A TEXT-BOOK OF
PRACTICAL ORGANIC CHEMISTRYINCLUDING
QUALITATIVE ORGANIC ANALYSISBy
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 LondonAssociated 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 EDITIONTHE 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.
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 pagesa 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 EDITIONTHE 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
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 himresearch 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 madein many cases
the original source has been lost track ofit 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
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.
CONTENTSCHAPTER I THEORY OF GENERAL TECHNIQUE THEORY OF
DISTILLATION1.1. 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 LIQUIDS1.8. 1.9. Partially miscible
liquids. Critical solution temperature . . Influence of added
substances upon the critical solution temperature 17 20
THEORY OF MELTING AND FREEZING1.10. 1.11. 1.12. 1.13. 1.14.
1.15. 1.16. 1.17. 1.18. 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
1.19. 1.20. 1.21. 1.22.
. . .
. . .
. . .
. . .
.
CHAPTER II EXPERIMENTAL TECHNIQUE11.1. 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 . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . 4 6 5 3 55 5 7 57 60
xii11.7. 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.
CONTENTSPAGE 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 reagentsgases . .
. . . . .179 Inorganic reagentsliquids . . . . . . .186 Inorganic
reagentssolids . . . . . . .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 JOINTS11.54. 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
CONTENTS11.58. 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 IIIPREPARATION AND REACTIONS OF ALIPHATIC COMPOUNDS
PRELIMINARY LABORATORY OPERATIONS111.1. 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 . . . . . 229 229 . 230
.231 . 232
. . . . . . . . recrystallisation .
SATURATED ALIPHATIC HYDROCARBONS111.6. 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
ETHYLENIC HYDROCARBONS (ALKENES)111.10. 111.11. 111.12. Ainylene
Reactions and characterisation of ethylenic hydrocarbons
cz/cZoHexene . 239 .241 243
ACETYLENIC HYDROCARBONS (ALKYNES)111.13. Acetylene . .245
ALIPHATIC ALCOHOLS111.14. 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. 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 . . . . . . . . . . . . . . . . . . . . .
.
247. 249 250 .251 .252 . 253 . 254 . 254 . 255 . 255 . 256 257
258 . 259 . 260
ALKYL HALIDES111.28. 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)
270272 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 PAGE 275 276 277 277 280 281 284 285 285 288 . 289
.
.
.
POLYHALOGEN COMPOUNDS111.43. 111.44. 111.45. 111.46. 111.47.
111.48. Chloroform Bromoform lodoform Methylene bromide Methylene
iodide 1 : 2 : 3-Tribromopropane 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
297.297 299 299 300 300 301 302 303 304 304 .3 0 5 306 307 307
309 310 311 313 314 .315 318 . . . . . . . . . . . . 320 321 . 323
. 324 . 324 .325 .326 327 .327 . 330 335 336 338 340 .341 .348
.
.
.
.
.
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 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
ALIPHATIC KETONES 111.71. 111.72. 111.73. 111.74. 111.75. Methyl
n-hexyl ketone Diethyl ketone cyc/oPentanone Reactions and
characterisation of aliphatic ketones Acetone cyanohydrin . . . .
.
.
.
. .
. .
CONTENTS111.76. 111.77. 111.78. 111.79. n-Heptaldoxime . .
Pinacol a n d pinacolone . Diacetone alcohol Mesityl oxide . . . .
. . . . . . . .
xvPAGE .3 4 8 . 349 351 353
SATURATED ALIPHATIC MONOBASIC ACIDS111.80. 111.81. 111.82.
111.83. 111.84. 111.85. 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 .
354355 356 357 .357 . 358 . 360
ACID CHLORIDES OF ALIPHATIC CARBOXYLIC ACIDS111.86. 111.87.
111.88. Acetyl chloride n-Butyryl chloride Reactions and
characterisation of acid chlorides of aliphatic acids .
367367 368 369
ACID ANHYDRIDES OF ALIPHATIC CARBOXYLIC ACIDS 371111.89. 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 ESTERS111.95. 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
379382 383 384 385 . 385 386 387 . 387 388 389 389 . 390
. .
. .
.
.
ALIPHATIC AMIDES111.107. 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 . . . .
401401 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) . . . .
407407 408 408 409 410
xvi
CONTENTSALIPHATIC 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) . 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.
. . . . . . . . .
. . . . . . .
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 .442 444 . 445
. 446 449
POLYHYDRIC ALCOHOLS, FATS AND SOAPS 111.135. Saponification o f
a fat. Soap . . . . . . 111.136. Reactions and characterisation of
polyhydric alcohols . . CARBOHYDRATES111.137. a- and p-Glucose
penta-acetate . . . . 111.138. Mucic acid 111.139. Reactions a n d
characterisation o f carbohydrates . Photographs o f osazones . . .
. . 111.140. 111.141. 111.142. 111.143. 111.144. 111.145. 111.146.
111.147. 111.148. 111.149. 111.150. . . . .
.451 452 . . 453 t o face 4 5 5 459 460 460 .461 .463 466 466
467 467 468 . 470
UNSATURATED ALIPHATIC COMPOUNDSAllyl 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
. .
.
ETHYL ACETOACETATE111.151. Ethyl acetoacetate 111.152. Ethyl
n-propylacetoacetate and methyl n-butyl ketoiio .
475 477 .481 483 484 485 . 486 .488
DIETHYL MALONATE111.153. 111.154. 111.155. 111.156. Diethyl
malonate Ethyl n-butylmaloiiato n-Caproic acid (from ethyl n-butyl
malonate) . n-Propylmalonic acid . . . . . . . . .
