.0043 0. 0569 0 . 0*44 0.0130 0.0746 9.0433 0.0593 0.0148 0.0283 0.0029 14 0 c s 0.0010 0.2396 0 . 1 1 19 0.4090 0.0770 0.0233 0.0166 0.0287 0.0127 0.0271 0.0074 13 3 c PX 0.0140 0.1349 0 . 1227 0.1613 0.0550 0.0237 0.0169 0.0881 0.0050 0.0101 0.0009 1 * 0 c PV 0.0103 0.4523 0 . 11 70 0.6141 0.1642 0.0399 0.1132 0.0337 — 0.0 132 0.0137 0. 0077 1 ? 0 c PZ 0.0049 0.0968 0.0242 0.1464 0. 1364 0*0069 0.0169 0.0270 0.0169 0.0039 0.0015 10 9 c s 0.0281 0.0273 0. 0219 — 0.0347 0.0138 0.2436 0.2036 0.3777 0.1128 0.0024 0.0034 19 9 c PX 0.0034 0.0563 0 . 0 346 0.1124 0.0015 0.0379 0.1093 0.0331 0.0323 0 .0212 0.0018 20 9 c PV 0.01 18 0.0462 0. 1285 0.0035 0.0125 0.4344 0.2379 0.5518 0.2267 0.0074 0.0006 21 9 c PI 0.0019 0.0064 0.0147 0.0161 0.0232 0.1223 0.0731 0.1866 0.0989 9.0188 0.0008 22 10 H 3 0.0032 0.0047 0.0034 0.0023 0.0007 0.0049 0*0131 0.0087 0.0003 0.4032 0.0003 23 11 H S 0.9827 0.4439 0.02 70 0.0997 ••9399 9.0091 0.0471 0.0031 0*0092 0.1282 0.0134 24 12 C S 0.4438 0.9510 0 . 1202 0.0081 0.0027 0.1824 0.3639 0.0146 0. 1059 0.0017 0.0042 23 12 c PX 0.02 70 0.1202 1. 08 00 0.0638 0.0438 0.3493 0.6671 0.0284 0.2393 0.0498 0.0190 2 A 1 2 c PV 0.0997 0.008 1 0 . 06 JO 0.9917 0.0064 0. 0939 0.1090 0.0521 0.0536 9.0035 0 . 01 03 27 12 c PZ 0.9380 0.0027 0.0439 0.0064 0.9934 — 9. 1064 0*2471 8.0001 0. 0737 0.0059 0.0024 23 13 c s 0.0001 0.1624 0 . 3495 0.0839 0.1064 0.9663 0.1309 0.0073 0.0016 0.4427 0. 0 1 27 29 1 3 c PX 0.0471 0.3639 0 . 6671 0 . 1090 0.2471 0.1309 1. 1134 0.0428 0.0470 4.0476 0.0273 30 13 c PV 0.0031 0.0146 0.0284 0.0321 0.0001 0.0073 0.0428 0.9763 0.0148 0.0137 0.0070 31 13 c PZ 0.0092 0.1039 0.2393 0. 0336 0.0737 0.9016 0.0470 0.0148 1.0033 0.9452 0.0083 32 14 H s 0.1282 0.0017 0.0498 0.0053 0.0039 0.4427 8.0479 0.0137 0.9452 0.9700 0.0038 33 13 0 s 0.0 134 0.0042 0.0190 0.0103 0.0024 0.0127 9.0273 0.0070 0.0083 0.0058 1 . 7601 34 1 5 0 PX 0.0743 0.0083 0. 0095 0.0093 0.0262 0.0142 0.0090 0.0089 0.0190 0.0099 0.3026 33 1 5 0 PV 0.0482 0.0934 0.0703 0.0663 0.0601 0.0083 0.0008 0.0013 0.0076 0.0198 0. 1030 30 13 0 PZ 9.1316 0 . 02 J 9 0 . 0683 0.0136 0.0423 9.0349 9.1174 0.0121 0.0048 0.0066 0 . 1574 37 lo c s 0.0101 0.31 16 0.2827 0.3770 0. 1981 0.0130 0.0293 0.0 284 0.0002 0.0245 0.2533 30 1 t » c PX 0.0193 0.1192 0 . 04 06 0.1747 0.1101 0.0191 0.0897 0.0 130 0.0133 0.0002 0.3702 39 16 c PV 0 . 01 J 8 0.4013 0. 3558 — 0. 3394 0.2847 0.0331 0.0344 0.0023 0.0211 0.0422 C . 1 033 40 16 c PZ 0.0983 0.1432 0. 1685 0.1939 0.1314 0.0080 0.0747 0.0240 0.0102 0.0144 0.1328 41 17 c 3 -0.02J3 0.0148 0. 0367 0. 021 1 0.0020 0.3138 0.1901 0.4466 0.1576 0.0121 0.0166 42 1 7 c PX 0.0085 0.0063 0. 0739 0.0308 0.0130 0.0239 0. 1402 0.0632 0.0371 0.0139 0.0241 43 1 7 c PV 0.0414 0.0350 0.0466 0.0062 0.0193 0.4333 0.2536 0.4983 0.2427 0.0049 0. 0048 44 1 7 c PZ 0.0068 0.0138 0 . 068 7 0.0389 0.0045 0.0993 0.0922 0.1611 0.1808 0.1012 0.0017 4 *. 10 u 3 0.0054 0.0128 0.0251 0.01 16 0.0092 0.0040 0.0211 0.0061 0. 0035 0.0139 0. 0004 40 lo a PX 0.0053 0 . 01 53 0 . 0062 0.0083 0. 0173 0 . 01 32 0.0062 0.0 06 3 0.0141 0 .0639 0. 0083 4 7 18 ti PV 0.0220 -o.ooio 0. 0121 0.0069 0 . 0123 0.0963 0. 0626 0.0877 0.0336 0 .0486 0.0018 40 1 0 o PZ 0.0014 0.0363 0. 1097 0.0338 0.0060 0.0140 0. 0364 0.0 153 0.0333 0.1368 0.0032 49 19 H s 0.0206 0.0412 0.0563 0.0260 0. 0194 0.0393 0.0611 0.0162 0.0148 0.0237 0.0018 50 1 9 N PX 0 . 021 J -0.0194 0. 03 32 0.0009 0.0196 0.0107 0. 0278 0.0034 0. 0133 0.0260 0. 0126 3 1 19 N PV 0.01 13 0.0392 -0. 01 14 0.0098 0 . 0224 0.0432 0.0161 0.0 104 0. 0247 0.0147 0 . 01 52 32 19 N PZ 0.0755 0.0279 0.0033 0 . 009 1 0.0202 0.0213 0.0031 0.0063 0.0237 0.0748 0.0149 33 20 M s 0.0034 0.0029 0 . 01 65 0.0098 • 0.0029 0.0061 0.0111 0.0133 0.0037 0.0047 0. 0042 34 21 C 3 0.0001 0.0280 0. 0003 0.0263 0. 0190 0 . 0277 0 . 0062 0.0280 0.0157 0 .0007 0.0 1 29 S3 21 c PX 0. 0006 0 .0040 0.0059 0.0091 0.0002 0.0083 0.0040 0.0025 0.0075 0.0004 0.0073 50 21 c PV 0.0006 0.0487 0. 00 1 0 0.0392 -0.0303 0.0475 0.0114 0.0422 0.0249 0.0031 — 0.0068 37 21 c PZ 0.0001 -0.001 1 0. 0038 0« 0033 9.0089 9. 0939 0.0023 0.0070 0.0059 0.0000 0.0009 SO 22 H s 0.0164 0.0095 0 . 0040 8.0995 9 . 9999 9.9919 8.9989 0.0056 9.0044 0.0166 0.0039 39 23 H s 0.0129 -0.001 7 0 . 0074 9.0041 9.0967 9. 9932 9.9999 0.0937 8.0034 0.0123 0.0024

