The Alkaloids Chemistry and Physiology

879 Pages·1965·36.28 MB·English

by  R.H.F. Manske (Eds.)

THE ALKALOIDS
Chemistry and Physiology
VOLUME VIII
THE INDOLE ALKALOIDS
CONTRIBUTORS TO VOLUME Vm
A. R. BATTERSBY R. H. F. MANSKE
E. COXWORTH J. E. SAXTON
B. GILBERT E. SCHLITTLER
W. ASHLEYH ARRISON G. F. SMITH
A. HOFMANN A. STOLL
H. F. HODSON W. I. TAYLOR
THE ALKALOIDS
Chemistry and Physiology
Edited by
R. H. F. MANSKE
Dominion Rubber Research Laboratory
GueEph, Ontario, Canada
VOLUME VIII
THE INDOLE ALKALOIDS
1965
ACADEMIC PRESS * NEW YORK * LONDON
0
COPYRIGHT 1965, BY ACADEMIPCR ESSI NC.
ALL RIGHTS RESERVED.
NO PART OF THIS BOOK MAY BE REPRODUCED IN ANY FORM,
BY PHOTOSTAT, MICROFILM, OR ANY OTHER MEANS, WITHOUT
WRITTEN FERMISSION FROM THE PUBLISHERS.
ACADEMIC PRESS INC.
111 Fifth Avenue, New York, New York 10003
United Kingdom Edition published by
ACADEMIC PRESS INC. (LONDON) LTD.
Berkeley Square House, London W.1
LIBRARYO F CONGRESSC ATALOGC ARD NUMBE:R 5 0-5522
PRINTED IN THE UNITED STATES OF AICERICA.
LIST OF CONTRIBUTORS
Numbers in parentheses indicate the pages on which the authors' contributions begin.
A. R. BATTERSBTYh, e Robert Robinson Laboratories, University of Liverpool,
Liverpool, England (51 5)
E. COXWORTHS, askatchewan Research Council, Saskatoon, Saskatchewan,
Canada (27)
B. GILBERTC, entro de Pesquisas de Produtos Naturais, Faculdade Nacional de
Farmhcia, Rio de Janeiro, Brazil (335)
W. ASHLEY HARRISOND, ominion Rubber Research Laboratory, Guelph,
Ontario, Canada (679)
A. HOFMANNP,h armaceutical-Chemical Research Laboratories, Sandoz
Limited, Basel, Switzerland (725)
H. F. HODSONT, he Wellcome Research Laboratories, Beckenham, Kent,
England (515)
R. H. F. MANSKED, ominion Rubber Research Laboratory, Guelph, Ontario,
Canada (47,55,581,679,693)
J. E. SAXTONT,h e University, Leeds, England (1, 59, 93, 119, 159, 673)
E. SCHLITTLERR,e search Department, CIBA Pharmaceutical Company,
Division of CIBA Corporation, Summit, New Jersey (287)
G. F. SMITHT, he University, Manchester, England (591)
A. STOLLP, harmaceutical-Chemical Research Laboratories, Sandoz Limited,
Basel, Switzerland (725)
W. I. TAYLORR, esearch Department, CIBA Pharmaceutical Company,
Division of CIBA Corporation, Summit, New Jersey (203,237,249,269,785)
V
This Page Intentionally Left Blank
PREFACE
The explosive advance in the chemistry of the indole alkaloids in
recent years has been occasioned not only by their intrinsic interest as
problems in chemistry but by the possibility that some at least might have
therapeutic value. The last review by J. E. Saxton in Volume VII of this
series was confined to two hundred pages. The present volume consists
of nearly four times as many pages and it is pertinent to note that most
of the content is new. Material reported previously in these volumes is
only summarized to the extent that the present volume is self-consistent
but not repetitive.
Though there is not yet any evidence that the interest in indole
alkaloids has declined there is sufficient new material to warrant the
preparation of an up-to-date summary. The Editor is of the opinion that
most of the structural types that plants elaborate have now been
discovered: and it is likely that new alkaloids will largely fallinto presently
known types. Modern methods, depending as they do upon mass- and
NMR-spectra, are extremely powerful tools in this field of structural
investigations, and new types, if and when they occur, can be readily
recognized as such.
The twenty-two chapters in the present volume are to some extent
an arbitrary division of the subject matter. In consequence there is
occasional overlapping but such as there is appeared to be essential in
the interest of continuity and clarity. Cross references and references to
previous volumes are designed to expedite exhaustive study of a par-
ticular subject. Literature references are listed in the bibliography in the
order in which they appear in each chapter.
The entries in the subject index are limited to the important topics
for each substance or group ; substances mentioned only incidentally
are not included.
The Editor is again most grateful to the authors of this volume. All are
thoroughly competent in their chosen topics and their conscientious
labors are a pleasure to acknowledge.
R. H. F. MANSRE
January, 1965
vii
This Page Intentionally Left Blank
CONTENTS
...................................................
LIST OF CONTRIBUTORS V
PREFAC.E.. ............................................................ vii
.........................................
CONTENTOSF PREVIOUVSO LUMES xiv
Chapter 1. The Simple Bases
J. E. SAXTON
I. Introduction ...................................................... 1
I1. Abrine and Hypaphorine ........................................... 2
I11 . Gramine and Its Derivatives ........................................ 4
. .....................................
IV Tryptamine and Its Derivatives 8
V. Psilocin and Psilocybin ............................................. 10
VI . 5-Hydroxytryptamine and Its Derivatives ............................ 12
VII. Cryptolepiqe ...................................................... 19
References ....................................................... 21
Chapter 2. Alkaloids of the Calabar Bean
E . COXWORTH
I. Source of the Alkaloids ............................................. 27
I1. Alkaloids Isolated ................................................. 27
111. Physostigmine .................................................... 28
IV. Postulated Riosyntheses of the Physostigmine Ring System .............. 41
V. Geneserine ....................................................... 42
VI. Pharmacology .................................................... 43
.......................................................
References 44
Chapter 3. The Carboline Alkaloids
R. H . F. MANSKE
I. Introduction ...................................................... 47
I1. Occurrence ....................................................... 47
111. Properties ........................................................ 49
IV. Structure ......................................................... 49
.......................................................
References 52
Chapter 4 . The Quinazolinocarbolines
. . .
R H F MANSKE
. ......................................................
I Introduction 55
. .......................................................
I1 Occurrence 55
111. Structure ......................................................... 56
References ........................................................ 58
ix