A TEXT-BOOK OF

PRACTICAL ORGANIC
CHEMISTRY
INCLUDING

QUALITATIVE ORGANIC ANALYSIS
By

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

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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 indication of the new matter incorporated in the present edition.
It is impossible within the limitations of a short preface to give a detailed 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-H3PO4 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 orthophosphates) (IV,42) ; a-naphthaldehyde (Sommelet reaction) (IV,120) ; a-phenylcinnamic acid (Perkin reaction using triethylamine) (IV,124) ; p-nitrostyrene

(IV,129) ; p-bromonaphthalene and p-naphthoic acid (from 2-naphthylamine-lsulphonic acid) (IV,62 and IV,164) ; diphenic acid (from phenanthrene)
3. Chapter V. Quinaldine (V,2) ; 2-methyl-, 2 : 5-dimethyl- and 2-acetylthiophene (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-dimethylpyrazole (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) ; Oppenauer oxidation (VI,13) ; epoxidation and hydroxylation of ethylenic compounds (VI,15) ; Arndt-Eistert reaction (VI,17) ; Darzens glycidic ester condensation (VI,18) ; Erlenmeyer azlactone reaction (VI,19) ; Mannich reaction
(VI,20) ; Michael reaction (VI,21) ; Schmidt reaction (VI,23) ; Stobbe condensation (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 ct P " (VII,25) ; pseudosaccharin 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.

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vi


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 semimicro 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 qualitative 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 preparation of over a thousand pure compounds of very varied type. Many of

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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. Furthermore, new experiments for the elementary student have emanated from
these researches ; these have been tried out with large classes of undergraduate 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 manufacturers 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, particularly 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 introduction of any scheme of instruction which the teacher considers desirable.
Chapters V-X deal respectively with Heterocyclic and Alicyclic Compounds ; 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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viii

PREFACE TO FIRST EDITION

upon Organic Reagents in Inorganic and Organic Chemistry. It is
always a good plan to set advanced students or adequately-trained
laboratory assistants on the preparation of those compounds which are
required in the laboratory for organic and inorganic analysis ; the resulting cost is comparatively low (for o-phenanthroline, for example, it is less
than one-tenth of the commercial price) and will serve to promote the use
of these, otherwise relatively expensive, organic reagents in the laboratory.
Chapter XI is devoted to Qualitative Organic Analysis. The subject
is discussed in moderate detail and this, coupled with the various Sections
and Tables of Physical Constants of Organic Compounds and their
Derivatives in Chapters III and IV, will provide a satisfactory course
of study in this important branch of chemistry. No attempt has been
made to deal with Quantitative Organic Analysis in this volume.
The text-book is intended to meet the requirements of the student of
chemistry throughout the whole of his training. Considerable detail is

given in those sections of particular interest to the elementary student;
in the author's opinion it is the duty of a writer of a practical text-book
to lay a secure foundation of sound experimental technique for the
beginner. The subject matter of the book is sufficiently comprehensive
to permit the teacher to cover any reasonable course of instruction. It
will be observed that the scale of the preparations varies considerably ;
the instructor can easily adapt the preparation to a smaller scale when
such a step is necessary from considerations of cost and time or for other
reasons. Quantities of liquid reagents are generally expressed as weights
and volumes : the latter refer to a temperature of 20°. The book will be
suitable for students preparing for the Pass and Honours (General and
Special) B.Sc. of the Universities, the A.R.I.C. and the F.R.I.C. (Organic
Chemistry). It will also provide an introduction to research methods in
organic chemistry and, it is hoped, may serve as an intermediate reference
book for practising organic chemists.
Attention is directed to the numerous references, particularly in
Chapter II on Experimental Technique, to firms supplying specialised
apparatus. The author has usually had first-hand experience with this
apparatus and he feels that some readers may wish to know the present
source of supply and also from whom to obtain additional information.
It must be mentioned that most of the specialised apparatus has been
introduced to the market for the first time by the respective firms after
much development research and exhaustive tests in their laboratories.
A reference to such a firm is, in the writer's opinion, equivalent to an
original literature reference or to a book. During the last decade or two
much development work has been carried out in the laboratories of the
manufacturers of chemical apparatus (and also of industrial chemicals)
and some acknowledgement of the great help rendered to practical organic
chemists by these industrial organisations is long overdue; it is certainly no
exaggeration to state that they have materially assisted the advancement

of the science. A short list of the various firms is given on the next page.
ARTHUR I. VOGEL.
Woolwich Polytechnic, London, S.E. 18.
December 1946.

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CONTENTS
CHAPTER I
THEORY OF GENERAL TECHNIQUE
THEORY OF DISTILLATION
1.1.
1.2.
1.3.
1.4.
1.5.
1.6.
1.7.

Vapour pressure
.
.
.
.
.
.
.
.
Calculation of the boiling point at selected pressures .

Superheating a n d bumping
.
.
.
.
.
.
Fractional distillation
.
.
.
.
.
.
.
The breaking up of azeotropic mixtures
.
.
.
.
Steam distillation. Distillation of a pair of immiscible liquids
Distillation with superheated steam .
.
.
.
.

PAGE
1
2

.
3
.
5
. 1 2
.
12
. 1 5

.
.

SOLUTIONS OF LIQUIDS IN LIQUIDS
1.8.
1.9.

Partially miscible liquids. Critical solution temperature
.
.
Influence of added substances upon the critical solution temperature

17
20

THEORY OF MELTING AND FREEZING
1.10.
1.11.
1.12.
1.13.
1.14.

1.15.
1.16.
1.17.
1.18.

1.19.
1.20.
1.21.
1.22.

Melting point and vapour pressure
.
.
.
.
.
. 2 1
Effect of impurities upon the melting point
.
.
.
. 23
System in which the solid phases consist of the pure components and
the components are completely miscible in the liquid phase
. 24
Construction of equilibrium diagrams
.
.
.
.

. 2 6
System in which the two components form a compound possessing a
congruent melting point
.
.
.
.
.
.
. 2 9
System in which the two components form a compound with an
incongruent melting point
.
.
.
.
.
.
. 3 1
System in which the two components form a continuous series of
solid solutions
.
.
.
.
.
.
.
.
. 3 2

Mixed melting points
.
.
.
.
.
.
.
. 34
System in which the solid phases consist of the pure components and
the components are only partially miscible in the liquid state . 35
Theory of sublimation
Theory of the action of drying agents
Deliquescence a n d efflorescence .
.
Extraction with solvents .
.
.

.

.
.

.

.

.


37
39
. 43
. 44

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.

.

.
.


.
.

CHAPTER II
EXPERIMENTAL TECHNIQUE
11.1.
11.2.
11.3.
11.4.
11.5.
11.6.

Common laboratory apparatus .
Cleaning and drying of glassware
Use o f cork a n d rubber stoppers
Cutting and bending of glass tubing
Heating baths .
.
.
.
Cooling baths

.
.
.
.
.

.

.
.
.
.

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.
.
.
.
.

4 6
5 3
55
5 7
57
60


xii
11.7.
11.8.
11.9.
11.10.
11.11.
11.12.
11.13.
11.14.

11.15.
11.16.
11.17.
11.18.
11.19.
11.20.
11.21.
11.22.
11.23.
11.24.
11.25.
11.26.
11.27.
11.28.
11.29.
11.30.
11.31.
11.32.
11.33.
11.34.
11.35.
11.36.
11.37.
11.38.
11.39.
11.40.
11.41.
11.42.
11.43.
11.44.

11.45.
11.46.
11.47.
11.48.
11.49.
11.50.
11.51.
11.52.
11.53.