PAGE 166

156 34 35 36 37 30 39 40 4 1 42 43 44 1 1 H s 0.0001 0.0015 0.0040 -0.0047 -0. 00.01 -0.0047 -0.0045 -0.0007 -0.0014 -0.0004 0.0031 2 2 H 5 0.0000 0.0105 -0. 0041 -0.0342 -0.0147 -9.044* -o.ooot 0.0069 -0.0063 0.0071 0.0060 3 3 H S -0.0055 -0.0045 0.0130 0.0031 0.0071 0.0035 -0.0091 -0.0200 0.0029 -0.0394 -0.0069 6 6 O S 0.0015 0.0057 0.0104 -0.0137 -0.0019 -0.014* -9.0110 0.0 094 -0.0060 0.0130 0.0002 5 6 U PX -0.001 1 -0.0045 -0.0003 0.0146 0.0014 0.0145 0. 0115 -0.0055 0.0001 -0.0009 -0.0126 6 4 0 PY -0.0024 -0.0060 -0.01 06 0.0175 0.0010 0.0154 0.0126 -0.0209 0.0107 -0.0304 0.0017 7 4 o PZ 0.0020 0.0073 0. 0127 -0.0104 -0.0020 -0.0204 -0.0129 0.0054 -0.0062 0.0060 0.0110 a 3 c s 0.0002 -0.0005 -0.0017 0.0023 -0.000! 0.0020 0.0029 0.0005 0.0005 -0.0002 -0.0010 9 5 c PX 0.0001 0.001 1 0.0031 -0.0048 -0.0001 -0.0039 -0.0049 0.0014 -0.0010 0.0031 0.0025 10 5 c PY -0.0002 -0.0002 0. 0000 -0. 0007 0.0001 -0.0004 -0.0007 -0.0009 -9.0006 -0.0013 0.0014 II 5 c PZ 0.0003 0.001* 0.0025 -0.0030 -0.0000 -0.0037 -0.0022 0.0001 -0.0006 0.0004 0.0006 12 6 H 5 0.0003 0.0009 0. 0009 -0. 0024 -0.0005 -0.0021 -0.0015 0.0047 -9.0011 0.0053 -0.0003 13 7 N 5 -0.0020 -0.0006 0.0107 0.0269 v 0.021* 0.0299 -0.0115 -0.0322 -0.0037 -9.0334 0.0206 16 • c 5 -0.0105 -0.0052 0.0064 0.0002 -^. 001 5 -0. 0079 0.0000 0.0444 -0.0000 0.0450 -0.0155 IS 0 c PX 0.0112 0.0011 -0.0274 0.0134 -0.0045 0.0310 0.0361 0.0203 0.0147 0.0213 -0.0233 1* a c PY 0.02 74 0.0020 -0.03 73 0.0320 0.0097 0.0343 0.0340 -0.0352 0.0029 -0.0230 0. 0141 17 • c PZ -0.0010 0.0000 -0. 0050 0.0052 0.0021 -0.0070 -0.0076 0.0021 -0.0012 0.0024 -0.0115 10 9 c 3 -0.0064 -0.0130 -0.0138 0.0401 0.0110 0.0453 0.0230 -0.0017 0.0007 -0.0120 -0.0025 19 9 c PX 0.0005 0.001 7 0. 0085 -0.0220 0.0070 -0.0194 -0.0240 -0.0259 -0.0104 -0.0295 0.0224 20 9 c PY -0.0002 0.0001 -0. 0023 -0.0253 -0.0005 -0.0103 -0.0079 0.0393 0.0026 0.0404 -0.0361 21 9 c PZ 0.0005 0.0036 0.00 72 -0.0063 -o.oou -0.0034 -0.0140 0.0000 0.0014 0.0120 -0.0004 22 10 H 5 -0.0003 -0.0016 -0.0034 0.0052 0.000* 0.0049 0.0043 -0.0019 0.0025 -0.0024 -0.0014 23 11 H S 0.0745 0.0402 -0. 1316 0.0101 -0.0193 -0.0130 0.0903 -0.0233 -0.0003 -0.0414 0. 0060 26 12 c 3 -0.0005 -0.0934 -0. 0236 0.3116 0. lift 0.4015 4. I 452 0.0140 -0.0063 0.0350 0.0130 25 12 c PX 0.0095 0.0703 0. 0483 -0.2827 0.040* -0.3550 -0. 1605 0.0 367 -0. 0739 0.0466 0.0607 26 12 c PY 0.0093 0.0663 0. 0156 -0.3770 -0.1747 -0.3594 -0.1959 0.021 1 0.0300 -0.0062 —0. 0309 27 12 c PZ 0.0262 0.0601 -0. 0425 -0. 1901 -0.1101 -0.2047 0. 1314 0.0020 -0.0150 -9.0193 0.0045 20 13 c S 0.0142 -0.0003 0.0349 0.0150 0.0191 0.0531 -0.0000 0.3136 -0.0230 0.4335 -0.0995 29 13 c PX -0.0090 0.0000 -0. 