CONTENTS SOME ALIPHATIC DICARBOXYLIC ACIDS Malonicacid Glutaric
acid (from trimethylene dicyanide) . . . Pimelic acid (from benzoyl
piperidine) . . . . Glutaric acid (from cyc\opentanone) . . . .
Adipicacid cw-Dimethylsuccinic acid . . . . . . 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) . RESOLUTION OF A RACEMIC COMPOUND
xviiPAGE
111.157. 111.158. 111.159. 111.160. 111.161. 111.162.
. . . .
489 490 .491 . 492 . 493 494 .495 496 . 497 .4 9 7 498 .499 499
. 500
[11,163. 111.164. 111.165. 111.166. 111.167. 111.168.
. . .
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 IVPREPARATION AND REACTIONS OF AROMATIC COMPOUNDS
AROMATIC HYDROCARBONSIV,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 . . . . . . . . . . . . . . . . . . . . . . .
. .
508.511 .512 .513 .513 . 5 1 5 615 .516 . 6 1 7 . 518
NITRATION OF AROMATIC HYDROCARBONSIV, 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 . . . . . . . . . . . . .
523525 526 .5 2 6 . 527 527 527 . 528 . 531
of aromatic nitro compounds of aliphatic nitro compounds
HALOGENATION OF AROMATIC HYDROCARBONSIV,17. IV,18. 1V,19.
Chlorobenzene Bromobenzene . w-Bromonitrobonzene . . . . . . . . .
. . . . .
633535 .5 3 5 .5 3 7
xviii IV,20. IV,21. IV,22. IV,23. IV,24. IV,25. IV,26. IV,27.
IV,28.
CONTENTS 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 . . . . . . . . . . . . . . . hydro
. . PAGE537 538 538 539 541 541 542 542 542 548
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 . . . . . . . . .
549 550 551 552 552 558 559
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.
Aniline . . . . . . . . p-Phenylethylamine . . . . . .
a-Phenylethylamine . . . . . . a-Naphthylamine . . . . . .
p-Naphthylamine . . . . . . Benzylamine (Gabriel synthesis) . . . .
Pure methylaniline from commercial methylaniline Benzylaniline . .
. . . . . Dimethylaniline . . . . . . 7>-Nitrosodimethylaniline
. . . . . m-Nitroaniline . . . . . . . . . . . . . . . . . . . . .
. . . . .
. 563 . 566 . 567 . 568 . 568 . 569570
. 572 . 572 . 573 . 574576
ACETYLATION OF AROMATIC AMINES IV,45. IV,46. IV,47. IV,48.
IV,49. IV,50. IV,51. Acetanilide . . . Diacetyl-o-toluidine . . 2 :
4 : 6-Tribromoacetanilide jo-Bromoacetanilide . . jo-Bromoaniline .
. jo-Nitroacetanilide . . >-Nitroaniline . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . .
577 578 579 580 580 581 581 582
BENZOYLATION OF AROMATIC AMINES IV,52. IV,53. IV,54. Benzanilide
(Schotten - Baumann reaction) . Benzanilide . . . . . . Hippuric
acid (benzoyl glycine) . . . . . . . . . .
. 583 . 584585
582
SULPHONATION OF AROMATIC AMINES IV,55. IV,56. IV,57. IV.58.
Sulphanilic acid Naphthionic acid Orthanilic acid Metanilic acid .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
.
586 586 587 589
CONTENTS DIAZONIUM SALTSIV159. 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 . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . .
xixPAGE
590. 597 . 598 600 . 602 . 6 0 5 . 606 .607 . 607 . 609 .612 613
614 616 .615 616 .617 .617
. .
. .
.
. .
SOME AZO DYESTUFFSIV,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. . .
620622 623 624 . 625 625 . 626 . 627
. . .
. . .
. . .%
. . .
. . .
INTERMEDIATE PRODUCTS IN THE REDUCTION OF NITRO COMPOUNDSIV,83.
IV,84. IV,85. IV,86. IV,87. IV,88. (S-Phenylhydroxylamine
Nitrosobenzene Azoxybenzene . . . . . . Azobenzene Hydrazobenzene
(sT/w.-diphenylhydrazine) . Benzidine . . . . . .
628629 630 .631 631 .632 633
REDUCTION OF DIAZONIUM COMPOUNDS. ARYL HYDRAZINES 635IV,89.
IV,90. IV.91. Phenylhydrazine p-Nitrophenylliydrazine 2 :
4-Dinitrophenylhydrazine 636 637 638
AROMATIC DIAMINESIV,92. IV,93. o-Phenylenediamine
7/i-Phenylenediamine . . . . . . .
640640 .641
MISCELLANEOUS COMPOUNDS DERIVED FROM PRIMARY AMINESIV,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 . .
. . . . . . . . .6 4 2 . 642 . 643 . 644 645 . 647 . 648
xx
CONTENTSPHENOLS PAGE 664 667 668 669 669 671 . 671 . 676 .6 7 7
678 678 679 679 680 . 681
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 ALDEHYDESIV,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
. . . . . . . . . . . .
689693 .6 9 4 .6 9 5 697 698 . 700 701 703
CONDENSATION REACTIONS OF AROMATIC ALDEHYDESIV, 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 . .
706.711 712 714 714 715 716 717 .718 718 . 719 719 .720 .
720
AROMATIC KETONESIV, 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 . . . . . . . . . . . . . . . .
725729 732 .732 733 .734 .7 3 4 .736 737 .739 .7 4 0 740 .741
.741
CONTENTS QUINONES IV,149. IV,150. IV,151. IV 7 ,152.
