Contents.pdf

A TEXT-BOOK OF

PRACTICAL ORGANIC

CHEMISTRY

INCLUDING

QUALITATIVE ORGANIC ANALYSIS

ARTHUR I. VOGEL, D.Sc.(Lond.),D.I-C.,F.R.I.C.

Formerly Head of Chemistry Department, Woolwich Polytechnic ;

Sometime Beit Scientific Research Fellow of the Imperial College, London

With diagrams and 8 photographs

THIRD EDITION

LONGMAN

LONGMAN GROUP LIMITED

London

Associated companies, branches and representatives

throughout the world

First published 1948

New impression with minor

corrections, October 1948

Second Edition 1951

New impression with addition of

Chapter XII on Semimicro Technique

1954

Third Edition, 1956

New impression with corrections and

additions 1957

New impressions 1959, 1961, 1962, 1964,

1965, 1967, 1970, 1972, and 1974

ISBN 0 582 44245 1

PRINTED IN GREAT BRITAIN BY

LOWE AND BRYDONE (PRINTERS) LTD

THETFORD, NORFOLK

PREFACE TO THIRD EDITION

THE favourable reception accorded to previous editions by reviewers,

students and practising organic chemists has encouraged the author to

undertake an exhaustive revision of the entire text in the light of the

numerous developments in practical organic chemistry since the book

was first written (1945-46). The net result has been an increase in the

length of the volume by some 150 pages, a figure which gives some indi-

cation of the new matter incorporated in the present edition.

It is impossible within the limitations of a short preface to give a de-

tailed list of the numerous changes and additions. Some of the more

important new preparations include :

1. Chapter III. 1-Heptene (111,10) ; alkyl iodides (KI-H 3 PO 4 method)

(111,38) ; alkyl fluorides (KF-ethylene glycol method) (111,41) ; keten (nichrome

wire method) (111,90) ; ion exchange resin catalyst method for esters (111,102) ;

acetamide (urea method) (111,107) ; ethyl a-bromopropionate (111,126) ;

acetoacetatic ester condensation using sodium triphenylmethide (111,151).

2. Chapter IV. a-Chloromethylnaphthalene (IV,23) ; benzylamine (Gabriel

synthesis) (IV,39) ; AW-dialkylanilines (from amines and trialkyl orthophos-

phates) (IV,42) ; a-naphthaldehyde (Sommelet reaction) (IV,120) ; a-phenyl-

cinnamic acid (Perkin reaction using triethylamine) (IV,124) ; p-nitrostyrene

(IV,129) ; p-bromonaphthalene and p-naphthoic acid (from 2-naphthylamine-l-

sulphonic acid) (IV,62 and IV,164) ; diphenic acid (from phenanthrene)

3. Chapter V. Quinaldine (V,2) ; 2-methyl-, 2 : 5-dimethyl- and 2-acetyl-

thiophene (V,8-V,10) ; 2 : 5-dimethyl- and 2 : 4-dimethyl-dicarbethoxy-pyrrole

(V,12-V,13) ; 2-amino- and 2 : 4-dimethyl-thiazole (V,15-V,16) ; 3 : 5-dimethyl-

pyrazole (V,17) ; 4-ethylpyridine (from pyridine) (V,19) ; n-amyl-pyridines

from picolines) (V,28) ; picolinic, nicotinic and tsonicotinic acid (V,21-V,22) ;

(ethyl nicotinate and p-cyanopyridine (V,23-V,24) ; uramil (V,25) ; 4-methyl-

(coumarin (V,28) ; 2-hydroxylepidine (V,29).

4. Chapter VI. Reductions with potassium borohydride (VI,11) ; Oppen-

auer oxidation (VI,13) ; epoxidation and hydroxylation of ethylenic com-

pounds (VI,15) ; Arndt-Eistert reaction (VI,17) ; Darzens glycidic ester con-

densation (VI,18) ; Erlenmeyer azlactone reaction (VI,19) ; Mannich reaction

(VI,20) ; Michael reaction (VI,21) ; Schmidt reaction (VI,23) ; Stobbe con-

densation (VI,24) ; Willgerodt reaction (VI,25) ; unsymmetrical diaryls

(VI,27) ; syntheses with organoHthium compounds (VI,28) ; syntheses with

organosodium compounds (VI,29) ; syntheses with organocadmium compounds

(VI,30) ; some electrolytic syntheses (VI,31) ; chromatographic adsorption

(VI,33) ; ring enlargement with diazomethane (VI,34).

5. Chapters VII-IX. Diazomethane (p-tolylsulphonylmethylnitrosamide

method) (VII,20) ; Girard's reagents " T " and c t P " (VII,25) ; pseudo-

saccharin chloride (VII,26) ; 2 : 2'-dipyridyl (VIII,13) ; ninhydrin (VIII,14) ;

3-indoleacetic acid (IX,14).

A new feature is tha account of the electronic mechanisms (in outline)

of the numerous reactions described in the text. Although some of these

mechanisms may be modified in the near future, it is hoped that the brief

treatment scattered throughout the volume will stimulate the student's

interest in this important branch of organic chemistry. It will be noted

that many reactions are designated by name ; this may be undesirable

on pedagogical grounds but, in most cases, established usage and the

example set by the various volumes of Organic Reactions ( J. Wiley) may

be put forward in justification.

