ebook Pratical Organic Chemistry

598 Pages·2008·9.24 MB·english

PRACTICAL
ORGANIC CHEMISTRY
by
FREDERICK GEORGE MANN
Sc-D. (Cantab.), D.Sc. (Lond.), F.R.I.C., F.R.S.
FELLOW, TRINITY COLLEGE, CAMBRIDGE,
UNIVERSITY EMERITUS READER IN ORGANIC CHEMISTRY
and
BERNARD CHARLES SAUNDERS
C.B.E., M.A., Sc.D. (Cantab.), D.Sc. (Lond.), F.R.I.C., F.R.C. Path.
LONGMAN
London and New York
LONGMAN GROUP LIMITED
London
Associated companies, branches and representatives
throughout the world
Published in the United States of America
by Longman Inc., New York
Fourth Edition © Frederick George Mann and
Bernard Charles Saunders 1960
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 permission of the
Copyright owner.
First Published 1936
Second Edition 1938
New Impressions 1941,1942, 1943,I944, X946,1947, T949, *952
Third Edition 1952
New Impressions 1954, *955, I956, I957> J95<?
Fourth Edition 1960
New Impressions 1961, 1962, 1964, 1967, /970, /977
Neiv Impression with revisions 1974
New Impression KJ/5
Reprinted in paper covers, igj8
British Library Cataloguing in Publication Data
XEW IMPRESSION, 1974
The last (4th) Edition of this book appeared in 1960, and has been
followed by four New Impressions, the last in 1967. The rapid
and ceaseless changing of the presentation of organic chemistry—
both theoretical and practical—warranted an entirely new edition,
but this would have entailed a massive task, for which neither
Dr. B. C. Saunders nor I had time or opportunity to undertake.
The publishers therefore suggested that a new impression
should be prepared. This also proved a laborious task, partly
because of the many minor changes in nomenclature and—more
particularly—the presentation of names that the recommenda-
tions of the LU.P.A.C. required, and partly because all correc-
tions and additions were necessarily limited in length to the
space which the original text had occupied.
Several of my chemical colleagues have suggested that a new
edition of 'M. and S.' should now deal also with the chief
branches of modern spectroscopy. This would be an aim both
excellent and impracticable. Students have their own mono-
graphs on spectroscopy and their own teachers, whose exposition
should clarify the branches of this subject more rapidly and easily
than the printed text. An attempt to deal adequately with
spectroscopy in this volume would greatly increase its size and
probably fail in purpose—the fate of several books whose authors
have attempted this ambitious programme.
Wc are greatly indebted to Dr. D. K. C. Cooper, F.R.C.S.,
who has critically examined the section on First-Aid to ensure
that it now harmonises with modern medical practice.
F. G. Mann,
University Chemical Laboratory,
Cambridge.
March 1973.
PREFACE TO FOURTH EDITION
IN the preparation of this revised and extended edition, we have
had in mind two major factors.
First, considerably greater emphasis has been placed on semi-
micro techniques and their application to preparations, separa-
tions, analysis and physical determinations such as those of
molecular weight. We have therefore greatly expanded the
section on Manipulation on a semi-micro scale which was in the
Third Edition, and we have described many more preparations
on this scale, some independent and others as alternatives to
the larger-scale preparations which immediately precede them.
Some 40 separate preparations on the semi-micro scale are
described in detail, in addition to specific directions for the
preparation of many classes of crystalline derivatives required
for identification purposes. The equipment required for these
small-scale reactions has been selected on a realistic basis, and
care has been taken not to include the very curious pieces of
apparatus sometimes suggested as necessary for working on the
semi-micro scale.
Secondly, whilst retaining undiminished the full and clear
directions provided for students who are starting the study of
practical organic chemistry, we have extended the scope of the
work so that it covers most of the needs of students working for
an Honours or Special Degree.
To meet the needs of the advanced students, preparations
have now been included to illustrate, for example, reduction by
lithium aluminium hydride and by the Meerwein-Ponndorf-
Verley method, oxidation by selenium dioxide and by periodate,
the Michael, Hoesch, Leuckart and Doebner-Miller Reactions,
the Knorr pyrrole and the Hantzsch collidine syntheses, various
Free Radical reactions, the Pinacol-Pinacolone, Beckmann and
Arbusov Rearrangements, and the Bart and the Meyer Reactions,
together with many others.
These preparations, with those noted in the Preface to the
Third Edition, cover a considerable proportion of the standard
synthetic reactions. Most of these preparations come towards the
end of Part II (Preparations), and both elementary and advanced
students should have no difficulty in selecting the preparative
work they require.