7>-Benzoquinone (" quinorie " ) . . 1 : 2-Naphthoquinone
Quinhydrone Reactions a n d characterisation o f quinones . . . . .
. .
xxi PAGE 745 . 745 746 747 . 747 751 .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 . 785 791 791 792
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 AROMATIC ESTERS . . ,
. . . . . . . . . .
. . . . . . . . . .
acids .
IV,176. IV,177. IV,178. IV, 179. IV,180. IV,181. IV,182.
IV,183.
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
AROMATIC ACID ANHYDRIDES 794 IV,186. p-Chlorobenzoic anhydride .
. . . . . .7 9 4 IV, 187. Reactions and characterisation of acid
chlorides of aromatic acids . 795 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 AROMATIC ACID AMIDES
xxii
CONTENTS AROMATIC NITRILES PAGE 803 803 804 . 805 807 807 808 .
808 810 811812 812 813 815 816 817
IV,193. Benzonitrile IV, 194. Veratronitrile IV, 195. Reactions
and characterisation of aromatic nitriles
.
.
SOME AROMATIC PEROXIDES AND PER-ACIDS IV, 196. IV, 197. IV,198.
IV,199. Benzoyl peroxide p-Nitrobenzoyl peroxide Perbenzoic acid
(benzoyl hydrogen peroxide) Monoperphthalic acid AROMATIC ALCOHOLS
IV,200. IV,201. IV,202. IV,203. IV,204. IV,205. p-Tolyl carbinol
(p-methyl benzyl alcohol) . Benzhydrol (diphenylcarbinol) . . . .
Triphenylcarbinol Triphenylchloromethane . . . . . p-Phenylethyl
alcohol Reactions and characterisation of aromatic alcohols
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 VSOME 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) . . 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 REACTIONSVI, 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
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 COMPOUNDSVIII,1.
Congo reel 979
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)
980 981 982 . 983 . 984 . 985 .987 .987 989 991 991 992 993
CHAPTER IX SOME PHYSIOLOGICALLY ACTIVE COMPOUNDSIX,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 . . . . . . .
. . . . . . . . . 996 996 998 .9 9 9 . 1000 1001
CONTENTS1X,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 . . . . . .
xxv PAGE. 1002 . 1003 . 1005 . 1007 1009 . 1010 . 1011 1012
CHAPTER X SYNTHETIC POLYMERSX,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 ANALYSISXI,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 TECHNIQUEXII,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 CHEMISTRYA,L A,2. A,3. A,4. A,5.
A,6. A,7. A,8. A,9. A,10. INDEX 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 1165
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 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
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
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.
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
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
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
3]
THEORY OF GENERAL TECHNIQUE
observed boiling point t, and p is the barometric pressure. For
water, alcohols, acids and other associated liquids, it is better
to use the expression : A* = 0-0010 (760 p)(t + 273). 1,3.
Superheating and bumping. If a liquid is heated in a flask by means
of a Bunsen burner and wire gauze placed below it, the formation of
bubbles of vapour at the lower surface of the liquid in contact
with the heated glass is facilitated by the presence of air
dissolved in the liquid or adhering as a film to the glass and by
roughness on the surface of the4-0
3-0
CL o20
I = Ether \\=Acetone1-0 _lll= Water
IV- Bromobenzene
20
30 1000T
4-0
Fig. /, 2, 1.
glass. If a minute bubble of air is formed (this will be at
atmospheric pressure), it will serve as a nucleus for a larger
bubble of vapour. At the boiling point the liquid (at 760 mm.
vapour pressure itself) will deliver vapour in relatively large
quantity to the air bubble. With the heat supply at hand, the total
pressure inside the bubble soon rises above that of the atmosphere
and is sufficient to overcome the pressure due to the column of
liquid; a vapour bubble is then expelled. Hence, if a source of
minute air bubbles or other nuclei is available in the liquid,
boiling will proceed quietly. If, however, the liquid is largely
free from air and if the walls of the flask are clean and very
smooth, bubbles are formed with greater difficulty and the
temperature of the liquid may rise appreciably above the boiling
point; it is then said to be superheated. When a
4
PRACTICAL ORGANIC CHEMISTRY
[I,
bubble does eventually form, the vapour pressure corresponding
to the temperature of the liquid far exceeds the sum of the
pressures of the atmosphere and of the column of liquid, hence
vapour is evolved, the bubble increases in size rapidly and at the
same time the temperature of the liquid falls slightly. These
experimental conditions lead to irregular ebullition and the liquid
is said to bump. Various methods are available for preventing, or
at least considerably reducing, bumping in a liquid. An obvious
method is to surround the flask containing the liquid by a bath
charged with a suitable fluid, the temperature of which is not
allowed to rise more than 20 above the boiling point of the liquid.
Bubbles of vapour may now rise from points around the edge of the
liquid and not only from the bottom of the flask. Furthermore, the
danger of superheating is considerably reduced. The procedure most
frequently employed to prevent bumping of a liquid during
distillation under atmospheric pressure is to add a few fragments
of unglazed porous porcelain (often termed " porous pot," " boiling
stones " or " boiling chips "the term " porous pot " will be used
frequently in this book).* These emit small quantities of air and
promote regular ebullition. It must be emphasised that the " porous
pot " is added to the cold liquid before distillation is commenced.
Under no circumstances should " porous pot " be dropped into a
liquid which has already been heated to boiling : the sudden
evolution of vapour may result in spray and sometimes of a large
proportion of the liquid being ejected from the mouth of the flask.
