Proton Transfer: Proton Transfer of Related Reactions

275 Pages·1977·12.727 MB·English

by  C. H. Bamford, C. F. H. Tipper

COMPREHENSIVE CHEMICAL KINETICS
COMPREHENSIVE
Section 1. THE PRACTICE AND THEORY OF KINETICS
Volume 1 Tlie Practice of Kinetics
Volume 2 Tlie Theory of Kinetics
Volume 3 The Formation and Decay of Excited Species
Section 2. HOMOGENEOUS DECOMPOSITION AND ISOMERISATION
REACTIONS
Volume 4 Decomposition of Inorganic and Organometallic Compounds
Volume 5 Decomposition and Isomerisation of Organic Compounds
Section 3. lNORGANIC REACTIONS
Volume 6 Reactions of Non-metallic Inorganic Compounds
Volume 7 Reactions of Metallic Salts and Complexes, and Organometallic
Com pounds
Section 4. ORGANIC REACTIONS (6 VOlUmeS)
Volume 8 Proton Transfer
Volume 9 Addition and Elimination Reactions of Aliphatic Compounds
Volume 10 Ester Formation and Hydrolysis and Related Reactions
Volume 12 Electrophilic Substitution at a Saturated Carbon Atom
Volume 13 Reactions of Aromatic Compounds
Section 5. POLYMERISATIONR EACTIONS( 3 volumes)
Volume 14 Degradation of Polymers
Volume 14A Free-radical Polymerisation
Volume 15 Non-radical Polymerisation
Section 6. OXIDATION AND COMBUSTION REACTIONS (2 volumes)
Volume 17 Gas-phase Combustion
Section 7. SELECTED ELEMENTARY REACTIONS (1 volume)
Volume 18 Selected Elementary Reactions
Additional Sections
HET1:ROGENEOUS REACTIONS
KINETICS AND TECHNOLOGICAL PROCESSES
CHEMICAL KINETICS
EDITED BY
C. H. BAMFORD
M.A., Ph.D., Sc.D. (Cantab.), F.R.I.C., F.R.S.
Campbell-Brown Professor of Industrial Chemistry,
University of Liverpool
AND
C. F. H. TIPPER
Ph.D. (Bristol), D.Sc. (Edinburgh)
Senior Lecturer in Physical Chemistry,
Universitj)o f Liverpool
VOLUME 8
PROTON TRANSFER
ELSEVIER SCIENTIFIC PUBLISHING COMPANY
AMSTERDAM - OXFORD - NEW YORK
1977
ELSEVIER SCIENTIFIC PUBLISHING COMPANY
335 Jan van Galenstraat
P.O.B ox 211, Amsterdam, The Netherlands
Distributors for the United States and Canada:
ELSEVIER/NORTH-HOLLAND INC.
52, Vanderbilt Avenue
New York, N.Y. 10017
With 20 illustrations and 60 tables
ISBN: 0-444-41512-2
Copyright 0 1977 by Elsevier Scientific Publishing Company, Amsterdam
All rights reserved. No part of this publication may be reproduced, stored in a
retrieval system, or transmitted in any form or by any means, electronic,
mechanical, photocopying, recording, or otherwise, without the prior written
permission of the publisher,
Elsevier Scientific Publishing Company, Jan van Galenstraat 335, Amsterdam
Printed in The Netherlands
COMPREHENSIVE CHEMICAL KINETICS
ADVISORY BOARD
Professor S. W. BENSON
Professor SIR FREDERICK DAINTON
Professor G. GEE
the late Professor P. GOLDFINGER
Professor G. S. HAMMOND
Professor W. JOST
Professor G. B. KISTIAKOWSKY
Professor V. N. KONDRATIEV
Professor K. J. LAIDLER
Professor M. MAGAT
Professor SIR HARRY MELVILLE
Professor G. NATTA
Professor R. G. W. NORRISH
Professor S. OKAMURA
Professor N. N. SEMENOV
Professor Z. G. SZABO
Professor 0. WICHTERLE
Contributors to Volume 8
J. E. CROOKS Department of Chemistry,
King’s College,
University of London, England
F. HIBBERT Department of Chemistry,
Birkbeck College
University of London, England
A. V. WILLI Am-Barkenkamp-8,
D-208 1, Hasloh, West Germany
Section 4 deals almost exclusively with reactions recognized as organic
in a traditional sense, but excluding (unless very relevant) those already
considered in Sections 2 and 3 and biochemical systems. Also, oxidations,
e.g. of hydrocarbons by molecular oxygen, polymerization reactions and
fully heterogeneous processes are considered later. The relationships of
mechanism and kinetics, e.g. the effect of structure of reactants and of
solvent, and isotope effects, are fully discussed. Rate parameters of