CONTENTS
PAGE
Mechanical agitation
.
.
.
.
.
.
.
. 6 2
Gas absorption traps
.
.
.
.
.
.
.
. 7 1

Calibration of thermometers
.
.
.
.
.
.
. 7 2
Experimental determination of t h e melting point.
.
.
. 75
Miscellaneous forms o f melting point apparatus .
.
.
. 80
Experimental determination o f t h e boiling point .
.
.
. 83
Typical assemblies of apparatus for distillation and refluxiiig
.
86
Fire hazards attending the distillation of inflammable solvents
.
90
Fractional distillation. Distillation with a fractionating column . 91
Simple apparatus for fractionation
.
.

.
.
.
. 9 3
Improved apparatus f o r fractional distillation
.
.
.
. 94
Still heads for fractionating columns .
.
.
.
.
.102
Distillation under diminished pressure (" vacuum " distillation) . 103
Fractional distillation under diminished pressure
.
.
.108
Water pumps
110
Oil pumps
110
Manometers and manostats
.
.
.
.
.

.112
Refinements in the technique of distillation under diminished
pressure
.
.
.
.
.
.
.
.
.
.116
Precision fractional distillation under diminished pressure .
. 119
Molecular distillation
120
Purification of solid organic compounds by crystallisation. (General
considerations
.
.
.
.
.
.
.
.
.122
Experimental details for recrystallisation .
.

.
.
.125
Preparation of a fluted filter paper
.
.
.
.
.
.127
Removal of traces of colouring matter and resinous products. Use
of decolourising carbon .
.
.
.
.
.
.
.127
Difficulties encountered in recrystallisation .
.
.
.
.129
Filtration with suction
.
.
.
.
.

.
.
.130
Drying of the recrystallised material .
.
.
.
.
.132
Filtration of small quantities of material with suctioif .
.
.133
Miscellaneous apparatus for filtration with suction
.
.
.133
Recrystallisation in an atmosphere of inert gas .
.
.
.135
Evaporation of the solvent
.
.
.
.
.
.
.135
Drying of solid organic compounds .
.

.
.
.
.136
Drying of liquids or of solutions of organic compounds in organic
solvents
.
.
.
.
.
.
.
.
.
.139
Technique of steam distillation .
.
.
.
.
.
.145
Modifications of the steam distillation apparatus .
.
.
. 146
Technique of extraction with solvents
.
.

.
.
.149
Extraction by chemically active solvents .
.
.
.
.151
Continuous extraction of liquids or solids by solvents .
.
.152
Technique of sublimation
.
.
.
.
.
.
.154
Chromatographic adsorption
.
.
.
.
.
.
.156
Purification of the common organic solvents
.
.

.
.163
Inorganic reagents—gases
.
.
.
.
.
.
.179
Inorganic reagents—liquids
.
.
.
.
.
.
.186
Inorganic reagents—solids
.
.
.
.
.
.
.190
Calculation of yields
201
General instructions f o r work i n t h e laboratory .
.

.
. 204
Safety precautions .
.
.
.
.
.
.
.
.205

APPARATUS WITH INTERCHANGEABLE GROUND
GLASS JOINTS
11.54.
11.55.
11.56.
11.57.

Interchangeable ground glass joints .
.
.
.
.
. 206
Types o f ground glass joints
.
.
.
.

.
.
. 210
Apparatus with interchangeable ground glass joints suitable lor
general use Lu preparative organic chemistry .
.
.
.212
Electric heating mantles (tor use in fractional distillation, etc.) . 221

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CONTENTS
11.58.
11.59.
11.60.

xiii

PAGE
Apparatus for the continuous extraction of solids or liquids by
solvents
222
Lubrication o f ground glass joints
.
.
.
.
.

. 225
Typical assemblies .
.
.
.
.
.
.
.
.226

CHAPTER III
PREPARATION AND REACTIONS OF ALIPHATIC
COMPOUNDS
PRELIMINARY LABORATORY OPERATIONS
111.1.
111.2.
111.3.
111.4.
111.5.

Determination o f melting points
.
Mixed melting points
Determination o f boiling points .
.
Fractional distillation
.
.
.

Purification of solid organic compounds by

.

.

.

.

111.6.
111.7.
111.8.
111.9.

Reactions and characterisation of saturated aliphatic hydrocarbons 234
n-Octane (Wurtz reaction)
236
n-Hexane (hydrocarbon from Qrignard reagent)
.
.
.
. 237
n-Octane (Clemmensen reduction oj a ketone)
.
.
.
. 238

.

.
.
.
.
.
.
.
recrystallisation .

. 229
229
. 230
.231
. 232

SATURATED ALIPHATIC HYDROCARBONS

ETHYLENIC HYDROCARBONS (ALKENES)
111.10.
111.11.
111.12.

Ainylene
Reactions and characterisation of ethylenic hydrocarbons
cz/cZoHexene

111.13.

Acetylene


.

239
.241
243

.

.245

ACETYLENIC HYDROCARBONS (ALKYNES)

ALIPHATIC ALCOHOLS
111.14.
111.15.
111.16.
111.17.
111.18.
111.19.
111.20.
111.21.
111.22.
111.23.
111.24.
111.25.
111.26.
111.27.

247


n-Arnyl alcohol (from ethyl n-valerate) .
.
.
Tetramethylene glycol (1:4-butanediol)
n-Heptyl alcohol (from n-heptaldehyde)
.
.
CT/cZoHexylcarbinol (from cyclohexyl chloride)
.
n-Hexyl alcohol (from n-butyl bromide)
.
.
n-Nonyl alcohol (from n-heptyl bromide)
.
.
Methyl n-amyl carbinol (from methyl n-amyl ketone)
Methyl n-butyl carbinol (from methyl n-butyl ketone)
Methyl tso-propyl carbinol
.
.
.
.
Di-n-butyl carbinol (from n-butyl bromide) .
.
Dimethyl n-butyl carbinol
Triethyl carbinol
.
.
Dimethyl n-propyl carbinol
.

.
.
.
Reactions and characterisation of aliphatic alcohols

.

.

.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.

.
.


.
.

ALKYL HALIDES
111.28.
111.29.
111.30.
111.31.

n-Butyl chloride (ZnCl2 - HCl method)
sec.-Butyl chloride (ZnCl2-HCl method)
iso-Butyl chloride (SOC12 - Pyridine method)
n-Hexyl chloride (SOC19 method)

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. 249
250
.251
.252
. 253
. 254
. 254
. 255
. 255
. 256
257
258
. 259
. 260


270

.

.

.

272
273
.274
274


xiv
111.32.
111.33.
111.34.
111.35.
111.36.
111.37.
111.38.
111.39.
111.40.
111.41.
111.42.

CONTENTS
cycloHexyl chloride (HCl - CaCl2 method)

tert.-Butyl chloride (HCl method)
isoPropyl bromide (HBr method)
n-Butyl bromide (HBr-H2SOt method)
n-Butyl bromide (KBr-H2SOt method)
n-Butyl bromide (red P-Br 2 method)
1:4-Vuodobuta,ne(KI-H3POt method)
isoPropyl iodide (HI method)
n-Butyl iodide (red P and / 2 method)
n-Hexyl
fluoride
Reactions a n d characterisation o f alkyl halides

.

.

.

POLYHALOGEN COMPOUNDS
111.43.
111.44.
111.45.
111.46.
111.47.
111.48.

297

Chloroform
Bromoform

lodoform
Methylene bromide
Methylene iodide
1 : 2 : 3-Tribromopropane

.297
299
299
300
300
301

ESTERS OF INORGANIC ACIDS
111.49.
111.50.
111.51.
111.52.
111.53.
111.54.
111.55.

n-Butyl sulphite
n-Butyl phosphate
n-Butyl borate
n-Propyl thiocyanate
.
.
n-Amyl nitrite
1-Nitro-n-butane (AgNO2 method)
Nitromethane


.

.

.

302

.

303
304
304
.3 0 5
306
307
307

.