If the distillation has been interrupted, it is recommended that
two or three small fragments of fresh " porous pot" be added before
the heating is resumed ; the " porous pot " initially added, from
which the air has been partially removed by heating, will probably
be largely ineffective owing to their absorption of the liquid on
cooling. A useful device to prevent bumping of liquids during
distillation consists of a glass tube, 2-3 mm. in diameter, bent in
a U-form with one arm somewhat shorter than the other ; it should
be long enough to extend from the bottom of the flask for a short
distance into the neck in order that it should remain in an upright
position (Fig. /, 3, 1, a). If for any reason a shorter U-tube is
desired, a glass rod may be sealed on as in Fig. 7,3, 1,6. The
short arm of the U-tube should be just above the level of the
liquid in the flask, whilst the long arm should rest on the bottom
of the flask just above the source Fig. /, 3, I. f teat. With a
large flask it is advantageous to employ two or three U-tubes, the
short arm of one should be just above the fluid level at the start
of the distillation ; the short arms of the other U-tubes should be
of different lengths and below the initial level of the liquid.*
The action of this and other anti-bumping devices (e.g.t minute
carborundum chips) is dependent upon the fact that the
transformation of a superheated liquid into the vapour will take
place immediately if a vapour phase (e.gr., any inert gas) is
introduced. The effect may be compared with that produced by the
introduction of a small quantity of a solid phase into a
supercooled liquid, e.g., of ice into supercooled water.
4]
THEORY OF GENERAL TECHNIQUE
5
Other aids for promoting regular boiling include the addition of
the following :fragments of pumice stone or of carborundum ; small
strips of Teflon (a tetrafluoroethylene polymer) tape, ca. " wide,
or of shredded Teflon (the strip may be washed with an organic
solvent, dried and reused) ; small pieces of platinum wire (use is
made of the well-known property of platinum in absorbing large
quantities of gases) ; sufficient glass wool to fill the flask and
to rise 4-5 mm. above the surface of the liquid ; long capillary
tubes sealed at a point about 0 5 mm. from the end (the short
capillary end is immersed in the liquid, thus filling the small
cavity with air, which is evolved in fine bubbles when the liquid
is heated). The boiling point of a pure liquid, if properly
determined, has a definite and constant value at constant pressure,
say, that of the atmosphere. The boiling point of an impure liquid
will depend to a large extent on the physical nature of the
impurities. If all the impurities are non-volatile, the liquid will
have a constant boiling point and the impurities will remain behind
when the liquid has been distilled. If, however, the impurities are
themselves volatile, the boiling point may rise gradually as the
liquid distils or it may remain constant at a particular stage of
the distillation due to the formation of a constant boiling point
mixture of two or more substances. The separation of liquids by
distillation forms the subject of the next Section. 1,4. Fractional
distillation. The aim of distillation is the separation of a
volatile liquid from a non-volatile substance or, more usually, the
separation of two or more liquids of different boiling point. The
latter is usually termed fractional distillation. The theoretical
treatment of fractional distillation requires a knowledge of the
relation between the boiling points, or vapour pressures, of
mixtures of the substances and their composition ; if these curves
are known, it is possible to predict whether the separation is
difficult or easy or, indeed, whether it will be possible. At the
outset it will be profitable to deal with an ideal solution
possessing the following properties : (i) there is no heat effect
when the components are mixed ; (ii) there is no change in volume
when the solution is formed from its components ; (iii) the vapour
pressure of each component is equal to the vapour pressure of the
pure substances multiplied by its mol fraction * in the solution.
The last-named property is merely an expression of Raoult's law,
viz., the vapour pressure of a substance is proportional to the
number of mols of the substance present in unit volume of the
solution, applied to liquid-liquid systems. Thus we may write :PA =
K*A
(1),
where pA is the vapour pressure of the substance and XA is its
mol fraction in the solution. If XA = 1, i.e., we are dealing with
the pure substance A, then pA = K = pA', the vapour pressure of the
pure substance at the given temperature. Substituting this value in
equation (1), we have :PA = PA' ZA
( 2 )
i.e., the vapour pressure of a component of a solution at a
given temperature is equal to the vapour pressure of the pure
substance multiplied by its mol fraction in the solution. This is
another form of Raoult's law.* The mol fraction of any constituent
in a mixture is defined as the number of mols, or gram molecules,
of that constituent divided by the total number of mols, or gram
molecules, in the mixture.
6
PRACTICAL ORGANIC CHEMISTRY
[I,
Let us consider a mixture forming an ideal solution, that is, an
ideal liquid pair. Applying Raoult's law to the two volatile
components A and B, we have :PA = PA XA and pa = pB' x&
(3).
The total pressure p will be :P = PA + PB = P ZA + P* *B.
The vapour pressures are proportional to the mol fractions in
the vapour phase, hence the composition of this phase will be given
by :*/=-PA + P*
and
*B. = -J--
PA + PB
The relative concentrations of either constituent, say B, in the
vapour and liquid phases will be :xj_XB=
pB
^ PB_'
PA+PB' PB
__!_
___
(4).
If p/ = pB', xB'/xB is unity, since in the liquid phase XA + %*
= ! If pB' > pA', the concentration of B will be greater in the
vapour phase, and if pB' < pA', it will be less. This may,
perhaps, be made clear with the aid of an example. Let us assume
that the two components A and B have vapour pressures of 60 and 100
mm. of mercury respectively, and that the mol fraction of A is 0-25
and of B is 0-75. Then for the solution : pA = 0-25 x 60 = 15 mm.