1174 -0.0295 -0.0097 -0.0344 0.0747 0.1 901 0.1402 0.2536 -0.0922 30 13 c PY -0.0009 -0.0013 -0.0121 0.0204 -0.0130 0.0025 0.0240 •0.4466 0.0032 -0.4983 0. 1611 31 13 c PZ 0.0190 0.0076 0.0040 -0.0002 -0.0135 0.0211 0.0102 0.1576 -0.0371 0.2427 0. 10 00 32 1* H s 0.0099 0.0190 0.0066 -0.0245 -0. 0002 -0.0422 -0.0144 0.0121 0.0159 -9.0049 -0.1012 33 IS 0 s -0.3026 -0.1030 -0. 1574 0.2553 -0.3702 -0.1053 -0.1520 0.0 166 -0.0241 -0.0040 0.0017 36 15 0 PX 1.3144 -0.1930 -0.0749 0.4813 -0.4290 -0.1*45 -0.4030 0.0 346 -0.0402 -0.0160 0.0247 35 IS 0 PY -0.1930 1 .0719 0.0518 0.1102 -0.1700 0.2102 -0.2155 -0.0030 -0.0010 0.0147 0.0213 3* IS o PZ -0.0749 0.0510 1.3890 0.1910 -0.4072 -0.2103 0.6230 0.0335 -0.0103 -0.0150 -0. 0650 37 16 c s 0.4013 0.1102 0.1910 1.030 0 -0.0670 0.0297 -0.0112 -0.0001 -0.0123 -9.0059 0.0001 30 16 c PX -0.4290 -0.1700 -0.4872 —0.067 0 0.801* 0.0131 0.0479 0.011 1 —0. 03 84 0.0089 -0.0069 39 16 c PY -0.1645 0.2182 -0. 21 03 0.0297 0.0131 0.9260 0.0400 -0.0001 0.0003 -0.0032 -0.0077 60 1* c PZ -0.4030 -0.2155 0.6230 -0.0112 0.0479 0.0400 0.8111 -0.0G03 -0.0064 0.0046 0.0356 61 17 c s 0.0346 -0.0030 0. 0335 -0.0001 O.OItl -0.0001 -9.0003 1.0304 0.0720 0.0124 0. 0 155 62 17 c PX -0.0402 -0.0010 0 . 01 as -0.0123 -0. OJ04 0.0005 -0.0064 0.0720 0.0765 -0.0059 0.0360 63 17 c PY -0.0160 0.0147 -0.0158 -0.0059 0.0009 -0.0032 0.0046 0.0 124 -0.0059 0.9370 -0.0354 66 17 c PZ 0.0247 0.0213 -0. 0650 0.0001 -0.0069 -0.0077 0.0356 0.0 155 0.0366 -0.0354 0.0011 65 10 o 3 -0.0078 0.0035 0.0035 0.0171 0.0229 -0.0107 -0.0025 0.2553 0.3350 -0.2029 0. 1360 66 ia o PX 0.0350 -0.0027 -0. 0169 -0.0345 -0.0412 0.0276 0.0227 -9.4 399 -0.3091 0.3320 -0. 3997 67 la o PY -0.0051 -0.0079 0.0229 0. 0064 0.0153 0.0081 -0.0164 0.2400 0.3391 0.0450 0.2599 60 10 0 PZ -0.0223 -0.0270 0 . 06 56 -0.0346 -0.0130 0.0295 -0.0642 -0.1 720 -0.4043 0.2559 0.6702 69 19 N 3 -0.0666 0.1076 -0.0130 0.2741 0.3209 -9.3309 0.0401 0.2740 -0.3092 -0.2525 -0.0754 50 19 H PX 0.0524 -0.0926 0.0506 -0.3447 -0.2802 0.4239 -0.0943 0.3 957 -0.4403 -0.3569 -0. 1477 51 19 N PY -0.0356 0.0573 0.0143 0.2719 0.3347 -0.2177 0.0227 0.1 765 -0.2620 -0.0405 -0.0441 52 19 H PZ 0.1001 0.0431 -0.2157 -0.0595 -0.1424 0.0052 0.3474 0.0660 -0.1030 -0.0232 0.3309 53 20 H 3 0.0059 -0.0265 0.0004 -0.0320 -0.0417 0.0315 -0. 0057 0.0361 -0.0641 -9.0400 -0.0141 56 21 C 3 -0.0127 0.001 1 -0. 0107 0.0065 -0.0030 -0.0037 0.0031 0.0000 0.0040 -0.0042 -9.0039 55 21 C PX 0.0094 -0.0216 0. 0047 -0.001 5 -0.0027 0.0301 0. 0020 0.0034 -0.0014 -0.0310 -0.0042 56 21 57 21 PZ S 5 0.0037 -0.0006 ••01*2 0 . 01 « 0 . 00*3 0325 0. 0379 —0.0*20 0.0200 0 . 00*0 -0.0172 0.0005 0.0325 • 0026 •0050 0.0131 0.0030 -0.0065 -0.0056 0.0*25 -0.0326 SO 23