In earlier editions, Part III (Reactions and Identification of
viii PREFACE TO FOURTH EDITION
Organic Compounds) was designed to give students a thorough
training in the general reactions of the simpler members of each
of the main classes of organic compounds, and in the methods
by which an unknown compound could be first allocated to its
class and then identified. Clearly, more advanced students will
meet a wider range of members of each class of compound, and
the final identification must usually be based on the melting-
points of crystalline derivatives. We have therefore inserted in
the account of each class a note of the types of crystalline deriva-
tives which can be most rapidly and reliably prepared, with full
experimental details. Our Tables of Melting-points of deriva-
tives, given at the end of the book, have been very considerably
extended, so that the advanced student, who, like the elementary
student, must first allocate his unknown compound to its class,
can now prepare one or more crystalline derivatives, and com-
plete the identification by reference to these tables. The pre-
paration of these crystalline derivatives gives the student a
further and very valuable exercise in semi-micro preparations.
It should be emphasised that in Sections 10-27 °f ^ai"t HI,
i.e., the sections which are each devoted to one class of com-
pound, the simpler or more common members are still clearly
specified, and their reactions discussed, so that again the less
advanced student can readily discern the range of the material
which is his immediate concern.
For the more advanced student, we have extended the section
on Quantitative Semi-micro Analysis, and we have included a
section dealing with Special Techniques in Separation and
Purification, namely Adsorption Chromatography, Paper Chro-
matography, and Ion-Exchange Processes.
The use of more complex or more costly articles of equipment,
such as catalytic hydrogenation apparatus, autoclaves, polari-
meters, ultraviolet absorption spectrometers, etc., has not been
described, because the type of such apparatus employed in different
laboratories varies considerably, and students must be taught the
use of their own laboratory equipment.
In the First Edition of this book, we included a short section
to illustrate some of the more simple or the more clearly defined
reactions which are promoted by enz\mes. It was hoped that
this section might stimulate the interest of younger chemists in
the preparative value oi such Tcactioris, but organic chemists still
largely ignore this branch oi preparative work. We have now
deleted certain portions of this section, and emphasised other
portions having greater current interest.
PREFACE TO FOURTH EDITION ix
Throughout this edition the nomenclature adopted is in
general that recommended by the International Union of Pure
and Applied Chemistry, and by the Chemical Society (1959).
In the preparation of this edition, we are indebted for much
help to many of our colleagues, and in particular to Dr. P. Sykes,
Dr. F. B. Kipping, Dr. P. Maitland, Dr. J. Harley-Mason and
Dr. R. E. D. Clark. We have maintained the standard which
was self-imposed \vhen this book was first written, namely, that
all the experiments in the book had been critically examined,
and then performed either by the authors, or under their super-
vision. The heavy load of work \vhich this has involved would
have been impossible without the willing, patient, and very
considerable help of AIr. F. C. Baker and Mr. F. E. G. Smith.
F. G. M.
Cambridge, 1960 B.C.S.
PREFACE TO THIRD EDITION
FOR the production of this edition, we have made a thorough and
critical revision of the whole contents of the book, based on our
experience of its use in the laboratory and on the general advance
in organic chemical practice. In addition to this general revision.
however, we have extended the book in three main directions.
The book as originally planned was intended to meet the needs
primarily of pupils'in the senior forms at schools and of under-
graduates up to the level of a Pass Degree. We have extended
Parts II and III dealing with Preparations and with the Reactions
and Identification of Organic Compounds so that the book should
now cater fully for the needs of students working for Honours
Degrees. In particular, the Preparations now include examples
of most of the more simple standard reactions: for this pur-
pose we have now added, for example, preparations illustrating
the Benzidine Transformation, the Ullmann Condensation,
the Benzilic Acid Rearrangement, the Reformatsky Reaction, the
Clemmensen Reduction, the Fischer Indolisation Reaction, the
Mannich Reaction, and the Diels-Alder Reaction. It is probable
that preparative work on a much smaller scale than has hitherto
been customary in teaching laboratories will become more
common in future. To meet this need, we have added a short
section to Part I, describing the design and use of apparatus for
this purpose, and we have also included some examples of these
small-scale preparations as alternatives to the larger preparations
in Part II.
In Part III, dealing with the Reactions and Identification of
Organic Compounds, greater emphasis has now been placed on
the preparation of suitable crystalline derivatives. Quite apart
from the importance of these derivatives for purposes of identi-
fication, encouragement is thereby given to the student to gain
experience in small-scale preparative work.