ALIPHATIC ETHERS
111.56.
111.57.
111.58.
111.59.
111.60.

Diethyl ether
Di-n-butyl ether

Ethyl n-hexyl ether
cycloHexyl ethyl ether
Reactions and characterisation of aliphatic ethers

309

.

.

ALIPHATIC ALDEHYDES
111.61.
111.62.
111.63.
111.64.
111.65.
111.66.
111.67.
111.68.
111.69.
111.70.

n-Butyraldehyde
n-Hexaldehyde (catalyst method)
n-Hexaldehyde (ethyl orthoformate method) .
.
n-Hexaldehyde (from n-amyl cyanide)
.
.
Acetaldehyde (from paraldehyde)

.
.
.
Formaldehyde
Hexamethylenetetramine (hexamine) .
.
.
Acetal (acetaldehyde diethylacetal)
Reactions and characterisation of acetals
.
.
Reactions and characterisation of aliphatic aldehydes

Methyl n-hexyl ketone
Diethyl ketone
cyc/oPentanone
Reactions and characterisation of aliphatic ketones
Acetone cyanohydrin
.
.
.
.
.

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310
311
313
314

.315
318

.
.
.

.
.
.

.

.

.
.

.
.

ALIPHATIC KETONES
111.71.
111.72.
111.73.
111.74.
111.75.

PAGE
275

276
277
277
280
281
284
285
285
288
. 289

320
321
. 323
. 324
. 324
.325
.326
327
.327
. 330
335

.
.

.
.

336

338
340
.341
.348


CONTENTS
111.76.
111.77.
111.78.
111.79.

n-Heptaldoxime
.
.
Pinacol a n d pinacolone
.
Diacetone alcohol
Mesityl oxide

.

xv

.
.

.
.


.
.

.
.

PAGE
.3 4 8
. 349
351
353

.
.

.

SATURATED ALIPHATIC MONOBASIC ACIDS
111.80.
111.81.
111.82.
111.83.
111.84.
111.85.

354

iso-Butyric acid
n-Heptoic acid
n-Butyl n-butyrate

n-Valeric acid (hydrolysis of n-butyl cyanide)
.
.
.
cM-Methylethylacetic acid (carbonation of a Grignard reagent) .
Reactions and characterisation of aliphatic carboxylic acids .

355
356
357
.357
. 358
. 360

ACID CHLORIDES OF ALIPHATIC CARBOXYLIC ACIDS

367

Acetyl chloride
n-Butyryl chloride
Reactions and characterisation of acid chlorides of aliphatic acids

367
368
369

111.86.
111.87.
111.88.


.

ACID ANHYDRIDES OF ALIPHATIC CARBOXYLIC ACIDS 371
111.89.
111.90.
111.91.
111.92.
111.93.
111.94.

Acetic anhydride
Keten
n-Caproic anhydride.
.
.
.
.
.
.
.
Succinic anhydride .
.
.
.
.
.
.
.
Maleic anhydride
Reactions and characterisation of acid anhydrides (aliphatic)


372
372
.374
.375
376
. 376

ALIPHATIC ESTERS
111.95. n-Butyl acetate
111.96. terJ.-Butyl acetate
111.97. n-Butyl formate
111.98. ct/c/oHexyl acetate
111.99. Diethyl adipate (azeotropic mixture method) .
.
111.100. Diethyl adipate (benzene method)
111.101. n-Propyl n-valerate
111.102. iso-Propyl lactate (ion exchange resin catalyst method)
111.103. Diethyl maleate (silver salt method)
111.104. Ethyl n-valerate (from n-butyl cyanide)
111.105. Ethyl vinylacetate (acid chloride method)
111.106. Reactions and characterisation of aliphatic esters

379

.

.

.


.

.

.

382
383
384
385
. 385
386
387
. 387
388
389
389
. 390

ALIPHATIC AMIDES
111.107.
111.108.
111.109.
111.110.

Acetamide (from ammonium acetate or from acetic acid) .
Acetamide (from ethyl acetate)
n-Caproamide
Reactions and characterisation of aliphatic amides

.

401
.
.

.

401
403
404
. 404

ALIPHATIC CYANIDES (NITRILES)
111.111.
111.112.
111.113.
111.114.
111.115.

Acetonitrile
n-Amyl cyanide (n-capronitrile) .
.
.
.
.
.
n-Butyl cyanide (n-valeronitrile)
.
.

.
.
.
Trimethylene dicyanide (glutaronitrile)
.
.
.
.
Reactions and characterisation of aliphatic cyanides (nitriles)

www.pdfgrip.com

407
.
.
.
.

407
408
408
409
410


xvi

CONTENTS
PAGE
413

.414
.415
.416
.416
.417
. 4 1 8
419
. 420
.426

111.116.
111.117.
111.118.
111.119.
111.120.
111.121.
111.122.
111.123.
111.124.

ALIPHATIC AMINES
Methylamine hydrochloride (from acetamide)
.
Methylamine hydrochloride (from formalin)
.
Dimethylamine hydrochloride .
.
.
.
Trimethylamine hydrochloride .

.
.
.
n-Amylamine .
.
.
.
.
.
.
n-Heptylamine
.
.
.
.
.
Di-n-butylamine
Reactions and characterisation of aliphatic amines
N-Nitrosodimethylamine (dimethyInitrosamine) .

111.125.
111.126.
111.127.
111.128.
111.129.
111.130.
111.131.
111.132.
111.133.
111.134.


SUBSTITUTED ALIPHATIC MONOBASIC ACIDS
Monochloroacetic acid
.
.
.
.
.
.
.
Monobromoacetic acid a n d ethyl bromoacetate .
.
.
Dichloroacetic acid
Trichloroacetic acid
Glycine (aminoacetic acid)
.
.
.
.
.
.
a-Amino-n-caproic acid (norleucine) .
.
.
.
.
Ethyl cyanoacetate
Reactions a n d characterisation o f amino acids .
.

.
Urea
Thiourea (thiocarbamide) .
.
.
.
.
.
.

427
.428
. 429
431
431
. 432
. 432
433
. 435
441
.442

POLYHYDRIC ALCOHOLS, FATS AND SOAPS
111.135. Saponification o f a fat. Soap .
.
.
.
.
.
111.136. Reactions and characterisation of polyhydric alcohols .

.

444
. 445
. 446

.
.
.
.
.
.

.
.
.
.
.
.

.
.

.
.

CARBOHYDRATES

449


111.137. a- and p-Glucose penta-acetate .
.
.
.
111.138. Mucic acid
111.139. Reactions a n d characterisation o f carbohydrates .
Photographs o f osazones .
.
.
.
.

.

.

.451
452
.
. 453
t o face 4 5 5

.
.

UNSATURATED ALIPHATIC COMPOUNDS
111.140.
111.141.
111.142.
111.143.

111.144.
111.145.
111.146.
111.147.
111.148.
111.149.
111.150.

Allyl alcohol
Crotonaldehyde
pp-Dimethylacrylic acid
Maleic and fumaric acids .
.
.
.
.
.
Crotonic acid and vinylacetic acid
.
.
.
.
Sorbic acid
Diallyl (hexadiene-1,5)
2 : 3-Dimethyl-l : 3-butadiene
Dimethylethynyl carbinol
10-Undecynoic acid
Catalytic reduction with Adams' platinum oxide catalyst

.


459
460
460
.461
.463
466
466
467
467
468
. 470

.

475
477
.481

.
.

483
484
485
. 486
.488

.
.


ETHYL ACETOACETATE
111.151. Ethyl acetoacetate
111.152. Ethyl n-propylacetoacetate and methyl n-butyl ketoiio

DIETHYL MALONATE
111.153.
111.154.
111.155.
111.156.

Diethyl malonate
Ethyl n-butylmaloiiato
n-Caproic acid (from ethyl n-butyl malonate) .
n-Propylmalonic acid
.
.
.

www.pdfgrip.com

.
.