PAGE 167

157 45 46 47 46 46 36 SI 32 S3 34 53 1 1 H S 0*0003 0*0003 0* 0002 -0*0636 -6*6667 —6*3611 -6*9666 6*6663 -6.0004 0.0000 0.0000 2 2 H 3 -0*0002 0*0044 -0*0032 -6*012! 6*6664 -6*6607 6*0027 -0*0102 -0*0016 -6.0021 0.0002 3 3 H S 0*0033 -0*0060 0* 0106 0*0076 -6*0636 -6*0032 -0.0006 0.0126 0*0006 -6.0011 -0*0010 4 4 0 5 0*0013 ^.0*0007 -0*0033 -0*0116 -0.0032 -6*0033 -0.0029 -0.0012 -0*0021 0.0013 0.0003 S 4 o PX -0.0006 -0.0024 0*0030 0*0121 -0.0002 0.0016 -0.0003 0.0023 0.0010 0.0002 -0.0002 * 4 0 py -0*0023 0.0032 0.0042 0*0025 0.0163 0.0146 0.0000 -0.0 C36 0.0032 -0.0031 -0.0003 7 4 0 PZ 0*0013 0*0013 -0*0013 -0*0123 -0*0027 -6*0041 -0.0013 -0.0064 -0.0017 0.0000 0.0003 • 3 c s -0*0003 -0*0001 0.0000 0*0023 0. 0006 0.0010 0.0003 0.0001 0.0003 -0.0001 -0.0001 • 3 c PX 0*0003 0*0002 -0*0010 -0.0036 -0.0016 -0.0020 -0.0011 -0.0C03 -0.0007 0.0004 0.0001 to 3 c py 0*0001 0*0006 0. 0003 -0.0011 0.0009 0.0003 0.0007 -0.0006 0.0002 -0.0003 -0.0001 II 5 c Pl 0.0001 -0*0002 -0.0007 -0.0023 -6*0013 -0*0013 -0.0006 0.0003 -0*0004 0.000! 0.0001 12 6 N s 0*0002 -0*0001 -0*0012 -0*0669 -0*0016 -6*0620 -0.0006 0.0000 -0.6006 0.0006 0*0001 13 7 M 3 0*0044 -0*0003 0*0137 —0*9209* ^P*6114 0*0110 -0. 0003 -0.0011 0*0041 0.0636 0.0009 14 d C S -0*0029 0*0006 -0.0143 0*0108 0.0316 -0*0271 0.0300 0.0 104 -0*0039 -0.0047 -0.0012 13 0 c PX -0.0026 -0.0006 -0. 0040 0*0123 -0.0120 0*0133 -0.0129 -0.0 120 0.0026 0.0043 0.0013 16 a c py 0.0004 0.0003 0.0034 -0*0031 -0.0462 0.0433 -0.0404 -0.0328 0.0090 0.0112 0.0043 17 0 c Pl -0.0003 -0.0007 -0.0037 0*0036 0.0094 -6*0066 0.0123 0.0024 -0.0016 -0.0020 -0.0002 10 9 c s -0*0077 0.0178 -0.0070 -0*6063 0.0332 0.0332 0.0271 -0.0132 0. 0094 -0.0037 -0.0020 19 9 c PX 0*0004 0.0055 0.0004 -0.0101 0.0033 0.0093 0.0033 -0.0063 0.0021 -0.0021 -0.0003 20 9 c py 0.0069 -0.0274 0. 0009 0.0437 -0.0464 -0.0333 -0.0322 0.0262 -0.0136 0.0122 0.0012 21 9 c PZ 0*0021 -0*0034 -0.0077 -0.0034 -0.0140 -6*0133 -0.0126 0.0027 -0.0037 0.0033 0.0012 22 10 H s -0.0004 0*0006 0. 0009 0.0027 0*0022 0*0026 0.0013 -0.0003 0.0009 -0.0004 0. 0000 23 11 H s 0.0034 -0*0053 0*0220 -0*0014 -0*0206 6*0213 -0*0113 -0.0733 0.0034 0.0001 -0.0006 24 12 c s 0.0120 -0*0133 -0* 0010 -0*0363 -0.0412 -0*0164 -0.0392 -0.0279 0.0029 0.0280 0.0040 25 12 c PX 0.0251 -0*0062 0.0121 -0.1097 -0.0343 -0*0332 -0.0114 -0.0033 -0.0165 0.0003 0.0059 26 12 C PY -0.01 16 0.0083 -0.0069 0.0336 0.0260 -0*0009 -0.0066 0.0 091 -o.ooaa -0.0263 -0.0091 27 12 c PZ -0.0092 0.0173 -0.0123 0.0060 6.0164 9*0163 0.0224 -0.0202 -0.0029 -0.0190 -0.0002 28 13 C s 0.0040 -0.0132 -0.0963 0.0140 -0.0393 0*0107 -0.0432 0.0213 -0.0061 0.0277 0.0083 29 13 C PX -0.021 1 -0.0062 -0. 06 26 0.0364 0.0611 -0*0270 0.0161 -0.0031 -0.0111 -0.0062 0. 