Mechanistic Studies Of The Reactions Of Some

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Mechanistic Studies Of The Reactions Of Some

Transcript Of Mechanistic Studies Of The Reactions Of Some

MECHANISTIC STUDIES OF THE REACTIONS OF SOME ALLYLIC HALIDES A thesis presented by Mohammac Rahimizadeh for the degree of Doctor of Philosophy of the University of London
September 1977

A review of nucleophilic substiWtion is set forth, in which the diffPrent techniques available for the elucidation of reaction mechanism are described. Allylic solvolytic reactions are briefly summarised.
An account is given of the synthesis of several new (reactive) allyli.c chlorides. A chlorination method particularly useful for the preparation of very reactive or volatile allelic chlorides is described.
The solvolytic reactions (solvolyses) of 5-chloropent-3-en-l-yne and 3-chloro-pent-4-en-l-yne are studied and possible mechanisms are propounded. The solvolytic mechanism for the former compound is of a bimolecular type and it is suggested that the rate determining step is fortnation of a nucleophilically solvated ion-pair intermediate. However, for the latter compound the mechanism has a unimolecular character, and product distributions are explained by the involvement of two discrete ion-pair intermediates. It is suggested that the rearrangement ana solvolysis reactions have the same ion-pair intermediate for the 3-(qiloro compound.
The isomerisation of 3-chloro-pent-4-en-l-yne has been studied in sulpholane at different salt concentrations. The reaction is shown to follow unimolecular kinetics in the absence of lithium chloride (chloride ion). However, lithium chloride accelerates the reaction so that the composite rate of rearrangement becomes dominated by a bimolecular nrocess.

To my Parents

I am most grateful to my supervisor Dr E S Weight for his patience, guidance and encouragement during the course of this research. I am also indebted to Professor Sir Derek Barton for the opporunity of working in the Chemistry Department.
The technical co-operation of Mr R Carter and his staff is greatly appreciated. My special thanks go to Mr J Bilton for his friendly assistance, Mrs J Lee in obtaining mass spectra and Mr E Pepper for his cooperation with instrument service. I would like to express my sincere thanks to Mrs B Day and Mrs I Hamblin in the Organic Store for their friendship.
My deepest thanks go to my friends and colleagues Mr J Bilton, Ms M A Baguena and Dr N Kyriakidis whose friendship will always be remembered. I would also like to mention my late friend Mr H Rahman. I also wish to thank Miss B Johnston for typing the manuscript. Finally, I am greatly indebted to the Ministry of Science and Higher Education of Iran for providing financial support.

INTRCDUCTION CHAPTER 1 1. Nucleophilic Substitution Reactions
1.1 Normal Bimolecular Nucleophilic substitution
1.2 Abnormal Bimolecular Nucleophilic substitution
1.3 Unimolecular Nucleophilic Substitution 1.4 Nucleophilic Substitution of Borderline
Type Substrates 1.5 Ion-pair Intermediate in the Reactions
of Allylic Substrates 1.6 Allylic Solvolytic Reactions
CHAPTER 2 2. Result and Discussion of Synthetic Work

Page 1
6 6 9 13 15 19 29


3. Result and Discussion of Solvolytic Reactions of

3-chloro-pent-4--en-i-yne and 5-chloro-pent-3-en-



3.1 The Vinyl-acetylene System


3.2 Solvolysis of 3-chloro-pent--4-en-1-yne


3.2.1. The Effect of Solvent Ionizing



3.2.2 The Salt Effect


3.2.3 The Common Ion Effect


3.2.4 Result and Discussion


3.3 Solvolysis of 5-chloro-pent-3-en-l-yne


3.3.1 Result


3.3.2 Discussion and Conclusion



4. Rearrangement of 3-chloro-pent-4-en-l-yne


4.1 Introduction and Result


4.2 Discussion and Conclusion



5. Experimental


5.1 Preparations of Materials


5.2 Solvents

5.3 Salts


5.4 Kinetics


5.5 Examples of Kinetic Runs







The chemistry of allylic compounds, which have

the part-structure 1, has played an important part in the

development of theoretical organic chemistry. These

substances owe their importance to the high reactivity that

they display in nucleophilic substitution and to the fact

that they readily undergo rearrangement reactions. For

this reason allylic intermediates are widely used in organic


C = C - C X


In addition, allylic systems are found in many

natural products, such as alkaloids, steroids and terpenes.

Allylic systems are particularly common among the terpenes,

and allylic substitution reactions are widely used in the

synthesis of essential oils, vitamin A and its analogs, and

other un$aturated compounds.

Rearrangements in allylic compounds have been long 1/ known. A typical isomeric rearrangement is the conversion
2/ of 1-phenylallyi ester into its 3-isomer:—

PhCH = CHCH2 OCOR (1) 3/
It was first clearly recognised by Burton and Ingold chat such reactions may involve migration of a nucleophilic 02 anionic fragment from one end of the alllic system to the other. They are frequently found to accompany nucleophilic displacements in the allylic system. Rearrangement


reactions of this type belong to the class of reactions

known as anionotropic rearrangement. The term anionotropy,

introduced by Ingold refers to molecular rearrangement



where the migrating groups are anions as OH, OR Cl etc.


Anionotopy has been redefined by Braude as the migration

of a group or atom in which that group or atom retains the

electrons by which it was originally bound to the molecule.

The equilibrium in an anionotopic system can be considered

quite independently of the mechanism of the rearrangement

but depends on the free energy difference (AG) between the

isomeric structures expressed in equation (2).

A G == - RT to K


For qualitative and semiquantitative discussion it is usually
sufficiently accurate to identify (AG) with the change in heat content and to discuss the effect of substituents attached to the carbon atoms C1, C 2 and C3 in terms of what is known of the stabilization energies resulting from the presence of substituents adjacent to the C1-C2 double bond in the first isomer and the C2-C3 double bond in the second isomer. For example, the equilibrium mixture of cinnamJ ana 1-phenylallyl chlorides contains no detectable quantities of the latter (equation 1) and the composition of the equilibrium mixture between crotyl and l-methyl-allyl ehorides
5/ or bromides :
(75-85)% CH3-CH==CH-Ci 2X

CH3-CHX-CH==CH2 (15-25)%


depends on the halides and the temperature. A study of the

aniontropic rearrangement occurring during a displacement

reaction can yield valuable information concerning the

mechanism of the latter reaction. Allylic halides display the properties of ease of nucleophilic substitution and anionotropic mobility to a high degree, and in the following sections mechanistic aspects of these reactions . will be discussed with particular reference to solvolytic reactions. Isomerization reactions of allylic alcohols, esters and ethers have been reviewed by Braude. De Wolfe
(4, 6, 7) and Young.
ReactionsSynthesisSolvolytic ReactionsDiscussionIsomer