(Hg) and pB = 0-75 x 100 = 75 mm. (Hg). The total pressure will be
: p = PA + PB = 90 mm. (Hg). The composition of the vapour phase
will be : x: = 15/90 = 0 - 167 and xj = 75/90 = 0 - 833. Thus a
solution containing mol fractions of 025 and 0-75 of A and B
respectively is in equilibrium with a vapour containing 16-7 and
83-3 mol per cent, of A and B respectively. The component B with
the higher vapour pressure is relatively more concentrated in the
vapour phase than in the liquid phase. If the compositions of the
vapour phase for various mixtures of the same two components are
calculated and plotted against the vapour pressures, a diagram
having the general features shown in Fig. /, 4, I is obtained. The
abscissae represent the composition of both the liquid and the
vapour phases, and the ordinates the total vapour pressure of the
liquid. The curve labelled vapour gives the composition of the
vapour in equilibrium with the solution having the vapour pressure
corresponding to the ordinate. Thus the liquid with composition l
and vapour pressure p represented by the point m is in equilibrium
with vapour of composition //. Since the mixture is an ideal
solution of the two liquids, the vapour pressures are additive and
the liquid vapour pressure - composition curve AmB is a straight
line. The composition of the vapour in equili-
THEORY OF GENERAL TECHNIQUEbrium with the various mixtures is
given by Am'B, falling below the liquid vapour pressure -
composition line. Figure /, 4, I is therefore the vapour pressure
diagram for an ideal liquid pair. The diagram shows clearly that
the vapour in equilibrium with the ideal solution of two liquids is
richer in the more volatile component than is the solution ; it
follows, therefore, that the two components could be separated by
fractional distillation. Only a limited number of examples are
known of mixtures which obey Raoult's law over the whole range of
concentration and give straight line plots of the vapour pressure
(ordinates) against the composition of the liquid expressed in mol
fractions (abscissae). These include : w-hexane and n-heptane at
30; ethyl bromide and ethyl iodide at 30; n-butyl chloride and
n-butyl bromide at 50 ; and ethylene dibromide and propylene
dibromide at 85. In most cases, however, liquid pairs deviate from
Raoult's law. The deviations may be either positive or negative,
i.e., the vapour pressure may be either greater or less than that
calculated. If both components exhibit positive deviations (e.g.,
carbon disulphide and acetone at 35), the total vapour pressure
curve will be greater than that calculated and the curve passes
through a maximum. If the two components show negative deviations
(e.g., acetone and chloroform at 35), Mot fractionofBthe total
vapour pressure curve ~Mol. fraction of A will be less than that
calculated Fig. /, 1. and the curve will pass through a minimum. It
can be shown that when the vapour pressure is a maximum or a
minimum, the composition of the vapour is the same as that of the
liquid with which it is in equilibrium. The normal boiling point of
a liquid is the temperature at which the vapour pressure of the
liquid is equal to the pressure of the atmosphere. Hence for the
study of fractional distillation it is better to construct a
diagram in which the boiling points are ordinates and the
compositions are abscissae at constant (i.e., atmospheric)
pressure. In the vapour pressure - composition curves the vapour
pressure is plotted against the composition at constant
temperature, whereas in the boiling pointcomposition curves the
boiling point is plotted against the composition at constant
pressure. The two curves are similar in type except that they are
inverted (see Figs./, 4, 2 and 7,4,3 below). In the boiling
point-composition diagram two curves are obtained, one giving the
composition of the liquid and the other that of the vapour with
which it is in equilibrium at the boiling point. The vapour phase
is relatively
PRACTICAL ORGANIC CHEMISTRY
[I.
richer in the component which results in a lowering of the
boiling point when added to the mixture, or, alternatively, the
liquid phase is richer in the component which raises the boiling
point. Three classes of curves will be considered : those in which
(1) the boiling point rises steadily with change of composition
from the more volatile to the less volatile component, (2) the
boiling point reaches a minimum, and (3) the boiling point reaches
a maximum. (1) The boiling point increases regularly. The boiling
point-composition diagram for such a system is shown in Fig. /, 4,
2 (the complementary vapour pressure - composition diagram is
depicted in Fig. /, 4, 3 for purposes of comparison only). Let us
consider the behaviour of such a liquid pair upon distillation. If
a solution of composition Z^ is heated, the vapour pressure will
rise until at the point Zx it is equal to the pressure of the
atmosphere, and boiling commences at temperature t. The com-
Liquid
/ Vapour
IOO%A
V2
L,
IOO;;B
i oo 7. A Composition
IOO;:B
Composition
Fig. /, 4, 2.
Fig. /, 4, 3.
position of the vapour first distilling is Vl ; it is richer in
A, the lower boiling point component, than was the original
solution. As the boiling proceeds, the residue becomes increasingly
richer in B, the higher boiling point component; consequently the
boiling point will rise, say, to t2 and the composition of the
residue will gradually change to L2, whilst that of the distillate
(vapour) will change from Fx to F2. Thus from a solution of initial
concentration/^, a distillate is obtained of composition
approximating to (V l + F2)/2 and a residue of composition L2. The
distillation has thus effected a partial separation of A and B, and
it is clear that by repeated distillation an almost complete
separation of the two components can be made. For this purpose,
each fraction collected between suitable temperature limits is
redistilled ; with each fractionation the separation of the two
components is improved. It is evident that the greater the slope of
the boiling point curve, the greater is the difference in
composition between the liquid and the vapour ; hence the greater
the difference in the boiling points of the two liquids forming the
mixture, the more easily can they be separated by distillation. In
practice, it is usual to employ a fractionating column to reduce
the
4]
THEORY OF GENERAL TECHNIQUE
9
number of distillations necessary for reasonably complete
separation of the two liquids. A fractionating column is designed
to provide a continuous series of partial condensations of the
vapour and partial vaporisations of the condensate and its effect
is, indeed, similar to a number of separate distillations. The
effect of partial condensation will be evident from Fig. /, 4, 2.