0040 30 13 c py -0.0061 0.0063 0. Od 77 -0.0133 0.0162 0*0034 -0.0104 -0.0063 0.0133 -0.0200 -0.0023 31 13 c PZ -0*0035 0.0141 -0.0336 -0.0333 -0.0146 0*0133 -0.0247 -0*0237 -0.0037 0.0137 0.0073 32 14 H a 0*0139 -0.0639 0* 04 86 0.1366 -0*0237 -0* 0290 -0.0147 0.0748 -0.0047 0.0007 0.0004 33 15 o s -0.0004 0.0083 0.0018 -0.0032 -0.0016 0*0126 0.0152 0.0 148 0.0042 -0.0129 0.0073 34 1 5 0 PX -0.0070 0.03S0 -0.0051 -0.0223 -0.0666 0*0524 -0.0356 0.1 081 0.0039 -0.0127 0.0094 33 IS u py 0.0035 -0.0027 -0. 0079 -0. 0270 0. 1076 -0*0926 0. 0573 0.0431 -0.0263 0.001 1 -0.0216 36 IS u PZ 0.0033 -0.0169 0. 0229 0.0656 -0.0136 0*0306 0.0143 -0.2137 0.0004 -0.0187 0.0047 37 16 c •• 0.01/1 -0.0343 0.0064 -0. 0346 0. 274 t -0.3447 0.2719 -0.0 595 -0.0320 0.0063 -0.0013 33 16 C PX 0.0229 -0.0412 0.0153 -0.0130 0.3209 -0*2602 0.3347 -0.1 424 -0.0417 -0.0030 -0.0027 J9 1 e C PT -0.0 l 07 0.0276 0. 0081 0.0293 -0.3389 0*4239 -0.2177 0.0052 0.0313 -0.0037 0.0301 40 16 C PZ -0.0023 0.0227 -0.0184 -0.0642 0.0401 -0*0943 0.0227 0.3474 -0.0037 0.0031 0.0020 41 17 C s 0.2353 -0.4399 0. 2400 -0.172 8 0.2740 0*3937 0.1765 0.0066 0.0561 0.0066 0.0034 42 17 c PX 0.3JS0 -0.3091 0. 3391 -0.4043 -0.3892 -0*4403 -0.2628 -0.1830 -0.0641 0.0040 -0.0014 43 17 c py -0.2029 0.3320 0. 04 58 0.2359 -0.2323 -0*3369 -0.0485 -0.0232 -0.0480 -0.0042 -0.0316 44 17 c PZ 0*1360 -0.3997 0.2599 0.6702 -0.0734 -0*1477 -0.0441 0.3 309 -0.0141 -0.0039 -0.0042 45 18 0 s 1*7600 0.3462 -0.2052 0. 1401 -0.0020 -0* 0092 0.0190 -0.0 122 0.0033 -0.0 102 -0.0016 46 Id Q PX 0*3462 1.4332 0.3051 -0.0494 0.0080 0*0796 0. 0203 0.1 012 0.0067 0.0104 0.0030 47 Id a py -0*2032 0.3051 1. 7584 0.0131 0.0884 0*0611 0.0343 -0.0365 0.0086 -0.0099 -0.0013 40 10 0 PZ 0*1401 -0.0494 0.0131 1.3642 0.0274 0*0390 -0.0006 -0.2105 -0.0017 0.0137 0.0066 4* 19 N s -0*0020 0.0888 0. 0884 0.0274 1.1837 0.0040 0.0030 -0.0079 -0.0064 0.2S45 0. 0660 SO 19 N PX -0.0092 0.0796 0. 0811 0.0590 0.0040 1.1693 -0.0030 -0.0669 0.0457 -0.0514 0. 1384 51 19 N py 0.0 190 0.0203 0. 0343 -0.0008 0.0030 -0.00 JO 1. 1194 -0.0170 -0.0043 -0.4164 -0. 1063 52 19 H PZ -0.0122 0.1012 -0.0365 -0.2105 -0.0079 -0.0669 -0.0170 1. 7 038 -0.0030 -0.0169 -0.0112 33 20 H s 0.0033 0.0067 0.0086 -0.001 7 -0. 0064 0.0437 -0.0043 -0.0038 0.9940 0.4979 -0.6326 54 21 C 5 -0.0 1 02 0*0104 -0.0099 0.0137 0.2343 -0.0314 -0.4164 -0.0 169 0.4979 1.0219 -0.01 14 55 21 C PX -0.0016 0*0050 -0. 0013 0.0066 0. 0660 0.1364 -0.1065 -0.0 112 -0.0326 -0.0114 0.9669 56 21 c py -0.0372 -0*0005 -0.0253 0.0189 0.3032 -0.1003 -0.6661 -0.0344 -0.1761 -0.0820 -0.0094 37 21 c PZ -0.0026 0*0101 -0.0036 -0.0156 0.0205 -0.01 13 -0.0339 0.1 526 -0.0907 -0.0033 0.0006 50 22 H s -0.0016 0*0129 -6.0126 -6.0366 -0*6039 -6*6369 0*0646 0.1 030 -0.0314 0.4994 0.4302 59 23 H 3 0*0018 -0*0166 0*0619 6.6464 -6*0641 -6*6673 6*6664 -0.0969 -0.0282 0.4968 0.2686

