Chemistry of Heterocyclic Compounds. Volume 48. Pyrroles. Part I

752 Pages·32.32 MB·english

by  Jones R.A.

PYRROLES
Part One
This is a part of rhe forty-eighrh volume in the series
THE CHEMISTRY OF HETEROCYCLIC COMPOUNDS
THE CHEMISTRY OF HETEROCYCLIC COMPOUNDS
A SERIES OF MONOGRAPHS
EDWARD C. TAYLOR, Editor
ARNOLD WEISSBERGER, Founding Editor
PYRROLES
Part One
THE SYNTHESIS AND THE
PHYSICAL AND CHEMICAL ASPECTS
OF THE PYRROLE RING
Edited by
Alan Jones
R.
School of Chemical Sciences
University East Anglia
of
Norwich, U.K.
AN INTERSCIENCE" PUBLICATION
JOHN WILEY & SONS
NEW YORK CHICHESTER BRISBANE TORONTO SINGAPORE
An Interscience" Publication
Copyright :( 1990 by John Wiley & Sons, Inc.
All rights reserved. Published simultaneously in Canada
Reproduction or translation of any part of this work
beyond that permitted by Section 107 or 108 of the
1976 United States Copyright Act without the permission
of the copyright owner is unlawful. Requests for
permission or further information should be addressed to
the Permissions Department, John Wiley & Sons, Inc.
Library of Congress Cataloging in Publication Data:
Pyrroles , edited by R. Alan Jones.
p. cm. (The Chemistry of heterocyclic compounds, ISSN
0069-3154: v. JX. pt. I-)
"An Interscience publication."
Includes bibliographical references.
Contents: pt. I. The synthesis and the physical and chemical
aspects of the pyrrole ring.
ISBN 0-471-6'753 4 (PI. I)
I. Pyrrol. 1. Jones, Alan (Richard Alan) 11. Series:
R.
Chemistry of heterocyclic compounds; v. 48. pt. I. etc.
QD401. P994 89 I6553
I990 ~
547'.593 dc20 CI P
1 0 9 8 7 6 5 4 3 2 1
Contributors
Hugh J. Anderson Albert Gossauer
Department of Chemistry Institut fur Organishe Chemie der
Memorial University of Universitat Freiburg
Newfoundland Freiburg, Switzerland
St. John’s, Newfoundland, Canada
Anthony H. Jackson
Marino Artico School of Chemistry and Applied
Dipartimento di Studi Farmaceutici Chemistry
Facolta di Farmacia University of Wales College of
Universita degli Studi di Roma “La Cardiff
Sapienza” Cardiff. U.K.
Rome, Italy
Charles E. Loader
Gerritt P. Beana Department of Chemistry
Department of Chemistry Memorial University of
Western Illinois University Newfoundland
Macomb, Illinois St. John’s, Newfoundland, Canada
Derek J. Chadwick’ Petr Nesvadba
Department of Organic Chemistry lnstitut fur Organishe Chemie der
The Robert Robinson Laboratories Universitat Freiburg
University of Liverpool Freiburg, Switzerland
Liverpool, U.K.
Michael P. Sammes
Nicholas Dennisc Department of Chemistry
School of Chemical Sciences University of Hong Kong
University of East Anglia Hong Kong
Norwich, U.K.
Present uflrliution: Department of Chemistry and Biochemistry, University of Boulder, Boulder,
Colorado.
*Present ufiliution: The Ciba Foundation, 41 Portland Place, London WIN 4BN.
‘ Present uflliurion: Graduate School of Science and Technology, Bond University, Gold Coast,
Queensland 4229, Australia.
V
The Chemistry of Heterocyclic Compounds
Introduction to the Series
The chemistry of heterocyclic compounds is one of the most complex and
intriguing branches of organic chemistry. It is of equal interest for its theoretical
implications, for the diversity of its synthetic procedures, and for the physio-
logical and industrial significance of heterocyclic compounds.
The Chemistry of Heterocyclic Compounds, published since 1950 under the
initial editorship of Arnold Weissberger, and later, until Dr. Weissberger’s death
in 1984, under our joint editorship, has attempted to make the extraordinarily
complex and diverse field of heterocyclic chemistry as organized and readily
accessible as possible. Each volume has dealt with syntheses, reactions, proper-
ties, structure, physical chemistry and utility of compounds belonging to a
specific ring system or class (e.g., pyridines, thiophenes, pyrimidines, three-
membered ring systems). This series has become the basic reference collection for
information on heterocyclic compounds.
Many broader aspects of heterocyclic chemistry are recognized as disciplines
of general significance which impinge on almost all aspects of modern organic
and medicinal chemistry, and for this reason we initiated several years ago a
parallel series entitled General Heterocyclic Chemistry which treated such topics
as nuclear magnetic resonance, mass spectra, and photochemistry of heterocyclic
compounds, the utility of heterocyclic compounds in organic synthesis, and the
synthesis of heterocyclic compounds by means of 1,3-dipolar cycloaddition
reactions. These volumes were intended to be of interest to all organic and
medicinal chemists, as well as to those whose particular concern is heterocyclic
chemistry.
It has become increasingly clear that this arbitrary distinction creates as many
problems as it solves, and we have therefore elected to discontinue the more
recently initiated series General Heterocyclic Chemistry, and to publish all
forthcoming volumes in the general area of heterocyclic chemistry in The
Chemistry of Heterocyclic Compounds series.
EDWARCD. TAYLOR
Department of Chemistry
Princeton Unioersity
Princeton, New Jersey 08544
vii
Foreword
Pyrrole is a remarkable substance; it is highly reactive, versatile in that
reactivity and is of crucial importance for living systems. In both animal and
plant kingdoms, the brightly colored materials which have become known as the