If the temperature of the vapour is lowered, it will partly
condense giving a liquid richer in B and leaving the vapour richer
in A. The vapour passing up the column will accordingly contain
more of A than did the vapour which left the boiling liquid.
Similarly the liquid returning to the flask will contain relatively
more of the less volatile component B. A fractionating column
consists essentially of a long vertical tube through which the
vapour passes upward and is partially condensed; the condensate
flows down the column and is returned eventually to the flask.
Inside the column the returning liquid is brought into intimate
contact with the ascending vapour and a heat interchange occurs
whereby the vapour is enriched with the more volatile component A
at the expense of the liquid in an attempt to reach equilibrium.
The conditions necessary for a good separation are :(i) there
should be a comparatively large amount of liquid continually
returning through the column ; (ii) thorough mixing of liquid and
vapour ; and (iii) a large active surface of contact between liquid
and vapour. Excessive cooling should be avoided ; this difficulty
is particularly apparent with liquids of high boiling point and may
be overcome by suitably insulating or lagging the outer surface of
the column or, if possible, by surrounding it with a vacuum jacket
or an electrically heated jacket. Various types of laboratory
fractionating columns are described in Sections 11,15-11,18. (2)
Minimum boiling point. Typical boiling point - composition curves
for systems of this kind are shown in Fig. /, 4, 4. If a solution
of composition Ll is heated, the vapour pressure will rise until at
the point ^ it is equal to the pressure of the atmosphere and
boiling commences at ^. The composition of the vapour first
distilling is Vv As the boiling proceeds the temperature rises from
^ to 22, and during this period distillates with compositions
ranging from Vl to V2 will be obtained. If the distillate be
redistilled, the vapour approaches the composition of the minimum
boiling point system, as can be seen from the figure. Hence
fractional distillation will result in a distillate of composition
Lm, although the final residue will approach A. Similarly, a
solution of composition LI when distilled commences to boil at Z/,
i.e., at a temperature // the vapour (and therefore the distillate)
will have the composition F/. As the distillation continues the
composition of the vapour changes to V2' and the liquid to L2'.
Fractional distillation will, in this case, yield a solution of
composition L^, and the residue will approach B. The liquid mixture
can then be separated only into the component present in excess
(either A or B) and the mixture of minimum boiling point. The
liquid represented by LM will distil over completely without change
of composition since at the boiling point the vapour has the same
composition as the liquid. Such systems which distil unchanged are
called azeotropic mixtures (Greek : to boil unchanged). The
composition and boiling point of such constant boiling point
mixtures vary with the pressure and consequently they are not
chemical compounds.
10
PRACTICAL ORGANIC CHEMISTRY
[I.
V,IOOZA CompositionFig.
V,'
V,1
L,1 U1
ioo;.B
/, 4, 4.
Examples of azeotropic mixtures of minimum boiling point are
collected in Table /, 4, A.TABLE I, 4, A. AZEOTROPIC MIXTURES OF
MINIMUM BOILING POINT
COMPONENT A
COMPONENT B
B.P. OP % OF A j AZEOTROPIC (BY wr.) IN I MIXTURE MIXTURE |78-15
80-4 87-7 79-9 92-6 39-0 63-0 54-0 71-8 99-4 100-0 77-5 68-2 76-7
53-5 59-4 74-8 41-8 105-44-4
Water, 100-0 Water, 100-0 Water, 100-0 Water, 100-0 Water, 100-0
Methyl alcohol, 64-7 Ethyl alcohol, 78-3 Methyl alcohol, 64-7 Ethyl
alcohol, 78-3 Water, 100-0 Water, 100-0 Benzene, 80-2 Ethyl
alcohol, 78-3 Ethyl alcohol, 78-3 Methyl alcohol, 64-7 Ethyl
alcohol, 78-3 Ethyl alcohol, 78-3 Methyl alcohol, 64-7 Acetic acid,
118-5
Ethyl alcohol, 78-3 tsoPropyl alcohol, 82-4 n-Propyl alcohol, 97
2 terJ.-Butyl alcohol, 82-6 Pyridine, 115-5 Methyl iodide, 44-5
Ethyl iodide, 72-3 Methyl acetate, 57 0 Ethyl acetate, 77-2 Butyric
acid, 163-5 Propionic acid, 140-7 cycZoHexane, 80-8 Benzene, 80-2
Toluene, 110-6 Chloroform, 61-2 Chloroform, 61-2 Methyl ethyl
ketone, 79-6 Methylal, 42 2 Toluene, 110-6
12-1 28-3 11-8 43-07-2 13 19 31
18-4 17-755
32-468
12-5 18-2
7-0 40 28 i
(3) Maximum boiling point. A typical boiling point - composition
diagram is shown in Fig. /, 4, 6. By reasoning analogous to that
given
THEORY OF GENERAL TECHNIQUE
11
under (2), it is evident that fractional distillation of a
liquid mixture of composition L{ will yield ultimately a specimen
of almost pure A and a residue of composition LMa, which will
eventually distil unchanged. Similarly, a liquid mixture of
composition L/ will give ultimately pure B and a residue LMa, which
will itself distil unchanged. Thus distillation will afford
ultimately the component present in excess of the constant boiling
point mixture and the constant boiling point mixture itself.