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1 1 H 9 96 0.0000 37 0.0000 38 0.00 02 59 0.0001 2 2 H 9 -0.0034 -0.0007 -0.0000 0.0030 3 3 M 9 -0.0013 0.0004 0.0022 -0.0027 4 4 O 9 0.0023 0.0001 0.0007 0.0006 3 4 a PX 0.0002 0.0002 -0. 0002 -0.0009 6 4 a PY -0.0000 -0.0006 -0. 0023 -0.0001 7 4 a PZ 0.0003 -0.0003 0.0000 0.0007 • 9 c 9 -0.0002 -0.0001 -0. ooot -0.0001 4 9 c PX 0.0009 0.0002 0.0002 0.0002 10 9 c PY -0.0009 0.0000 -0.0001 0.0001 II 9 c PZ 0.0003 0.0001 0. 0002 0.0000 12 4 N 9 0.0011 0.0001 0.0002 0.0002 13 7 H 9 0.0092 0.0002 -0.0034 -0.0023 14 8 c 9 -0.0100 0.0002 0.0004 0.0016 19 0 c PX , 0.0073 0.0002 -0.0049 -0.000 1 16 6 c PY 0.0200 -0.0010 -0.0144 -0.0017 17 4 c PZ -0.0044 0.0009 0.0022 0.0000 19 4 c 9 -0.0122 -0.0010 -0.0034 0.001 1 19 9 c PX -0.0034 0.0000 -0.0020 0.0009 29 9 c PY 0.0226 0.0024 0.0000 -0.0020 21 9 c PZ 0.0069 0.0019 0.0017 -0.0003 22 19 H 9 -0.0009 -0.0001 -0.0004 -O.OOOI 23 It H 9 0.0006 0.0001 -0.0164 0.0129 24 12 c 9 0.0467 -0.0011 — 0. 0009 -0.0017 23 12 c PX 0.0010 0.0030 0. 0046 0.0074 26 12 c PY -0.0392 0.0033 0.0003 0.0041 27 12 c PZ -0.0309 -0.0064 0.0008 0.0067 29 13 c 9 0.0479 0.0030 0.0010 -0.0032 24 13 c PX -4.0114 0.0023 0.0055 0.0099 36 13 c PY -0.0422 -0.0070 -0.0030 -0.0037 31 13 c PZ 0.0249 -0.0039 -0.0044 0.0034 32 14 H 9 0.4431 4.0000 0.0164 -0.0129 32 19 o S -4.0046 4.0009 0.0039 0.0024 34 19 o PX -0.0050 0.0067 0.0124 -4.0106 39 IS o PY -0.0219 0.0024 0.0162 -0.0043 39 19 a PZ -0.0249 -0.0090 -0.0329 0.0379 37 14 c 9 0.00(17 -6.0004 0.0201 0.0367 36 14 c PX -0.0232 0.0002 0.0130 0.0470 39 14 c PY -0.0094 0.0041 -0.0420 -0.0295 40 14 c PZ 0.0004 -0.0412 0.0436 -4.0366 61 17 c 9 0.0019 0.0004 -0.0060 -4.0172 42 17 c PX 0.0224 0.0014 0.0005 0.0329 43 17 c PY -0.0024 -0.0030 0.0131 0.0036 46 17 c PZ -0.0049 -0.0034 0.0429 -0.0324 49 14 o 9 -0.0072 -0.0026 -0.0010 0.0010 44 14 0 PX -0.0009 0.0101 0.0129 -0.0100 47 14 0 PY -0.0233 -0.0036 -0.0120 0.0019 44 19 o PZ 0.0109 -0.0130 -0.0304 0.0404 44 19 M 9 4.9032 0.0209 -0. 0099 -0.0041 50 19 M PX -0.1009 -0.0113 -0.0369 -0.0072 91 19 M PY -0.6441 -0.0339 0.0040 0.0046 92 19 M PZ -4.0344 0.1926 0. 1030 -0.0999 93 20 * H 9 -4.1741 -0.0907 -0.0314 -o.otoo 94 21 c 9 -0.0020 -0.0033 0.4994 0.4966 39 21 c PX -0.0094 0.0000 0.4302 0.2000 94 21 c PY 0.9023 -0.0039 -0.3202 -0.3944 97 21 c_ _PZ -0.0039 0.9023 -0.6410 0.7176 94 22 M 9 -4.3262 -6.6616 1 • 0964 -4.0447 99 23 N 9 -4.3949 6.7176 -4.0467 1.4466 TUTM. ENCR6V • •I32«4I7901U3< 1 H 1.01 1 0 2 H 0.9702 3 H 1 .0220 4 a 6.2300 9 c 3.0506 6 M 1 .0149 7 H 1 .0050 a C 3.9912 9 C 3. 7060 10 M 1.0197 11 H 0.9027 12 C 4.0161 13 C 4.061 3 14 H 0.9700 15 O 6.3362 16 c 3.6579 17 c 1.6510 10 o 6.3359 19 N 3.1764 20 H 0.9940 21 C 3.0933 22 H 1 .0093 23 H I .0055 DIPOLE MOMENTS COMPONENTS X DENSITIES 0.2453? S.P 0.33304 P.O 0.00000 IOTA*. 0.50440 1.01443 0.13740 0.00000 1.93242 0.62006 1.07014 0.00000 1.69002 01 POLE MOMENT* 2.66192 OCBVES