.
.


CONTENTS


xvii
PAGE

111.157.
111.158.
111.159.
111.160.
111.161.
111.162.

SOME ALIPHATIC DICARBOXYLIC ACIDS
Malonicacid
Glutaric acid (from trimethylene dicyanide) .
.
.
Pimelic acid (from benzoyl piperidine) .
.
.
.
Glutaric acid (from cyc\opentanone) .
.
.
.
Adipicacid
cw-Dimethylsuccinic acid .
.
.
.
.
.


[11,163.
111.164.
111.165.
111.166.
111.167.
111.168.

ALIPHATIC SULPHUR COMPOUNDS
n-Hexyl rnercaptan (n-hexyl thiol) .
.
.
Di-n-propyl sulphide
.
.
.
.
.
.
Diethyl disulphide
Potassium ethyl xanthate .
.
.
.
.
.
Ethyl S-ethyl xanthate
Reactions and characterisation of mercaptans (thiols) .

.

.
.
.

.
.
.

489
490
.491
. 492
. 493
494
.495
496
. 497
.4 9 7
498
.499
499
. 500

RESOLUTION OF A RACEMIC COMPOUND
111.169. Determination o f t h e rotatory power
.
.
.
.
. 503

111.170. Resolution of sec.-octyl alcohol (cM-2-octanol) into its optically
active components (d- a n d Z-2-octanol) .
.
.
.
. 506

CHAPTER IV
PREPARATION AND REACTIONS OF AROMATIC
COMPOUNDS
AROMATIC HYDROCARBONS
IV,1.
n-Butylberkzene (Wurtz - Fittig synthesis)
.
IV,2.
iso-Propylbenzene (cumene)
.
.
.
IV,3. terf.-Butylbenzene .
.
.
.
.
IV,4.
Diphenylmethane
.
.
.
.

.
IV,5.
Triphenylmethane .
.
.
.
.
IV,6.
Ethylbenzene
IV,7.
n-Propylbenzene
.
.
.
.
.
IV,8.
n-Amylbenzene
.
.
.
.
.
IV,9.
Characterisation o f aromatic hydrocarbons .

508
.
.
.

.
.

.
.
.
.
.

.
.
.
.
.

.
.
.

.
.
.

.
.
.

NITRATION OF AROMATIC HYDROCARBONS
IV, 10.
IV,11.

IV,12.
IV,13.
I V.I 4.
IV,15.
IV,16A.
IV,16B.

Nitrobenzene
a-Nitronaphthalene
m-Dinitrobenzene
.
.
2 : 4-Dinitrotoluene
p-Bromonitrobenzene
.
2 : 2'-Dinitrodiphenyl
Reactions and characterisation
Reactions and characterisation

.

.

.

.

.

.


.

.

.

.

523
.
.
.

of aromatic nitro compounds
of aliphatic nitro compounds

HALOGENATION OF AROMATIC HYDROCARBONS
IV,17.
IV,18.
1V,19.

Chlorobenzene
Bromobenzene
.
w-Bromonitrobonzene

.
.


.
.

.
.

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.
.

.
.

.
.

.511
.512
.513
.513
. 5 1 5
615
.516
. 6 1 7
. 518

.
.


525
526
.5 2 6
. 527
• 527
527
. 528
. 531

633
535
.5 3 5
.5 3 7


xviii

CONTENTS

IV,20.
IV,21.
IV,22.
IV,23.
IV,24.
IV,25.
IV,26.
IV,27.
IV,28.

a-Bromonaphthalene

.
.
.
.
.
.
lodobenzene .
.
.
.
.
.
.
.
Benzyl chloride (chlorination o f toluene)
.
.
.
Benzyl chloride (chloromethylation of benzene)
lodobenzene dichloride .
.
.
.
.
.
lodosobenzene
.
.
.
.

.
.
.
lodoxybenzene
.
.
.
.
.
.
.
Diphenyliodonium iodide .
.
.
.
.
.
Reactions and characterisation of halogenated aromatic
carbons
.
.
.
.
.
.
.
.

PAGE


.
.
.
.
.
.
.
hydro
.
.

SULPHONATION OF AROMATIC HYDROCARBONS
IV,29.
IV,30.
IV,31.
IV,32.
IV,33.
IV,33A.

Sodium benzenesulphonate
.
.
.
.
.
Sodium jo-toluenesulphonate
.
.
.
.

.
Sodium p-naphthalenesulphonate
.
.
.
.
p-Toluenesulphonic acid .
.
.
.
.
.
Reactions and characterisation of aromatic sulphonic acids
Reactions and characterisation of aromatic sulphonamides

.
.
.
.
.

Aniline .
.
.
.
.
.
.
.
p-Phenylethylamine .

.
.
.
.
.
a-Phenylethylamine .
.
.
.
.
.
a-Naphthylamine .
.
.
.
.
.
p-Naphthylamine .
.
.
.
.
.
Benzylamine (Gabriel synthesis) .
.
.
.
Pure methylaniline from commercial methylaniline
Benzylaniline .
.

.
.
.
.
.
Dimethylaniline
.
.
.
.
.
.
7>-Nitrosodimethylaniline .
.
.
.
.
m-Nitroaniline
.
.
.
.
.
.

.
.
.
.


Acetanilide
.
.
.
Diacetyl-o-toluidine .
.
2 : 4 : 6-Tribromoacetanilide
jo-Bromoacetanilide .
.
jo-Bromoaniline
.
.
jo-Nitroacetanilide .
.
£>-Nitroaniline
.
.

.
.
.
.
.
.
.

.
.
.
.

.
.
.

.
.
.
.
.
.
.

.
.
.
.
.
.
.

.
.
.
.
.
.

.
.
.

.
.
.

. 563
. 566
. 567
. 568
. 568
. 569

.
.
.
.

.
.
.
.

. 572
. 572
. 573
. 574

570

.
.

.
.
.
.
.

576

.
.
.
.
.
.
.

.
.
.
.
.
.
.

BENZOYLATION OF AROMATIC AMINES
IV,52.
IV,53.
IV,54.

Benzanilide (Schotten - Baumann reaction) .

Benzanilide .
.
.
.
.
.
Hippuric acid (benzoyl glycine) .
.
.

.
.
.

.
.

Sulphanilic acid
Naphthionic acid
Orthanilic acid
Metanilic acid

.
.
.
.

.
.
.

.

.
.
.
.

.
.
.
.

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.
.
.
.

.
.
.
.

.
.
.
.

577

578
579
580
580
581
581
582

.
.

582

. 583
. 584

SULPHONATION OF AROMATIC AMINES
IV,55.
IV,56.
IV,57.
IV.58.

549
550
551
552
552
558
559


ACETYLATION OF AROMATIC AMINES
IV,45.
IV,46.
IV,47.
IV,48.
IV,49.
IV,50.
IV,51.

542
548

AROMATIC AMINES AND THEIR SIMPLE DERIVATIVES
IV,34.
IV,35.
IV,36.
IV,37.
IV,38.
I V,39.
IV,40.
IV,41.
IV,42.
IV,43.
IV.44.

537
538
538
539
541

541
542
542

585

.
.
.
.

.
.
.
.

586
586
587
589


CONTENTS

xix
PAGE

DIAZONIUM SALTS
IV159. Solid phenyldiazonium chloride .
.