V,
V2
L, L2 LMa Composition Fig. /, 4t 5.
V/ I007.B
Examples of azeotropic mixtures of maximum boiling point are
tabulated below ; these are not as numerous as those of minimum
boiling point.TABLE I, 4, B. AZEOTBOPIO MIXTURES or MAXIMUM BOUJNO
POINTB.P.OF
ONENT A
COMPONENT B
AZEOTBOPIO MIXTURE 107-1 120-0 108-6 126 127 120-5 338 203 64-7
139-7 64-8 186-2
% OF B (BY WT.) IN MIXTURE
00-0 00-0 00-0 00-0 00-0 00-0 00-0 00-0 56-4 ,id, 118-5 rm, 61-2
181-5
Formic acid, 100-8 Hydrofluoric acid, 19-4 Hydrochloric acid,
84-0 Hydrobromic acid, 73 Hydriodic acid, 35 Nitric acid, 86 0
Sulphuric acid, m.p. 10-5 Perchloric acid, 110-0 Chloroform, 61-2
Pyridine, 115-5 Methyl acetate, 57 0 Aniline, 184-4
77-537
20-22 47-6 57-068
i ! ; ;
98-3 71-680
6523 58
12
PRACTICAL ORGANIC CHEMISTRY
[I,
1,5. The breaking up of azeotropic mixtures. The behaviour of
constant boiling point mixtures simulates that of a pure compound,
because the composition of the liquid phase is identical with that
of the vapour phase. The composition, however, depends upon the
pressure at which the distillation is conducted and also rarely
corresponds to stoichiometric proportions. The methods adopted in
practice will of necessity depend uppn the nature of the components
of the binary azeotropic mixture, and include : (1) Distillation
with a third substance which alters the vapour pressure ratios in
the azeotrope. This method is of particular value in industry for
the production of absolute ethyl alcohol from the azeotropic
mixture containing 95-6 per cent, of alcohol or from aqueous
alcohol. Upon the addition of benzene and distillation through a
suitable fractionating apparatus, a ternary azeotropic mixture of
water, alcohol and benzene of minimum boiling point, 64-85, and
containing 7 - 4 per cent, of water, 18'5 per cent, of alcohol and
74-1 per cent, of benzene passes over first, followed by a second
azeotropic mixture of benzene and alcohol (b.p. 68-25, containing
32-4 per cent, of benzene), and finally absolute ethyl alcohol. By
carrying out the fractional distillation under pressure, the water
content of the ternary mixture is increased. (2) Chemical methods
may be employed if the reagent attacks only one of the components.
Thus quicklime may be employed for the removal of water in the
preparation of absolute ethyl alcohol. Also aromatic and
unsaturated hydrocarbons may be removed from mixtures with
saturated hydrocarbons by sulphonation. (3) Preferential adsorption
of one of the components may be used for the same purpose. Charcoal
or silica gel may be employed to adsorb one of the constituents of
an azeotrope in preference to the other. If the adsorbate is
readily recoverable, the process will have practical applications.
(4) Fractional extraction may sometimes find application, since the
components distribute themselves in a different proportion in the
solvent (compare Section 11,44). (6) Fractional crystallisation is
occasionally employed. The mixture is dissolved in a suitable
solvent, the whole frozen, and then aUowed to melt slowly in a
centrifuge in order that the successive fractions may be removed as
they are formed. The various melts are then fractionally distilled.
If necessary, the fractional crystallisation may be repeated. 1,6.
Steam Distillation. Distillation of a Pair of Immiscible Liquids.
Steam distillation is a method for the isolation and purification
of substances. It is applicable to liquids which are usually
regarded as completely immiscible or to liquids which are miscible
to only a very limited extent. In the following discussion it will
be assumed that the liquids are completely immiscible. The
saturated vapours of such completely immiscible liquids follow
Dalton's law of partial pressures (1801), which may be stated :
when two or more gases or vapours which do not react chemically
with one another are mixed at constant temperature each gas exerts
the same pressure as if it alone were present and that
6]
THEORY OF GENERAL TECHNIQUE
13
the sum of these pressures is equal to the total pressure
exerted by the system. This may be expressed :P = Pl+P2+ +Pn
where P is the total pressure and pl9 p2, etc., are the partial
pressures of the components. If a mixture of two immiscible liquids
be distilled, the boiling point will be the temperature at which
the sum of the vapour pressures is equal to that of the atmosphere.
This temperature will be lower than the boiling point of the more
volatile component. Since one of the liquids is water, steam
distillation at atmospheric pressure will result in the separation
of the higher boiling component at a temperature below 100a
considerable advantage if the compound decomposes at or near its
own individual boiling point; the process would also be useful for
separation from non-volatile or from undesirable (e.g., tarry)
substances. When a mixture of immiscible liquids is distilled, the
boiling point of the mixture remains constant until one of the
components has been almost completely removed (since the total
vapour pressure is independent of the relative amounts of the two
liquids) : the boiling point then rises to that of the liquid
remaining in the flask. The vapour passing over from such a mixture
contains all the components in proportion by volume to the relative
vapour pressure of each. The composition of the vapour can easily
be calculated as follows : Assuming that the gas laws are
applicable, it follows that the number of molecules of each
component in the vapour w^ill be proportional to its partial
pressure, i.e., to the vapour pressure of the pure liquid at that
temperature. If pA and pB are the vapour pressures of the two
liquids A and B at the boiling point of the mixture, then the total
pressure P is given by :r=P* + PB
(1),
and the composition of the vapour by :
Jp* "A/WB = PA!