We have also added an entirely new section dealing with semi-
microanalysis. In our original Introduction (p. ix) we justified
the retention of macro-methods of quantitative analysis on the
grounds that they formed an excellent introduction to micro-
methods and also afforded a valuable training in exact manipula-
tion generally. By now, however, the macro-estimation par-
ticularly of carbon and hydrogen and of nitrogen has disappeared
entirely from most laboratories. On the other hand, the micro-
PREFACE TO THIRD EDITION xi
methods developed so largely by Pregl, and which usually require
no more than 5 mgm. of material, necessitate prolonged training
and an impeccable experimental technique, and give consistently
reliable results only in the hands of full-time analysts. They are
consequently unsuitable for students. The semi-micro methods
of analysis, which usually require 20-50 mgm. of material, form
an ideal compromise for student-training, for the necessary
technique can be acquired after only a few attempts. These
methods moreover provide the student with very valuable
manipulative exercise, and serve as an introduction to the hand-
ling of even smaller quantities of material which may arise in
his post-graduate work. This section on Semi-microanalysis has
been designed and written by Dr. P. Sykes, and is based on his
experience of teaching such methods in the Cambridge labora-
tories. We wish to thank him sincerely for a valuable contribution
to this work.
In the original planning of this book we were at pains to
ensure that the preparations in particular were designed to
afford a minimum expenditure of time, materials and heating.
We hope that the economy thus introduced will be especially
appreciated in view of the recent heavily increased cost of
chemicals, fuel and laboratory service. This increased cost,
incidentally, must necessarily increase the attraction of the
small-scale preparations referred to above.
We are grateful to our colleagues for many valuable discussions
and suggestions: in particular we would mention Dr. F. B.
Kipping, Dr. P. Maitland, Dr. G. W. Kenner and Mr. J. Harley-
Mason.
We should also like to express once again our sincere thanks
for the considerable help we have received from our laboratory
assistants, Mr. F. C. Baker and Mr. F. E. Smith.
F.G.M.
B.C.S.
PREFACE TO SECOND EDITION
THE two chief additions which have now been made are the
Sodium Carbonate-Zinc Method as an alternative to Lassaigne's
Sodium Fusion Method for detecting elements in organic com-
pounds, and the Tables of Physical Constants which have been
included in the Appendix. These Tables have been compiled
to cover a very much wider scope of organic compounds than
those described in this book. In addition to the general utility
of these Tables, we hope that they will be of value to students
wishing to extend their practice in the identification of organic
compounds beyond the range given in Part III of this book.
This range has been deliberately limited in order to enable
students to obtain a firm grasp of the methods of identifying
simple compounds, and these methods have therefore been based
almost entirely on chemical reactions alone. When the range of
organic compounds to be identified is extended, and particularly
when higher homologues are being investigated, identification by
the physical properties of derivatives becomes increasingly
necessary, and the Tables of Physical Constants should con-
siderably facilitate this extension.
We wish to express our gratitude to the chemists who have
made suggestions with regard to the subject-matter of this book:
many of these suggestions have now been incorporated in this
edition. Wre would warmly welcome further suggestions for
improving its contents.
F.G.M.
B.C.S.
INTRODUCTION
THIS laboratory manual of organic chemistry has been compiled
primarily to cover the work required for Part I of the Natural
Sciences Tripos at Cambridge University, the General B.Sc.
course at London University, and the Pass Degree courses at
other universities. At the same time, however, it has been
carefully arranged to cover adequately the needs of students pro-
ceeding to the M.B. examinations in organic chemistry at the
various universities. Moreover, since the introductory work
has been given in considerable detail, the book is suitable for
senior pupils at schools (more particularly for Higher Certificate
and University Entrance Scholarship candidates), and should
therefore be sufficient to cover both their school and university
needs.
This work is based largely on the authors' experience with the
teaching of practical organic chemistry to very large classes of
students at Cambridge University. For such classes experimental
directions involving the utmost economy in chemicals and
apparatus, and also in the students' time, are obviously required.
Therefore the whole of the experimental work described in this
book has been repeatedly checked by the authors themselves (and
for the most part by their classes also) in order to obtain the
desired results with a minimum expenditure of materials and
time. In the section on Organic Preparations in particular, this
detailed investigation of each preparation has frequently enabled
unexpected simplifications and economies to be introduced, more
particularly as many text-books still contain experimental direc-
tions which have frequently remained unchanged since their
original publication in chemical journals many years ago, and
in which, moreover, occasional errors both in fact and in tran-
scription have thus remained uncorrected. It is almost uni-
versally found that departments of organic chemistry are more
costly to maintain than other science departments, primarily
because of the heavy consumption of organic reagents and sol-
vents, and the economies which have now been effected will, we
think, be appreciated by most teachers of practical organic
chemistry.
Teachers of chemistry (and of the sciences generally) will have
found that many students appear to dissociate their practical work
sharply in their minds from their theoretical knowledge. Many
xiii