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BIBLIOGRAPHY 1. H. Standinger, W. Heuer, Ber.,_67, 1164 (1934) 2. G.B. Butler, Acc. Chem. Res., JJ5_, 370 (1982) 3. G.B. Butler, R.J. Angelo, J. Am. Chem. Soc., _79_> 3128 (1957) 4. P.J. Flory, J. Am. Chem. Soc., _59_, 241 (1937) 5. D.S. Breslow, Pure Appl. Chem., 45_, 103 (1976) 6. T.F. Gray, Or., G.B. Butler, J. Macromol. Sci.-Chem., A9(l), 45 (1975) 7. A.L.J. Beckwith, Tetrahedron, 2ZJ18)« 3073 (1981) 8. (a) B. Capon, C.W. Rees, Annual Reports, _61_, 261 (1964); (b) B. Capon, Quart. Rev., JL8_, 45 (1964) 9. (a) P. Bischof, Tetrahedron Letters, 1291 (1971); (b) P. Bischof, Heir. Chim. Acta., 63_, 1434 (1980) 10. (a) R.D. Rieke, N.A. Moore, J. Org. Chem., 37, 413 (1972); (b) R.D. Rieke, N.A. Moore, Tetrahedron Letters, 2035 (1969) 11. (a) M. Julia, M. Maurny, Bull. Soc. Chim. Fr., 1603 (1968); (b) M. Julia, C. Descoins, M. Baillarge, B. Jacquet, D. Ugnen, F.A. Groeger, Tetrahedron, _31_» 1737 (1975); (c) A.L.J. Beckwith, T. Lawrence, J. Chem. Soc. Perkin Trans. II, 1535 (1979) 12. (a) A.L.J. Beckwith, W.B. Gara, J. Chem. Soc. Perkin Trans. II, 593 , 795 (1975); (b) A.L.J. Beckwith, G.F. Meijs, Ibid. Chem. Commun., 136 (1981) 13. (a) D.L. Struble, A.L.J. Beckwith, G.E. Gream, Tetrahedron Letters 3701 (1968); (b) A.L.J. Beckwith, G.E. Gream, D.L. Struble, Aust. J. Chem., 25, 1081 (1972) 14. A.L.J. Beckwith, "Essays on Free Radical Chemistry" (Chem. Soc. Publ. No. 24, p. 239, Chem. Soc., London, 1970) 159

PAGE 170

160 15. A.L.J. Beckwith, I. A. Blair, G. Phi T 1 i pou , Tetrahedron Letters, 2251 (1974) 16. T.W. Smith, G.B. Butler, J. Org. Chem., 43^, 6 (1978) 17. (a) M. Julia, Pure Appl. Chem., 40, 553 (1974); (b) M. Julia, Acc. Chem. Res., £, 386 (1971) 18. (a) R.S. Mulliken, J. Am. Chem. Soc., 74, 811 (1952); (b) R.S. Mu Hi ken, J. Phys. Chem.,_56_, 801 (1952T 19. R.S. Mulliken, J. Chem. Phys., 61, 20 (1964) 20. M.J.S. Dewar, C.C. Thompson, Tetrahedron Supp., No. 7, 97 (1966) 21. (a) E.M. Kosower, Prog. Phys. Org. Chem., _3, 81 (1965) (b) E.M. Kosower "Introduction to Physical Organic Chemistry" (Wiley, New York, 1968) 22. H.K. Hall, Jr., Angew. Chem. Int. Ed., 22, 440 (1983) 23. R. Foster, "Molecular Complexes," Vol . 2, p. 172 (Crane Russak & Co. Inc., 1974) 24. H.K. Hall, Jr., T. Gotoh, Polym. Preprints, 26(1) , 34 (1985) 25. G.B. Butler, K.G. Olson, Macromolecules, _16_, 707 (1983) 26. R.B. Seymour, G.A. Stahl, D.P. Garner, R.D. Knapp, Polym. Preprints, 17(1) , 216 (1976) 27. Y. Lai, G.B. Butler, J. Macromol. Sci.-Chem., A21 (11 & 12), 1547 (1984) 28. Merck & Co., Inc., "Deuterated NMR Sol vents— Handy Reference Data" (Merck & Co., Inc., Quebec, 1978) 29. A.J. Gordo, R.A. Ford, "The Chemists Companion: A Handbook of Practical Data, Techniques and References" (John Wiley & Sons, New York, 1972) 30. L.F. Hatch, T.L. Patton, J. Am. Chem. Soc., 76_, 2705 (1954) 31. K. Baucom, Ph.D. Dissertation, University of Florida, 1971 32. K. Ramarajan, K. Ramalingam, D.J. O'Donnell, K.D. Berlin, Org. Synthesis, _61_, 56 (1983) 33. A.F. Ferris, I.G. Marks, J. Org. Chem., 19_» 1971 (1954) 34. P. A. Levene, Org. Synthesis, Coll, 10, 12 (1930)

PAGE 171

161 35. R.M. Jacobson, R.A. Raths, J.M. McDonald, J. Org. Chem., 42(15), 2545 (1977) 36. C. Greenwood, H.M.R. Hoffman, J. Org. Chem., 37(4) , 611 (1972) 37. R.W. Rosenthal, L.H. Schwartzman, N.P. Greco, R. Proper, J. Org. Chem., 28, 2835 (1963) 38. B.E. Leggetter, R.K. Brown, Canadian J. Chem., 42_, 990-1004 (1964) 39. W. Reeve, A. Saddle, J. Am. Chem. Soc., 12, 1251 (1950) 40. R.C. Fuson, B.H. Wojcik, Org. Synthesis, _13_, 42 (1944) 41. W. Fickett, H.K. Garner, H.J. Lucas, J. Am. Chem. Soc., 73, 5066 (1951) 42. R.B. Moffett, Org. Synthesis Cum., Vol . 4, 834 (19//) 43. L.S. Boguslavskaya, A.B. Bulovyatava, A.P. Sinekov, Y.S. Ettis, Zh. Organiche. Khimii, 7(4) , 637 (1971) 44. A. J. Hill, E.J. Fischer, J. Am. Chem. Soc., 44, 2594 (1922) 45. R.M. Silverstein, G.C. Bassler, T.C. Morrill, "Spectrometric Identification of Organic Compounds" (4th Edition, John Wiley & Sons, New York, 1981) 46. (a) J. March, "Advanced Organic Chemistry" pp 342 (3rd Edition, Wiley Interscience, 1985); (b) S. Warren, "Designing Organic Synthesis" (J. Wiley & Sons Ltd., Great Britain, 1979) 47. K. Baucom, Ph.D. research. University of Florida 48. Insensitive nuclei enhanced by polarization transfer 49. M. Turushima, Y. Ando, K. Yetani, Yakugaku Zasshi,_93_» 1274 (1973) 50. M. Turushima, Y. Ando, K. Yetani, ibid, 93, 1285 (1973) 51. M. Turushima, Y. Ando, K. Yetani, ibid, _93_, 1294 (1973) 52. Dr. S. Mallakpour, University of Florida 53. (a) No. 22623 "The Sadtler Standard Spectra" (Sadtler Research Laboratories, Inc., U.S.A., 1976); (b) No. 3944 ibid (Sadtler Research Laboratories, Inc., U.S.A., 1967) 54. W.C. Herndon, J. Fever, J. Am. Chem. Soc., 5914 (1968) R. Arnaud, D. Faramond-Baud, M. Gelus, Theoret. Chim. Acta., 31, 335 (1973) 55.