IV,60. lodobenzene .
.
.
.
.
IV,61. p-Chlorotoluene
I V,62. p-Bromotoluene (Sandmeyer reaction) .
IV,63.r a - B r o m o t o l u e n e.
.
.
.
IV,64. o-Broinotoluene (Gattermann reaction).
IV,65. Benzenesulphinic acid
.
.
.
IV,66. p-Tolunitrile (p-tolyl cyanide) .
.
IV,67. Fluorobenzene
.
.
.
.
IV,68. o-Dinitrobenzene
.
.
.
.
IV,69. Phenol (from aniline)
IV,70. w-Nitrophenol

IV,71. Toluene (from p-toluidine)
IV,72. syw.-Tribromobenzene
•
•
•
IV,73. 3 : 3'-Dimethyldiphenyl
IV,74. Diphenio acid (from anthranilic acid) .
IV,75. Phenylarsonic acid .
•
.
.

590
.
.

.
.

.
.

.
.

.
.
.
.
.

.
.

.
.
.
.
.
.
.

.
.
.
.
.
.
.

.
.
.
.
.
.
.

•

•


•

•

.
.

.
.

.

.
.

SOME AZO DYESTUFFS
IV,76.
IV,77.
IV,78.
IV,79.
1V,80.
IV,81.
IV, 82.

Phenyl-azo-p-naphthol
Chrysoidine
Methyl orange .
.
Orange I I ((3-naphthol orange) .

Methyl red
Diazoaminobenzene .
.
.
p-Amino-azobenzene.
.
.

620

.

.

.

.
.

.
.

.
.

%

.

.


.
.

.
.

INTERMEDIATE PRODUCTS IN THE REDUCTION OF
NITRO COMPOUNDS
IV,83.
IV,84.
IV,85.
IV,86.
IV,87.
IV,88.

(S-Phenylhydroxylamine
Nitrosobenzene
Azoxybenzene .
.
.
.
.
.
Azobenzene
Hydrazobenzene (sT/w.-diphenylhydrazine) .
Benzidine

. 597
. 598

600
. 602
. 6 0 5
. 606
.607
. 607
. 609
.612
613
614
616
.615
616
.617
.617

.

.

.

.

.

.

622
623

624
. 625
625
. 626
. 627

628
629
630
.631
631
.632
633

REDUCTION OF DIAZONIUM COMPOUNDS. ARYL HYDRAZINES 635
IV,89.
IV,90.
IV.91.

Phenylhydrazine
p-Nitrophenylliydrazine
2 : 4-Dinitrophenylhydrazine

IV,92.
IV,93.

o-Phenylenediamine
7/i-Phenylenediamine

636

637
638

AROMATIC DIAMINES
.

.

.

.

640
.

.

.

640
.641

MISCELLANEOUS COMPOUNDS DERIVED FROM
PRIMARY AMINES
IV,94.
IV,95.
IV.96.
IV,97.
IV,98.
IV,99.

IV, 100.

Tliiocarbanilide (syra.-diphenylthiourea)
.
.
Phenyl wo-thiocyanate (from thiocarbanilide)
.
Phenyl iso-thiocyanate (from aniline) .
.
.
Phenylurea (cyanate method)
.
.
.
.
Phenylurea (urea method)
p-Iodoaniline
Reactions and characterisation of aromatic amines

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.
.
.
.

.
.
.
.


.

.

.6 4 2
. 642
. 643
. 644
645
. 647
. 648


xx

CONTENTS
PAGE
664

PHENOLS
IV,101.
IV,102.
IV,103.
IV, 104.
IV,105.
IV,106.
IV,107.
IV,108.
IV,109.

IV,110.
IV,111.
IV,112.
IV,113.
IV,114.

p-Cresol
(3-Naphthol
Phenyl acetate
Anisole
Phenyl n-butyl ether
Reactions and characterisation of aromatic ethers
o-Propiophenol a n d p-propiophenol .
.
.
o-and jo-nitrophenols
.
.
.
.
.
2 : 4-Dinitrophenol
Picric acid ( 2 : 4 : 6-trinitrophenol)
^-Bromophenol
o-Bromophenol
p-Iodophenol
Reactions a n d characterisation o f phenols .
.

.


.
.

.

.
.

.

.

AROMATIC ALDEHYDES
IV,115.
IV,116.
IV,117.
IV,118.
IV,119.
IV,120.
IV,121.
IV, 122.

Benzaldehyde
jo-Bromobenzaldehyde
.
.
.
jo-Nifcrobenzaldehyde
.

.
.
jo-Tolualdehyde
p-Naphthaldehyde
a-Naphthaldehyde (Sommelet reaction)
Mesitaldehyde
Salicylaldehyde

689

.
.

.
.

.
.

.
.

.

.

.

.


CONDENSATION REACTIONS OF AROMATIC ALDEHYDES
IV, 123.
IV,124.
IV,125.
IV,126.
IV,127.
IV,128.
IV,129.
IV,130.
IV,131.
IV,132.
IV,133.
IV,134.
IV, 135.

Benzyl alcohol and benzoic acid (Cannizzaro reaction) .
.
Cinnamic acid
Benzoin
Benzil
Benzilic acid
Benzalacetone
p-Nitrostyrene
Benzalacetophenone (chalcone) .
.
.
.
.
.
Ethyl cinnamate

p-Piperonylacrylic acid (3 : 4-methylenedioxycinnamic acid) .
a- and p-Benzaldoximes .
Hydrobenzamide
.
.
Reactions and characterisation of aromatic aldehydes .
.

AROMATIC KETONES
IV, 136.
IV,137.
IV, 138.
IV,139.
IV, 140.
IV,141.
IV, 142.
IV,143.
IV, 144.
IV,145.
IV,146.
IV,147.
IV, 148.

Acetophenone
Butyrophenone
jD-Bromoacetopherioiie
.
.
.
.

.
Benzophenone
Benzylacetophenone
.
.
.
.
.
Methyl'benzyl ketone
.
.
.
.
.
Phloroacetophenoiie .
.
.
.
.
.
a-Tetralone
o-Benzoylbenzoic acid
.
.
.
.
.
Anthraquinone
.
.

.
.
.
.
Anthrone
Benzophenone oxiine and Beckmann rearrangement
Reactions and characterisation of aromatic ketones

www.pdfgrip.com

667
668
669
669
671
. 671
. 676
.6 7 7
678
678
679
679
680
. 681

693
.6 9 4
.6 9 5
697
698

. 700
701
703

706
.711
712
714
714
715
716
717
.718
718
. 719
719
.720
. 720

725
.

.

.
.
.

.
.

.

.
.

.
.

.
.

.
.

729
732
.732
733
.734
.7 3 4
.736
737
.739
.7 4 0
740
.741
.741


CONTENTS


xxi

QUINONES

PAGE
745

IV,149.
IV,150.
IV,151.
IV 7 ,152.

7>-Benzoquinone (" quinorie "
)
.
.
1 : 2-Naphthoquinone
Quinhydrone
Reactions a n d characterisation o f quinones

IV,153.
IV,154.
IV, 155.
IV, 156.
IV, 157.
IV,158.
IV,159.
IV, 160.
IV,161.

IV,162.
IV,163.
IV,164.
IV, 165.
IV, 166.
IV, 167.
IV,168.
IV,169.
IV,170.
IV,171.
IV, 172.
IV,173.
IV, 174.
IV,175.

AROMATIC CARBOXYLIC ACIDS
Benzoic acid .
.
.
.
.
.
.
p-Nitrobenzoic acid
.
.
.
.
.
2 : 4 : 6-Trinitrobenzoic acid

2 : 4-Dinitrophenylacetic acid .
.
.
.
o-Chlorobenzoic acid
.
.
.
.
.
Terephthalic acid
o-Toluicacid
Phenylacetic acid (from benzyl cyanide]
.
.
p-Nitrophenylacetic acid .
.
.
.
.
7?-Aminophenylacetic acid
.
.
.
.
a-Naphthoic acid
p-Naphthoic acid
Diphenic acid (from phetianthrvne)
.
.