pigments of life such as haem, chlorophyll, vitamin B, and the cytochromes are
2,
constructed largely from the relatively simple monopyrrolic building block
porphobilinogen. Their biological interest has been one major driving force,
though by no means the only one, which has caused the massive surge of interest
in and research effort on the chemistry of pyrroles. There is now available an
amazing variety of chemistry amassed from these studies. What stands out
plainly is the powerful effect substituents on the pyrrole nucleus have on the
reactivity of the system, whether they be attached at carbon or at nitrogen. Those
who have worked personally with pyrrolic substances are acutely aware of this
aspect of their chemistry and, for example, use it to steer safely along a synthetic
route avoiding Scylla on the one hand and Charybdis on the other, Professor
Woodward’s synthesis of chlorophyll is a perfect example.
This topic of reactivity and all other relevant ones ranging from synthetic
methods, spectroscopic properties, and the physical and theoretical aspects are
all fully reviewed, in this first volume of several, by those who are authorities on
each particular area. In addition, I was pleased to see that there is extensive
authoritative coverage of the chemistry of those important isomers of pyrrole
itself, namely, the 2H-pyrroles and 3H-pyrroles.
Chemists working on pyrroles and their relatives, and it is a growing group,
should be grateful that the editor and his colleagues have worked together to
produce this invaluable assembly of information and analysis. This set of
volumes is certain to be a constant source of reference for all who enjoy the
chemistry of pyrroles and who wish to add further building blocks to the
marvelous edifice which is still evolving.
ALAN BATTERSBY
R.
Cambridge, U.K.
April I989
ix
Preface
This book, which is the first of a series devoted to the chemistry of pyrrole and
its derivatives, presents the basic structural, physical, and chemical properties of
1H-pyrrole and of the less prevalent 2H- and 3H-isomers, together the synthesis
of the three systems.
Since its initial detection in coal tar and bone oil by Runge in 1834, pyrrole has
been an intriguing compound; one which, although highly susceptible to
oxidation and polymerization, occupies a key role in life. Such was its import-
ance as the basic nitrogen heterocycle in porphins and chlorins that much of our
early knowledge of the simple ring system revolved around the biologically more
important derivatives. This is reflected to a large extent in the early authoritative
texts by Fischer and Orth, who provided the chemist with a comprehensive
review of the synthesis and basic chemical properties of the more stable
substituted pyrrole derivatives. The advent of sophisticated analytical and
separation techniques, developed over the past twenty years, and our ability with
faster computers to undertake more complex theoretical calculations, has
widened our horizons and we are now in a position to present a fuller, if not yet
complete, picture of the chemistry of pyrrole.
In the compilation of this first part of the series, I am indebted to the
contributing authors for their successful endeavors in providing comprehensive
surveys of the physical, theoretical, synthetic, and chemical aspects of our
present-day knowledge of the chemistry of the pyrrole ring. In particular, I
acknowledge the forebearance of the authors, who allowed me to conflate their
individual contributions on the chemical reactivity of the pyrrole ring into a
single cohesive chapter. My sincere thanks also go to my university colleagues
for their support and helpful advice and last, but by no means least, to my wife for
her continuing patience and understanding.
R. ALAN
JONES
Norwich, U.K.
July I989
xi
Contents
ABBREVIATIONS USED IN THE TEXT, TABLES, AND
................................
FORMULAS..... xv
1 PHYSICAL AND THEORETICAL ASPECTS OF
................................
1H-PYRROLES 1
DEREJK. CHADWICK
.................
2 THE SYNTHESIS OF 1H-PYRROLES. 105
GERRITPT. B EAN
.......
3 REACTIVITY OF THE 1H-PYRROLE RING SYSTEM 295
ANTHONYH . JACKSON, MARINAOR TICOH, UGHJ . ANDERSON,
CHARLEE.S L OADERAL, BERTG OSSAUEPRE,T RN ESYADBA,
and NICHOLDAES NNIS
4 PHYSICAL AND THEORETICAL ASPECTS, SYNTHESIS,
AND CHEMICAL REACTIVITY OF 2H- AND
................................
3H-PYRROLES 549
MICHAEL P. SAMMES
INDEX . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 729
...
Xlll
Abbreviations Used in the Text, Tables, and Formulas
ac acetyl
acac acetylacetonate
Ar aryl
t-BOC tert- bu tyloxycarbonyl
9-BBN 9-borobicyclo[3.3.1 Inonane
B PR by -product
Bu butyl
CASSCF complete-active-space self-consistent-field theory
CNDO complete neglect of differential overlap (molecular orbital
calculations)
CNDO/S CNDO adapted for spectroscopy
cr crude
Dabco I
,4-diazabicyclo[2.2.2]octane
DBU I ,8-diazabicyclo[ 5.4.0J undecene
DDQ 2,3-dichloro-5,6-dicyanIo ,-4 -quinone
DI BA L diisobutylaluminum hydride
DMAD dimethyl acetylenedicarboxylate
DMF dimethylformamide
DMSO dimethylsulfoxide
E electrophilic agent
EHT extended Huckel theoretical (calculations)
Et ethyl
GC gas chromatography
HAM 'hydrogenic atoms in molecules' modified SCF
HOMO highest occupied molecular orbital
HMO Huckel molecular orbital (calculations)
HMPA hexamethylphosphoric triamide
HSAB hard-soft acid--base (theory)
xv