PAGE 172

162 56. D.B. Chesnut, P.E.S. Wormer, Theoret. Chim. Acta., _20_, 250 (1971) 57. R. Lochmann, T. Weller, Int. J. Quantum Chem., Vol . X, 909 (1976) 58. R. Lochmann, H.J. Hofmann, Int. J. Quantum Chem., Vol. XI, 427 (1977) 59. J.A. Pople, D.L. Beveridge, "Approximate Molecular Orbital Theory" (McGraw Hill, New York, 1970) 60. (a) S. Diner, J.P. Malrien, P. Claverie, Theoret. Chim. Acta., JJ, 1 (1969); (b) J.P. Malrien, P. Claverie, S. Diner, Theoret. Chim. Acta., T3_, 18 (1969); (c) S. Diner, J.P. Malrien, F. Jordan, M. Gilbert, Theoret. Chim. Acta., _15_, 100 (1969); (d) F. Jordan, M. Gilbert, J.P. Malrien, U. Pincelli, Theoret. Chim. Acta., 15, 211 (1969) 61. Publication by Quantum Chemistry Program Exchange, Indiana University, Program No. 220/221 62. J.D. Dandey, P. Claverie, J.P. Malrien, Int. J. Quantum Chem., 8, 1 (1974) 63. (a) J.A. Pople, Santry, Segal, J. Chem. Phys., 43_, 5129 (1965); (b) J.A. Pople, G.A. Segal, J. Chem. Phys., 47, 5136 (1965); (c) J.A. Pople, G.A. Segal, J. Chem. Phys., 44, 3289 (1966); (d) D.P. Sentry, G.A. Segal, J. Chem. Phys., 47, 158 (1967); (e) J.E. Ridley, M. Zerner, Theoret. Chim. Acta., _32, 111 (1973); (f) J.E. Ridley, M. Zerner, Theoret. Chim. Acta., 42_, 223 (1976); (g) A.D. Bacon, M. Zerner, Theoret. Chim. Acta., j)3_, 21 (1979); (h) M. Zerner, G.H. Zeow, R.F. Kirchner, U.T. Mueller-Westerhoff , J. Am. Chem. Soc., 102_, 589 (1980) 64. QUIPU uses Quantum Chemistry Program Exchange Programs and the University of Florida, Quantum Theory Project programs and was written by Dr. G. Purvis. It is a local adaptation of the DuPont Molecular Modeling system, TRIBBLE developed by D. Pensak at DuPont's Central Research Division, Wilmington, Del. 65. The Cullen, Zerner version of PCIL0 by J.P. Daudey 66. G.B. Butler, A. Matsumoto, J. Polym. Sci., Polym. Letters Edition, 9_, 167 (1981) 67. G.B. Butler, A. Matsumoto, T. Kitamura, M. Oiwa, J. Polym. Sci., Polym. Chem. Edition, 19, 2531 (1981)

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BIOGRAPHICAL SKETCH Roy Joseph Noel Vaz was born on August 2, 1958, in Bombay, India. In 1974 he obtained the secondary school certificate via Sacred Heart High School, Santa Cruz, and after a year at St. Xavier's College, Bombay, joined the Indian Institute of Technology, Bombay. He obtained the M.S. (5 year integrated) in 1980 and subsequently enrolled at the University of Florida. He was awarded the DuPont teaching award in 1982 and is currently a member of the American MENSA. 163

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I certify that I have read this study and that in my opinion it conforms to acceptable standards of scholarly presentation and is fully adequate, in scope and quality, as a dissertation for the degree of Doctor of Philosophy. ,4 A. A George B. Butler, Chairman Professor of Chemistry I certify that I have read this study and that in my opinion it conforms to acceptable standards of scholarly presentation and is fully adequate, in scope and quality, as a dissertation for the degree of Doctor of Philosophy. A, ' C-t. C < /. f / / Merle A. Battiste Professor of Chemistry I certify that I have read this study and that in my opinion it conforms to acceptable standards of scholarly presentation and is fully adequate, in scope and quality, as a dissertation for the degree of Doctor of Philosophy. ' ' i ' Ken B. Wagener Associate Professor of Chemistry I certify that I have read this study and that in my opinion it conforms to acceptable standards of scholarly presentation and is fully adequate, in scope and quality, as a dissertation for the degree of Doctor of Philosophy. V Vsill, Wallace S Professor Brey, Jr. of Chemistry

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I certify that I have read this study and that in my opinion it conforms to acceptable standards of scholarly presentation and is fully adequate, in scope and quality, as a dissertation for the degree of Doctor of Philosophy. Christopher D. Batich Professor of Materials Science and Engineering 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. August, 1985 Dean, Graduate School