.
Hydrocinnamic acid
.
.
.
.
.
m-Nitrobenzoic acid .
.
.
.
.
.
3 : 5-Dinitrobenzoic acid
Homophthalic acid
Anthranilic acid
Diphenylacetic acid
Mandelicacid
Salicylic acid
Phenylpropiolic acid
Reactions and characterisation of aromatic carl>oxylie

IV,176.
IV,177.
IV,178.
IV, 179.
IV,180.
IV,181.
IV,182.
IV,183.


.

.

.

.

.

.

.

acids .

751
.755
.7 5 7
758
. 758
. 758
760
760
.761
.763
. 764
764
766

.768
. 768
.769
770
771
773
773
774
774
776
. 777

.

780
781
782
783
783
784
784
785
. 785

.
.

.
.


.
.

.
.

.
.
.

.
.
.

.
.
.

.
.
.

AROMATIC ESTERS
.
. ,

Methyl benzoate
Methyl salicylate
Benzyl acetate
Ethyl phenylacetate

Phenyl ciimamate
Phenyl benzoate
Ethyl a-naphthoate
Reactions and characterisation of aromatic esters

AROMATIC ACID CHLORIDES
IV,184. p-Nitrobenzoyl chloride
IV,185. Benzoyl chloride

. 745
746
747
. 747

.

791
791
792

AROMATIC ACID ANHYDRIDES
794
IV,186. p-Chlorobenzoic anhydride
.
.
.
.
.
.
.7 9 4

IV, 187. Reactions and characterisation of acid chlorides of aromatic acids . 795
AROMATIC ACID AMIDES

IV,188.
IV,189.
IV,190.
IV,191.
IV, 192.

797
Benzamide
797
Mercury benzamide
797
o-Toluamide
798
Reactions and characterisation of primary aromatic amides .
. 798
Reactions and characterisation of substituted aromatic amides
(aromatic acylated bases)
.
.
.
.
•
•
.801

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xxii

CONTENTS
PAGE
803

AROMATIC NITRILES
IV,193. Benzonitrile
IV, 194. Veratronitrile
IV, 195. Reactions and characterisation of aromatic nitriles

IV, 196.
IV, 197.
IV,198.
IV,199.

.

803
804
. 805

SOME AROMATIC PEROXIDES AND PER-ACIDS

807

Benzoyl peroxide
p-Nitrobenzoyl peroxide
Perbenzoic acid (benzoyl hydrogen peroxide)

Monoperphthalic acid

.

.

.

807
808
. 808
810

.

AROMATIC ALCOHOLS
IV,200.
IV,201.
IV,202.
IV,203.
IV,204.
IV,205.

811

p-Tolyl carbinol (p-methyl benzyl alcohol) .
Benzhydrol (diphenylcarbinol) .
.
.
.

Triphenylcarbinol
Triphenylchloromethane .
.
.
.
.
p-Phenylethyl alcohol
Reactions and characterisation of aromatic alcohols

812
812
813
815
816
817

COMPOUNDS DERIVED FROM AROMATIC
SULPHONIC ACIDS
IV,206.
IV,207.
IV,208.
IV,209.
IV,210.
IV,211.
IV,212.

Benzenesulphonyl chloride
jo-Toluenesulphonyl chloride
Dichloramine-T and chloramine T
Saccharin

.
.
.
n-Butyl jo-toluenesulphonate
Sodium £>-toluenesulphinate
Thiophenol
.
.
.

.
.
.

.
.
.

.
.
.

.
.
.

820

.
.

.

.

822
822
823
824
.825
.826
. 8 2 7

CHAPTER V
SOME HETEROCYCLIC AND ALICYCLIC COMPOUNDS
V,l.
V,2.
V,3.
V,4.
V,5.
V,6.
V,7.
V,8.
V,9.
V,10.
V,ll.
V,12.
V,13.
V,14.
V,15.
V,16.

V,17.
V,18.
V,19.

Quinoline
Quinaldine
Furfuryl alcohol and furoic acid
.
2-Furfuralacetone
Furylacrylicacid
Furoin
Furil
2-Methylthiophene
2:5-Dimethylthiophene
2-Acetylthiophene
Pyrrole
2: 5-Dimethylpyrrole
2: 4-Dimethyl-3:5-dicarbethoxypyrrole
Succinimide
2-Aminothiazole
2 : 4-Dimethylthiazole
2 : 5-Dimethylpyrazole
5 : 5-Dimethylhydantoin
4-JZthylpyridme (frompyridine) .
.

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.


.

.

.

.

.

.

.

829
831
.832
833
834
835
835
836
836
837
837
838
839
840
840
841

842
843
.844


CONTENTS
V,20.
V,21.
V,22.
V,23.
V,24.
V,25.
V,26.
V,27.
V,28.
V,29.
V,30.
V,31.
V,32.
V,33.

xxiii

PAGE
n-Amylpyridines (from picolines)
.
.
.
.
.

. 845
Picolinic acid
847
Nicotinic acid
848
Ethyl nicotinate
849
(3-Cyanopyridine
.
.
.
.
.
.
.8 5 0
Uramil
850
2-Phenylindole
851
Benzimidazole
.
.
.
.
.
.
.
.
.8 5 3
4-Methylcoumarin

853
2-Hydroxylepidine (4-methylcarbostyril) .
.
.
.
.855
Phenylbenzoyldiazomethane
.
.
.
.
.
.
.8 5 6
2-Carbethoxyct/cZopentanone
.
.
.
.
.
.
.8 5 6
cycZoButane-1 : 1-dicarboxylic 'acid and q/cZobutanecarboxylie
acid
857
q/c/oPropanecarboxylic acid
.
.
.
.

.
.
.859

CHAPTER VI
MISCELLANEOUS REACTIONS
VI, 1.
VI,2.
VI,3.
VI,4.
VI,5.
VI,6.
VI,7,
VI,8.
VI,9.
VI,10.
VI,11.
VI,12.
VI,13.
VI,14.

Acetylacetone
861
Benzoylacetone
.
.
.
.
.
.

.
.
.8 6 5
Phenylglyoxal
866
Apparatus f o r reactions under pressure
.
.
.
.
. 866
Raney nickel (catalyst)
870
Copper - chromium oxide catalyst
.
.
.
.
.
. 872
Hexamethylene glycol (1:6-Hexanediol)
873
Ethyl p-phenyl-p-hydroxypropionate
.
.
.
.
.874
pp-Dimethylglutaric acid
876

Reductions with lithium aluminium hydride
.
.
.
. 877
Reductions with potassium (or sodium) borohydride .
.
.881
Reductions with aluminium alkoxides
.
.
.
.
. 882
The Opperiauer oxidation
886
Oxidation of unsaturated compounds with ozonized oxj'gen (ozonolysis)
888
VI,15.
Epoxidation and hydroxylation of ethylenic compounds
.
. 893
VI,16.
Reactions in liquid ammonia. Some acetylenic compounds .
. 895
VI,17. The Arndt-Eistert reaction
902
VI, 1 8 . T h e Darzens glycidic ester condensation
.
.

.
.
. 906
VI,19. T h e Erlenmeyer azlactone reaction .
.
.
.
.
. 907
VI,20. The Mannich reaction
910
VI,21. The Michael reaction
912
VI,22. Cyanoethylation
.914
VI,23. The Schmidt reaction or rearrangement
.
.
.
.
.917
VI.24. The Stobbe condensation
919
VI,25. The Willgerodt reaction
923
VI,26. The Wohl-Ziegler reaction. Applications of JV-bromosuccinimide 926
VI,27. Synthesis o f unsymmetrical diaryls .
.
.
.

.
. 927
VI,28.
Syntheses with organou'thium compounds
.
.
.
. 928
VI,29. Syntheses with organosodium compounds .
.
.
.
. 933
VI,30.
Syntheses with organocadmium compounds
.
.
.
. 935
VI,31. Some electrolytic syntheses
.
.
.
.
.
.
. 937
VI,32. The diene synthesis (Diels-Alder reaction)
.
.