PREFACE TO THIRD EDITION

Chapter XII is concerned with Semimicro Technique. There can be

little doubt that preparations on a smaller scale than has hitherto been

customary have many advantages ; particular reference may be made to

cost, time and bench space, all of which are important factors in teaching

laboratories and also in training for research. Once the student has

mastered the special technique, no difficulty should be experienced in

adapting most of the preparations described in the book to the semi-

micro scale. A few examples of small-scale preparations are included

together with a suggested list of experiments for an elementary course.

Section A,7, " Applications of infrared and ultraviolet absorption

spectra to organic chemistry," should provide a brief introduction to

the subject.

It is regretted that the size of the volume has rendered the insertion of

literature references impossible : the Selected Bibliography (A,5) may

partly compensate for this omission. Section numbers are now included

in the headings of the pages—a feature introduced in response to requests

by many readers. The volume comprises virtually at least three books

under one cover, viz., experimental technique, preparations, and qualita-

tive organic analysis. It should therefore continue to be of value as a

one-volume reference work in the laboratory. Students at all levels will

find their requirements for laboratory work (excluding quantitative

organic analysis) adequately provided for and, furthermore, the writer

hopes that the book will be used as a source of information to supplement

their theoretical studies.

The author wishes to thank Dr. G. H. Jeffery, C. T. Cresswell, B.Sc.,

C. M. Ellis, M.Sc., Dr. J. Leicester and C. Kyte, B.Sc., for assistance with

the proof reading and for helpful suggestions ; Dr. G. H. Jeffery for

invaluable assistance in numerous ways ; and C. Kyte, B.Sc., and R.

Grezskowiak, B.Sc., for a number of original preparations and also for

checking and improving many of the new experimental procedures.

Criticisms and also suggestions for improving the book are welcomed.

ARTHUR I. VOGEL.

Woolwich Polytechnic, London, S.E. 18.

September 1955.

PREFACE TO FIRST EDITION

THE present volume is an attempt to give to students of practical organic

chemistry the benefit of some twenty years' experience in research and

teaching of the subject. The real foundations of the author's knowledge

of the subject were laid in 1925-1929 when, as a research student at the

Imperial College under the late Professor J. F. Thorpe, F.R.S., he was

introduced to the methods and experimental technique employed in a

large and flourishing school of research in organic chemistry. Since

that period the author and his students have been engaged inter alia in

researches on Physical Properties and Chemical Constitution (published

in the Journal of the Chemical Society) and this has involved the prepara-

tion of over a thousand pure compounds of very varied type. Many of

PREFACE TO FIRST EDITION

vii

the new procedures and much of the specialised technique developed and

employed in these researches are incorporated in this book. Further-

more, new experiments for the elementary student have emanated from

these researches ; these have been tried out with large classes of under-

graduate students over several sessions with gratifying success and have

now been included in the present text-book.

In compiling this book, the author has drawn freely from all sources

of information available to him—research notes, original memoirs in

scientific journals, reference works on organic chemistry, the numerous

text-books on practical organic chemistry, and pamphlets of manufac-

turers of specialised apparatus. Whilst individual acknowledgement

cannot obviously be made—in many cases the original source has been

lost track of—it is a duty and a pleasure to place on record the debt

the writer owes to all these sources. Mention must, however, be made

of Organic Syntheses, to which the reader is referred for further details

of many of the preparations described in the text.

The book opens with a chapter on the theory underlying the technique

of the chief operations of practical organic chemistry : it is considered

that a proper understanding of these operations cannot be achieved

without a knowledge of the appropriate theoretical principles. Chapter II

is devoted to a detailed discussion of experimental technique ; the

inclusion of this subject in one chapter leads to economy of space, par-

ticularly in the description of advanced preparations. It is not expected

that the student will employ even the major proportion of the operations

described, but a knowledge of their existence is thought desirable for the

advanced student so that he may apply them when occasion demands.

Chapters III and IV are confined to the preparation and properties

of Aliphatic Compounds and Aromatic Compounds respectively. This

division, although perhaps artificial, falls into line with the treatment in

many of the existing theoretical text-books and also with the author's

own lecture courses. A short theoretical introduction precedes the

detailed preparations of the various classes of organic compounds: it is

recommended that these be read concurrently with the student's lecture

course and, it is hoped, that with such reading the subject will become

alive and possess real meaning. The partition of the chapters in this

manner provides the opportunity of introducing the reactions and the

methods of characterisation of the various classes of organic compounds ;

the foundations of qualitative organic analysis are thus laid gradually,

but many teachers may prefer to postpone the study of this subject until

a representative number of elementary preparations has been carried

out by the student. The division into sections will facilitate the intro-

duction of any scheme of instruction which the teacher considers desirable.

Chapters V-X deal respectively with Heterocyclic and Alicyclic Com-

pounds ; Miscellaneous Reactions ; Organic Reagents in Inorganic and

Organic Chemistry ; Dyestuffs, Indicators and Related Compounds ;

Some Physiologically-Active Compounds; and Synthetic Polymers.

Many of these preparations are of course intended for advanced students,

but a mere perusal of the experimental details of selected preparations

by those whose time for experimental work is limited may assist to impress

them on the memory. Attention is particularly directed to the chapter

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