individual elementary steps, as well as of overall processes, are given if
available. We have endeavoured, in conformity with our earlier policy, to
organize this section according to the types of chemical transformation
and with the minimum of recourse to mechanistic classification. Never-
theless, it seemed desirable to divide up certain general processes on the
basis of their nucleophilic or electrophilic character.
As a general introduction, the first chapter deals with homogeneous
catalysis of organic reactions, mainly acid-base catalysis, but also with
nucleophilic catalysis and catalysis by metal ions. In Chapter 2, proton
transfer to and from carbon is discussed and in Chapter 3 proton transfer
to and from other atoms, mainly oxygen and nitrogen.
Liverpool
October. 1976 C. H. Bamford
C. F. H. Tipper
This Page Intentionally Left Blank
Contents
Preface . . . . . . . . . . . . . . . . . . . . . . . . . vii
Chapter 1 (A. V . Willi)
Homogeneous catalysis of organic reactions (mainly acid-base) . . . . . .
1. Introduction . . . . . . . . . . . . . . . . . . .
2 . Dependence of the rate of acid-base catalyzed reactions on pH and
buffer concentration . . . . . . . . . . . . . . . . . . 2
. . . . . . . . . . . . . . . . . . . . .
2.1 General 2
2.2 Selection of the pH scale . . . . . . . . . . . . . . . 2
2.3 Acid-base catalyzed reactions with interfering acid-base equilibria
of the substrate . . . . . . . . . . . . . . . . . . 3
2.4 pH dependence of acid-base catalyzed reactions with changing
rate-determining step . . . . . . . . . . . . . . . . 5
2.5 Experimental studies of general acid-base catalysis . . . . . . 1
.
3 Investigation of the mechanisms of acid-base catalyzed reactions . . . 8
3.1 Types of mechanism and nomenclature . . . . . . . . . . 8
3.2 Experimental criteria for the mechanisms of acid-base catalysis . . 10
3.2.1 General catalysis . . . . . . . . . . . . . . . . 1 0
3.2.2 Volume change on activation . . . . . . . . . . . 12
3.2.3 Entropy change on activation . . . . . . . . . . . 1 6
3.2.4 Zuker-Hammett hypothesis and Bunnett criterion . . . . 19
3.2.5 Solvent isotope effect . . . . . . . . . . . . . . 2 1
4 . Energy barriers and isotope effects in proton transfer reactions . . . . 24
4.1 A semi-empirical model of the energy barrier . . . . . . . . 24
4.2 Primary isotope effects and reacting bond orders . . . . . . . 27
5 . Survey of mechanisms of acid-base catalyzed readions . . . . . . 30
5.1 Mechanisms of acid catalysis . . . . . . . . . . . . . . 3 0
5.2 Mechanisms of base catalysis . . . . . . . . . . . . . . 32
5.3 The rate-determining step . . . . . . . . . . . . . . . 34
6 . Acid-base catalyzed formation and hydrolysis of epoxides . . . . . 35
6.1 Introduction . . . . . . . . . . . . . . . . . . . 3 5
6.2 Formation of epoxides . . . . . . . . . . . . . . . . 3 6
6.3 Hydrolysis of epoxides and related reactions . . . . . . . . . 37
6.3.1 Rate coefficients of ring-opening reactions of epoxides . . . 37
6.3.2 Mechanism of basic hydrolysis of epoxides . . . . . . . 39
6.3.3 Mechanisms of acidic hydrolysis of epoxides . . . . . . 39
6.3.4 Mechanisms of uncatalyzed hydrolysis of epoxides . . . . 4 1
7 . Acid catalyzed hydrolyses of acetals. ketals. and orthoesters . . . . . 4 2
7.1 Introduction . . . . . . . . . . . . . . . . . . . 42
7.2 Acetals . . . . . . . . . . . . . . . . . . . . . 44
7.3 Ketals . . . . . . . . . . . . . . . . . . . . . 48
7.4 Cyclic acetals and ketals . . . . . . . . . . . . . . . 49
7.5 Orthoesters . . . . . . . . . . . . . . . . . . . 5 2
8. Acid catalyzed hydrolysis of aliphatic diazo compounds . . . . . . 5 5
8.1 Introduction . . . . . . . . . . . . . . . . . . . 5 5
8.2 Ethyl diazoacetate . . . . . . . . . . . . . . . . . 56