.
.941
VI,33.
Some applications of chromatographic adsorption
.
.
. 944
VI,34. Ring enlargement with diazomethane. cycJoHeptanone from
ct/cJohexanone
.
.
.
.
.
.
.
.
. 9 4 6
VI,35. Dehydrogenation o f hydroaromatic compounds .
.
.
. 947
VI,36.
Preparation of palladium catalysts for hydrogenation .
. 949
VIf37.
Oxidation with lead tetra-acetate. n-Butyl glyoxylate
.
.951


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xxiv

CONTENTS
CHAPTER VII
ORGANIC REAGENTS IN INORGANIC AND
ORGANIC CHEMISTRY

PAGE
VII,1.
Dimethylglyoxime
953
VII,2.
Semicarbazide hydrochloride .
.
.
.
.
.
.954
VII,3.
Diphenylcarbazide
954
VII,4.
Diphenylcarbazone .
.
.
.

.
.
.
.
.9 5 5
VII,5.
Dithizone (diphenylthiocarbazone)
.
.
.
.
.
.955
VII,6.
Cupferron
.
.
.
957
VII,7.
Salicylaldoxime
957
VII,8.
a-Benzoinoxime
.
.
.
.
.
.

.
.
.9 5 8
VII,9.
a-Nitroso-p-naphthol
958
VII,10. Ammonium salt of aurin tricarboxylie acid ('* alnminon ") .
. 959
VII,11. jo-Nitrobenzene-azo-a-naphthol .
.
.
.
.
.
.9 6 0
VII,12. jo-Bromophenacyl bromide
.
.
.
.
.
.
.960
VII,13. £>-Nitrobenzyl bromide
961
VII,14. p-Phenylphenacyl bromide
.
.
.
.

.
.
.962
VII,15. 5 : 5-Dimethyl-1 : 3-cyc/ohexanedione (dimethyJdihydro-resorcinol) . 963
VII,16. Xanthhydrol
'
.
.964
VII,17. 1 : 3 : 5-Trinitrobenzene
965
VII,18. S-Benzyl-iso-thiuronium chloride
.
.
.
.
.
.965
VII,19. 3-Nitrophthalie anhydride
966
VII,20. Diazomethane
967
VII,21. 3 : 4 : 5-Triiodobenzoyl chloride
973
VII,22. 3 : 5-Dinitrobenzoyl chloride
974
VII,23. 1 : 2-c?/cZoHexanedione-dioxime (nioxime) .
.
.
.
. 974

VII,24. Quinaldinic acid
976
VII,25. Girard's reagents " T " and " P "
976
VII,26. Pseudo-saccharin chloride
.
.
.
.
.
.
.978

CHAPTER VIII
DYESTUFFS, INDICATORS AND RELATED COMPOUNDS
VIII,1.

Congo reel

VIII,2.
VIII,3.
VIII.4.
VIII,5.
VIII,6.
VIII,7.
VIII,8.
VIII,9.
VIII,10.
VIII,11.
VIII,12.

VIII,13.
VIII,14.

Indigo
Alizarin
Crystal violet
Copper phthalocyanine (Monastral Blue) .
.
.
.
Phenolphthalein
.
Fluorescein a n d eosin
.
.
'
.
.
.
.
.
p p -Tetramethyldiaminodiphenylmethane .
.
.
.
o-Sulphobenzoic anhydride
.
.
.
.

.
.
Sulphonephthaleins
JV-Phenylanthranilic acid
1 : 10-Phenanthroline
2 : 2'-Dipyridyl
Ninhydrin (indane-1 : 2 ; 3-trione hydrate)

979

980
981
982
. 983
. 984
. 985
.987
.987
989
991
991
992
993

CHAPTER IX
SOME PHYSIOLOGICALLY ACTIVE COMPOUNDS
IX,1.
IXf2.
IX,3.
IX,4.

IX,5.
IX,6.

Aspirin (acetylsalicylic acid)
.
.
Phenacetin
Antipyrine
Bromural (a-bromo-?'so-valerylurea) .
Benzocaine (ethyl p-aminobenzoate) .
Barbituric acid
.
.
.

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.

.

.

.

.
.

.
.


.
.

.
.

. 996
996
998
.9 9 9
. 1000
1001


CONTENTS

xxv
PAGE

1X,7.
1X,8.
IX,9.
IX,10.
IX, 11.
IX,12.
IX,13.
IX,14.

Diethylbarbituric acid (veronal)

.
.
.
.
Phenylethylbarbituric acid (phenobarbitone)
.
.
jo-Aminobenzenesulphonamide (sulphanilamide) .
.
2-(7>-Aminobenzenesulphonamido) pyridine (sulphapyridine)
Sulphaguanidine
2-Phenylquinoline-4-carboxylic acid (atophan) .
.
2 : 2-6is(p-Chlorophenyl)-l : 1 : 1 -trichloroethane (D.D.T.)
3-Indoleacetic acid

.
.
.
.
.
.

. 1002
. 1003
. 1005
. 1007
1009
. 1010
. 1011

1012

CHAPTER X
SYNTHETIC POLYMERS
X,l.
X,2.
X,3.
X,4.
X,5.
X,6.
X,7.
X,8.
X,9.

Brief introduction t o subject
.
.
.
.
Phenol-formaldehyde resin
Depolymerisation o f methyl methacrylate resin .
Formation o f a glyptal resin
.
.
.
.
Thiokol A (polyethylene polysulphide)
Phenylethylene (styrene)
Polystyrene
Ethy 1 enediamine - adipic acid polymer

.
.
Depolymerisation of a hexamethylenediamine - adipic
(Nylon " 66 ")

.

.

. 1014
1022
.
.
. 1023
.
.
. 1023
1024
1024
1025
.
.
. 1025
acid polymer
1025

CHAPTER XI
QUALITATIVE ORGANIC ANALYSIS
XI,1.
XI,2.

XI,3.
XI,4.
XI,5.
XI,6.
XI,7.
XI,8.
XI,9.

Basis o f qualitative organic analysis .
.
.
.
.
. 1026
Determination o f physical constants .
.
.
.
.
. 1028
Qualitative analysis f o r t h e elements .
.
.
.
.
. 1038
T h e solubilities o f organic compounds.
.
.
.

.
. 1045
The solubility groups
1050
Determination of the solubilities of organic compounds (for group
tests]
1055
Class reactions (reactions for functional groups)
.
.
. 1057
T h e preparation o f derivatives .
.
.
.
.
.
. 1081
Qualitative analysis of mixtures of organic compounds
.
. 1090

CHAPTER XII
SEMIMICRO TECHNIQUE
XII,1.
XII,2.
XII,3.
XII,4.

Introduction and general considerations

.
.
.
.
Some typical operations o n t h e semimicro scale .
.
.
Semimicro apparatus with interchangeable ground glass joints
Small-scale preparations .
.
.
.
.
.
.

.1101
. 1102
. 1109
.1110

APPENDIX
LITERATURE OF ORGANIC CHEMISTRY
A,L
A,2.
A,3.
A,4.
A,5.
A,6.
A,7.

A,8.
A,9.
A,10.

Beilstein's " Handbuch "
1115
Original sources of chemical information .
.
.
.
.1127
Secondary sources of chemical information. Abstracting journals . 1127
Locating an organic compound
.
.
.
.
.
.1128
Selected reference works on organic chemistry
.
.
.
.1128
Laboratory accidents and first aid
.
.
.
.
.

.1130
Applications of infrared and ultraviolet spectra to organic chemistry 1134
Densities and percentage compositions of various solutions .
. 1151
Density and vapour pressure of water : 0° to 35° C.
1162
Atomic weights
.
.
.
.
.
.
.
.
.1163

INDEX

1165

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NAME INDEX OF ORGANIC REACTIONS!
Acetoacetic ester condensation .
Arndt-Eistert reaction
Bart reaction .
Beckmann rearrangement
Benzidine rearrangement .