(2),
where nA and raB are the number of mols of the two substances in
a given volume of the vapour phase. But nA = wA/MA and nB = wB/MB,
where w is the weight of substance in a given volume of the vapour,
and M is the molecular weight. Hence :WB MBnB MBpB
The relative weights of the two components of the vapour phase
will be identical with the relative weights in the distillate,
i.e., the weights of the two liquids collecting in the receiver are
directly proportional to their vapour pressures and their molecular
weights. Equation (3) indicates the great value of steam
distillation, since the smaller the product M^j*^ the laiger is the
value of WB. Water has a small molecular weight and a comparatively
moderate vapour pressure, so that its value of 3/ApA is low. This
permits substances of high molecular weight and of low vapour
pressure to be separated economically on the technical scale. The
following figures are given by S. Young (1922).2*
14
PRACTICAL ORGANIC CHEMISTRYSUBSTANCE MOLECULAR WT. MB150 154
148
[I.PER CENT. IN DISTILLATE9-7 5-6 7-1
B.P.
pB AT
100
Carvone Geraniol Anethole Eugenol a-Santalol .
164 228
j
230 230 235 250 301
9 mm. 5 mm. 8 mm. 2 mm. -Toluidine, m.p. 43 Picric acid, m.p.
122-5 p-Toluidine, m.p. 43 COMPOUND DAB,m.p. 28-8 AB, m.p. 28-5AB,
m.p. 83-1
EuTEcncs16-0 24-0 8-0 19-9 36 80-6 50- 2 30-3 (66-5 %A). (32% 4)
(76% 4), (31 %^4) (94 % A), (42% A) (60% A), (19 %A)
AB9 m.p. 63-7
1,15. System in which the two components form a compound with an
incongruent melting point. In this system the compound formed
CompositionFig.
1, U, 1.
32
PRACTICAL ORGANIC CHEMISTRY
[I,
is so unstable that it decomposes completely at a temperature
below its melting point, so that the solid cannot be in equilibrium
with a liquid of the same composition as itselfin other words, it
has no true melting point. Such a system is exemplified by benzene
and picric acid : the equilibrium diagram is shown in Fig. /, 15, 1
(for clarity, the illustration is not drawn to scale). The point A
is the melting point of benzene, B that of picric acid, and C that
of the eutectic composed of solid benzene and the addition compound
(represented by the symbol AxBy). The curve CE is the equilibrium
curve for the compound AxByin the example under consideration x = 1
and y = 1with the submerged maximum at D. The point D is not
realised in practice because the compound decomposes completely at
E into solid picric acid and liquid benzene. The point E is spoken
of as the incongruent melting point of the compound (since the
composition of the liquid is not the same as that of the original
compound) or as the transition point. The curve EB represents the
equilibrium between solid B and the liquid. This system is rarely
encountered among compounds, but other examples are acetamide -
salicylic acid and dimethylpyrone - acetic acid ; it is, however,
comparatively common in alloy systems (e.g., gold - antimony,
AuSb2). 1,16. System in which the two components form a continuous
series of solid solutions. In all the preceding examples the
individual components (A or B or AxBy) form separate crystals when
solidifying from the melt. There are, however, a number of examples
of the separation of a homogeneous solid solution of A and B (or A
and AXBU, etc.). Before studying the equilibrium diagrams of these
systems, the significance of the term solid solution must be made
clear. A solid may dissolve completely in another solid to form a
solid solution in a manner analogous to the dissolution of one
liquid in another to yield a liquid solution. The solid thus
obtained is perfectly homogeneous and has been called mixed
crystals or isomorphous mixtures ; these two terms may suggest
heterogeneity and it is therefore better to employ the expression
solid solution, proposed by van't Hoff in 1890. The phenomenon is
different from the process of ordinary solution in a liquid since a
liquid has no space lattice of its own. The formation of a solid
solution involves the structural dissolution of one solid by
another crystalline solid : this process entails, particularly for
inorganic compounds, the spatial marshalling of the one in the
other with respect to a definite space lattice, and the resulting
solid solution therefore behaves as a single entity. The physical
properties of solid solutions are continuous functions of their
percentage composition. The conditions which must generally be
satisfied in the case of pairs of non-polar organic compounds are :
(a) their chemical constitution must be analogous, (b) their
molecular volumes must be approximately equal, and (c) their
crystal structures must be similar. The general case of two
compounds forming a continuous series of solid solutions may now be
considered. The components are completely miscible in the solid
state and also in the liquid state. Three different types of curves
are known. The most important is that in which the freezing points
(or melting points) of all mixtures lie between the freezing points
(or melting points) of the pure components. The equilibrium diagram
is shown in Fig./, 16, 1. The liquidus curve portrays the
composition of the liquid phase in equilibrium with solid, the
composition of
16]
THEORY OF GENERAL TECHNIQUE
33
which is given by the solidus curve. The composition of the
solid phase changes continuously with that of the liquid from
\vhich it separates. It is found experimentally, and can also be
deduced theoretically, that at any temperature the concentration of
that component by the addition
Liquid Solution
ISolid Solution
JOO'/oA 0/,B
Composition Fig. /, 16, 1.
0%A I007.B
of which the freezing point is depressed is greater in the
liquid than in the solid phase. It is evident from the figure that
upon cooling a fused mixture of two substances capable of forming
solid solutions, the temperature of solidification (freezing point)
will not remain constant during the separation of the solid, nor
will the temperature of liquefaction (melting point) of the solid
solution be constant. Thus, for example, if a liquid solution of
composition a is allowed to cool very slowly (so as to ensure
equilibrium conditions as far as possible), a solid of compo- 5
sition/will separa