plant alkaloids

475 Pages·2012·9.46 MB·English

THE
PLANT ALKALOIDS
BY
THOMAS ANDERSON HENRY
D.Sc. (Lond.), F.e.S.
Superintendent of Laboratories, Scientific and Technical
Department, Imperial Institute
LONDON
J. & A. C H U R C Ii ILL
7 GREAT MARLBOROUGH STREET
1913
Authority to use for comment the Pharma
copreia of the -United States of America,
Eighth Decennial Revision, in this volume,
has been granted by the 1?oard of Trustees
of the United States Pharmacopreial C011-
vention, which Board of Trustees is in no way
responsible for the accuracy of any translations
of the official weights and measures or for
any statements as to strength of official
preparati ons,
RAI.LAN'J'),N~~ & COMPAN), L'l'D
'l'A'-ISTOCl{ STREET COVEN.' GA[mm,
LONDON
PREFACE
IN certain respects the plant alkaloids rank among the most interest
ing of naturally occurring substances. For the most part they are
of very complex structure, so that the determination of _t heir
constit.ution and the discovery of methods of producing them
synthetically offer attractive problems to the chemist; and though
a great deli\l has been accomplished, much still remains to be done
in this direction. Their mode of origin and their function in plants
are still unknown, and these two questions, with the more important
I
one of correlating the structure of the alkaloids with their physio-
logical action, form stilI almost untouched fields for combined work
on the part of physiologists and chemists. Many of the alkaloids
are of great importance in medicine, and the manufacture of these
..
alkaloids and of products containing them constitutes important
branches of the" :fine chemical " industry.
In compiling this volume the author has kept in view these
various aspects of the subject, and the articles on all the more
important alkaloids describe not only the properties and the
<;hemistry of these products, but also their occurrence, methods of
estimation, and physiological action. In most cases the_ original
memoirs have been consulted and references to these are given in
foot-notes, but for descriptions of the physiological action of the
better-known alkaloids Professor Cushny's "Textbook of Pharma
cology and Therapeutics " has been largely utilised. The chemical
v
Authority to use ,for comment the Pharma
copceia of the -United States of Ame:rica,
Eighth Decennial Revision, in this volume,
has been gl'anted by the Board of Trustees
of the United States Pharmacopooial Con
vention, which Board of Trustees is in no way
responsible for the accuracy of any translations
of the official weights and measures or for
any statements as to strength of official
preparations,
BAI.LAN'l'YNB & COlllPANY Ui'D
'fAYlf;TOCK STREE1' Con;l"J GAllDJlK
LOl'lDOl'l
PREFACE
IN certain respects the plant alkaloids rank among the most inter
ing of naturally occurring substances. For the most part they
of very complex structure, so that the determination of_t
constitution and the discovery of methods of producing t
synthetically offer attractive problems to the chemist; and th,
a great deal has been accomplished, much still remains to be
in this direction. Their mode of origin and their function in II
are still u~known, and these two questions, with the more impo
one of correlating the structure of the alkaloids with their p]
logical action, form still almost untouched fields for combined
on the part of physiologists and chemists. Many of the alk
are of great importance in medicine, and the manufacture of
alkaloids an.d. of products containing them constitutes imp
branches of the" fine chemical" industry.
In compiling this volume the author has kept in vie~
various aspects of the subject, and the articles on all th
important alkaloids describe not only the properties a
chemistry of these products, but also their occurrence, met
estimation, and physIological action. In most cases the_
memoirs have been consulted and references to these are !
foot-notes, but for descriptions of the physiological actiOJ
better-known alkaloids Professor Cushny's "Textbook of :
cology and 'l'herapeutics " has been largely utilised. The
v
PREFACE
Vl
nomenclature and the system of abbreviations used are, with1a
few unimportant exceptioDB, those employed in the " Abstrac1 "
published by the Ohemical Society of London, with whic'_ most
English-speaking chemists are familiar.
For much laborious work in checking formulre and references
and in reading proofs the author is indebted to Mrs. Henry, B.A.,
B.Sc. (Lond.), and to Miss A. Holmes, B.A. (Lond.).
CONTENTS
P.A.GE
INTRODUCTION 1
PYRROLE GROUP 13
PYRIDINE GROUP 16
ALKALOIDS WITH DIHETEROCYCLIC NUCLEI 48
QUINOLINE GROUP 127
ISOQUINOLINE GROUP 199
GLYOJC4LINE GROUP 301
PURINE GROUP 312
ALKALOIDS DERIVED FROM ALIPHATIC AMINES 326
ALKALOIDS OF UNKNOWN CONSTITUTION 336
APPENDIX-RECENT WQRK ON ALKALOIDS 449
INDEX 453
vii