Benzilic acid rearrangement
Benzoin reaction (condensation)
Blanc chloromethylation reaction
Bouveault-Blanc reduction
Bucherer hydantoin synthesis .
Bucherer reaction .
Cannizzaro reaction
Claisen aldol condensation
Claisen condensation
Claisen-Schmidt reaction .
Clemmensen reduction
Darzens glycidic ester condensation .
Diazoamino-aminoazo rearrangement
Dieckmann reaction
Diels-Alder reaction
Doebner reaction .
Erlenmeyer azlactone synthesis
Fischer indole synthesis .
Fischer-Speier esterification
Fried el-Crafts reaction
Fries reaction .
Gabriel synthesis
Gattermann aldehyde reaction
Gattermann reaction
Gattermann-Koch reaction
Gomberg-Hey reaction
Grignard reaction

Guareschi reaction .
Haworth reaction

Hell-Volhard-Zelinsky reaction .
Hoesch reaction
Hofmann reaction .
Knoevenagel reaction
Knorr pyrrole synthesis
Kolbe-Schmitt reaction
Leuckart reaction
Mannich reaction
Meerwein-Ponndorf-Verley reduction
Michael reaction
Oppenauer oxidation

PAGE
. 475, 476*, 477-481
902, 903, 904* 905, 906
597, 617, 618
. 729, 741
629*, 633
. 709*. 715, 716
708*, 714
534, 639, 540
247, 249, 250, 812, 816
843*, 844
. 561*, 568, 569
706*, 711, 712, 811, 812, 832
. 710*, 718
. 477, 861*, 862*, 863-865
. 709, 710*, 716-718
238, 510, 515, 516, 728, 738
. 906* 907

. 622*, 626, 627
. 856, 857
. 941, 942*, 943
463, 465, 710, 711*, 719
. 907, 908*, 909, 910
. 851*, 852
. 379*, 380*, 382-383, et seq.
. 508, 509*, 512, 513, 515,
725, 726*, 728, 729-734,
811, 815
. 664*, 665*, 676, 677, 727
. 559, 560*, 566
. 689, 690*, 701-703
. 593, 609
. 689*, 697, 698
927, 928*
. 237, 240, 247, 248* 249*,
253, 255-259, 358-359,
394, 511, 516-517, 752,
756-757, 765, 781, 811,
813-815
. 876*, 877
. 726, 728*, 737, 738
. 427*, 429, 430
. 727*, 736, 737
. 413*, 414, 754, 773
490, 710, 711*, 719
. 839*, 840
754, 755*, 774-776
. 561, 567

. 910, 911*, 912, 1012, 1013
. 882*, 883-836
. 912, 913*, 914
. 886, 887*, 888

t A number of rearrangements and also the acetoacetic ester condensation are
included in the Name Index for the convenience of the reader. Other reactions
(including ring enlargement with diazomethane) for which mechanisms are given
will be found in the Index. The asterisk indicates the page where the mechanism
(in outline) is described.

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NAME INDEX OF ORGANIC REACTIONS
Pechmann reaction .
Perkin reaction
Pinacol-pinacolone rearrangement
Prileschajew epoxidation reaction
Reformatsky reaction
Reimer-Tiemann reaction
Rosenmund reduction
Sandmeyer reaction
Schiemann reaction
Schmidt reaction or rearrangement
Schotten-Baumann reaction
Skraup reaction
Sommelet reaction .
Stephen reaction
Stobbe condensation

Ullmann reaction
Willgerodt reaction .
Williamson synthesis
Wohl-Ziegler reaction
Wolff rearrangement
Wolff-Kishner reduction .
Wurtz reaction
Wurtz-Fittig reaction

XXVll

PAGE
. 853*, 854, 855
706, 707*, 708, 712-713
. 349*, 350, 351
. 893*, 894
. 874*, 875, 876
. 691, 692*, 703-705
. 691, 699
591, 592*, 594, 600-603, 751
594*, 595, 609-612, 618
. 917, 918*, 919
582, 584, 780, 784
828*, 829, 830, 991, 992
. 692, 693*, 700, 701
. 318*, 324, 691, 698
. 919, 920*, 922, 923
. 524, 527
. 923, 924*, 925
309, 665, 670, 671

926 927
. 903, 904*, 905', 906
. 510, 511*, 616
. 236, 237
. 508*, 511, 512

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CHAPTER I
THEORY OF GENERAL

TECHNIQUE

THEORY OF DISTILLATION
.,1. Vapour pressure. If a liquid is admitted into a closed vacuous
space, it will evaporate or give off vapour until the latter attains a definite
pressure, which depends only upon the temperature. The vapour is then
said to be saturated. Experiment shows that at a given temperature

0

20

40

6Q

60


100

120

I4Q

Temperature °C

Fig. /, 1, 1.

the vapour pressure of a liquid substance in contact with its own liquid
is a constant quantity and is independent of the absolute amount of liquid
and of vapour present in the system. The vapour pressure is usually
1

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2

PRACTICAL ORGANIC CHEMISTRY

[I,

expressed in terms of the height of a mercury column which will produce
an equivalent pressure.
The vapour pressure of a liquid increases with rising temperature. A
few typical vapour pressure curves are collected in Fig. /, 1, 1. When
the vapour pressure becomes equal to the total pressure exerted on the
surface of a liquid, the liquid boils, i.e., the liquid is vaporised by bubbles

formed within the liquid. When the vapour pressure of the liquid is the
same as the external pressure to which the liquid is subjected, the temperature does not, as a rule, rise further. If the supply of heat is increased,
the rate at which bubbles are formed is increased and the heat of vaporisation is absorbed. The boiling point of a liquid may be defined as the
temperature at which the vapour pressure of the liquid is equal to the
external pressure Exerted at any point upon the liquid surface. This
external pressure may be exerted by atmospheric air, by other gases, by
vapour and air, etc. The boiling point at a pressure of 760 mm. of mercury,
or one standard atmosphere, may be termed the normal boiling point.
If the pressure on the surface is reduced, say by connecting the vessel
containing the liquid with a pump, the boiling point is lowered ; the exact
value may be obtained by reference to a vapour pressure curve (see, for
example, Fig. /, 1, 1). It is therefore necessary to specify the pressure in
recording a boiling point : unless this is done, 760 mm. is understood.
Advantage is taken of the lower boiling point under diminished pressure
in the distillation of substances which decompose upon heating to the
boiling point under atmospheric pressure ; thus, ethyl acetoacetate, which
boils with decomposition at 180° under 760 mm. pressure, boils without decomposition at 78° under 18 mm. pressure (usually written as 78°/18 mm.).
1,2. Calculation of the boiling point at selected pressures. One
sometimes requires the boiling point of a liquid at a pressure which is
not recorded in the literature. This can best be calculated from the
vapour pressure - temperature curve. For most practical purposes this
may be assumed to have the form :
D

log p = A + T

where p is the vapour pressure, T is the temperature on the absolute
scale, and A and B are constants. If log p is plotted as ordinates against
rp as abscissae, a straight line is obtained.


Two values of p with the

corresponding values of T suffice. Values of p corresponding to any
absolute temperature or vice versa can be obtained from the graph. A
few typical log p-f/1 diagrams, using the data from which Fig./, 7, 1
was constructed, are shown in Fig. /, 2, 1 ; it will be seen that they
approximate to straight lines.
For distillations conducted at atmospheric pressure, the barometric
pressures are rarely exactly 760 mm. and deviations may be as high as
20 mm. To correct the observed boiling point to normal pressure
(760 mm.), the following approximate expression may be used :
A* = 0-0012 (760 — p) (t + 273),
where A* is the correction in degrees Centigrade to be applied to the

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