INTRODUq'P10~-
-"---
THE word alkaloid was at first used to describe all organic bases,
including the natural alkali:like substances which occur in plants.
At the time this name was introduced comparatively few of these
l!\:,ter substances were kno~n, and these were all alike in possessing
bas\' properties and in exhibiting physiological activity. These
two\"'aracteristics, in conjunction with their complex structure,
have ~0e it possible until recently to regard the natural alkaloids
"
as forming a, well-differentiated group of chemical compounds, but
recent work has tendec1 +A Tflnder indistinct the border lines between
this and other groups. On the one hand such simple basic sub
stances as ammonia and methylamine, and on the other substances
that contain nitrogen and are yet acidic rather than basic, have been
found in plants. And, again, complex substances closely related to
typical alka)oids and which must be regarded as belonging to the
class of alkaloids, though they have no marked physiological action,
are known. Konigs proposed to avoid this difficulty by confining
the name alkaloid to naturally occurring pyridine derivatives,
but this rules out such important substances as the purine
and glyoxalin~ derivatives, and for that reason can hardly be
accepto::l as a satisfactory use of the name. The term alkaloid is,
however, generally understood as meaning a' relatively co~plex
basic substance, occurring naturally, and possessing some physio
logical action, and it will be understood in that sense in this volume,
though the definition cannot be rigidly applied.
Certain of the alkaloids are common to plants and animals,
and there is no logical ground for the separate treatment of " vege
table alkaloids" and "animal alkaloids." Most of the animal
alkaloids are different in type from the majority of the vegetable
alkaloids, and they are even more difficult to isolate in a pure
state and to investigate. Further, the literature relating to animal
2 PLANT ALKALOIDS
alkaloids has grown rapidly in recent years, and their investiga.tion
has developed in many ways on special lines, so that for c:rractical
purposes they can be dealt with most conveniently :s a separate
class, and in this volume only alkaloids found in plants will be
considered.
A number of comparatively simple amino-substances, such as
asparagine (aminosuccinamic acid), have been recorded in recent'
years as occurring in plant seediings. Most of these substances
can scarcely be classed as alkaloids, and they are fully dea,lt
with, as a rule, in the larger text-books; on organic chemistry,
and for these reasons they are not described in detail in this
volume.
Olassification of Alkaloids
The chemistry of this group of compounds dates from 1817, when
Sertiirner announced his discovery of a crystalline, salt-forming,
physiologically active substance (morphine) in opium. This was
\
followed by Robiquet's discovery of narcotine in the same year,
and in the next year by Pelletier and Caventou's isolation of strych
nine. Since then a large number of such substances have been
isolated from plants and characterised. A good deal is now known
regarding the molecular structure of many of the more important
alkaloids, and syntheses have been effected of a considerable number
of them, It is possible, therefore, to classify many~f the alkaloids·
according to their nuclear structure. Any system of classification
is, however, liable to become obsolete soon after its introduction, as
the result of the great activity now being shown in the investigation
of alkaloids. Further, methods of investigation are noW" so delicate,
and the chemistry of cyclic compounds is becoming so much bet~er
understood; that far-reaching deductions regarding the structure
of compounds can be drawn from relatively few and simple
reactions and observations, so that for purposes of hard-and
fast classification the chemistry of alkaloids is in a very unstable
condition.
The vegetable alkaloids can, however, be arranged at present