The Practical Methods Of Organic Chemistry

372 Pages·1909·4.097 MB·English

by  Gattermann L.

THE PRACTICAL METHODS
OF
ORGANIC CHEMISTRY
LUDWIG GATTERMANN, PH.D.
PROFESSOR IN THE UNIVERSITY OF FREIBURG
WITH NUMEROUS ILLUSTRATIONS
TRANSLATED BY
WILLIAM B. SCHOBER, PH.D.
ASSISTANT PROFESSOR OF ORGANIC CHEMISTRY IN LEHIGH UNIVERSITY
THE SECOND AMERICAN -FROM. THEFOURTH GERMAN
EDITION
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THE MACMILLAN COMPANY
LONDON: MACMILLAN & CO., LTD.
1909
All rights reserved
COPYRIGHT, 1896, 1901,
Bv THE MACMILLAN COMPANY.
First printed September, 1901. Reprinted
September, 1903; July, 1905; January, 1906;
October, 1907; February, 1909.
J. S. CmMng & Co. — Berwick k Smith Co.
Tym czarownym rekom, ktorych
dotkniecie pokoj pozynosL
TRANSLATOR'S PREFACE
THE success of Professor Gattermann's book in the original
has warranted its reproduction in English. The translation is
intended for those students of chemistry who have not yet
become sufficiently familiar with scientific German to be able
to read it accurately without constant reference to a dictionary.
To such students this translation is offered, in the hope that it
will increase their interest in the science without causing a cor-
responding decrease in their efforts to acquire a knowledge of
German, which is indispensable to every well-trained chemist.
My grateful acknowledgments are due to my colleague, Dr.
H. M. Ullmann, for many valuable suggestions, and to Professor
Gattermann for his courtesy in pointing out several inaccuracies
in the German edition.
WILLIAM B. SCHOBER.
SOUTH BETHLEHEM, PENNSYLVANIA,
April, 1896.
PREFACE
THE present book has resulted primarily from the private needs
of the author. If one is obliged to initiate a large number of
students at the same time into organic laboratory work, it is
frequently impossible, even with the best intentions, to direct the
attention of each individual to the innumerable details of labo-
ratory methods. In order that students, even in the absence of
the instructor, can gain the assistance necessary for the carrying
out of the common operations, a General Part, dealing with
crystallisation, distillation, drying, analytical operations, etc., is
given before the special directions for Preparations. In the
composition of this General Part, it has been considered of
more value to describe the most important operations in such
a way that the beginner may be able to carry out the directions
independently, rather than to give as fully as possible the numer-
ous modifications of individual operations. In the Special Part,
to each preparation are added general observations, which relate
to the character and general significance of the reaction carried
out in practice; and the result follows, that the student during
the period given to laboratory work, becomes familiar with the
most varied theoretical knowledge, which, acquired under these
conditions adheres more firmly, as is well known, than if that
knowledge were obtained exclusively from a purely theoretical
Viu PREFACE
book. And so the author hopes that his book, along with the
excellent " Introductions " of E. Fischer and Levy, may here ar.d
there win some friends.
For the assistance given by his colleagues, in pointing out
deficiencies of his work, the author will always be grateful.
GATTERMANN.
HEIDELBERG, August, 1S94.
PREFACE TO THE SECOND AMERICAN
EDITION
IN the preparation of this new edition advantage has been
taken of the opportunity offered to correct a number of errors
in the first edition, and to make the text a reproduction of
the fourth German edition of Professor Gattermann's book. In
many cases the laboratory directions have been improved, a
number of new illustrations have been added, and the Special
Part now includes methods for the preparation of glycol, di-
methylcyclohexenone, s-xylenol, phenylhydroxylamine, nitroso-
benzene, p-tolyl aldehyde (Gattermann-Koch synthesis), salicylic
aldehyde (Reimer and Tiemann's oxyaldehyde synthesis), cuprous
chloride, the decomposition of inactive mandelic acid into its
active constituents, and a zinc dust determination. The prepara-
tions of acetylene and acetylene tetrabromide have been omitted.
WILLIAM B. SCHOBER.
SOUTH BETHLEHEM, PENNSYLVANIA,
May, 1901.
CONTENTS
GENERAL PART
Crystallisation . PAGE
m
Sublimation
14
Distillation .
10
Distillation with Steam
Separation of Liquid Mixtures. Separation by Extraction. Salting Out 41
Decolourising. Removal of Tarry Matter - . . . ,,
Drying . . . 47
Filtration ^ # „
Heating under Pressure . . . . .. . m -g
Melting-point 66
Drying and Cleaning of Vessels yO
ORGANIC ANALYTICAL METHODS
Detection of Carbon, Hydrogen, Nitrogen, Sulphur, and the Halogens . 72
Quantitative Determination of the Halogens. Carius' Method . . 75
Quantitative Determination of Sulphur. Carius' Method . . . 81
Quantitative Determination of Nitrogen. Dumas' Method . . . 85
Quantitative Determination of Carbon and Hydrogen. Liebig's Method 98
SPECIAL PART
I. ALIPHATIC SERIES
1. Reaction: The Replacement of an Alcoholic Hydroxyl Group by a
Halogen . . 112
2. Reaction: Preparation of an Acid-Chloride from the Acid . . 121
3. Reaction: Preparation of an Anhydride from the Acid-Chloride and
the Sodium Salt of the Acid 127
x£i CONTENTS
PAGE
4. Reaction: Preparation of an Acid-Amide from the Ammonium Salt
of the Acid ~ . . .131
5. Reaction: Preparation of an Acid-Nitrile from an Acid-Amide . 135
6. Reaction: Preparation of an Acid-Ester from the Acid and Alcohol 137
7. Reaction: Substitution of Hydrogen by Chlorine . . . .139
8. Reaction: Oxidation of a Primary Alcohol to an Aldehyde . . 143
9. Reaction: Preparation of a Primary Amine from an Acid-Amide of
the next Higher Series 151
10. Reaction: Syntheses of Ketone Acid-Esters and Polyketones with
Sodium and Sodium Alcoholate 155
XI. Reaction: Syntheses of the Homologues of Acetic Acid by means of
Malonic Ester 161
12. Reaction: preparation of a Hydrocarbon of the Ethylene Series by
the Elimination of Water from an Alcohol. Union with Bromine 166
13. Reaction: Replacement of Halogen Atoms by Alcoholic Hydroxyl
Groups 171
TRANSITION FROM THE ALIPHATIC TO THE AROMATIC
SERIES
Dimethylcvclohexenone and s-Xylenol from Ethylidenebisacetacetic Ester
(Ring Closing in a 1.5 Diketone) 176
II. AROMATIC SERIES
1. Reaction: Nitration of a Hydrocarbon 185
2. Reaction: Reduction of a Nitro-Compound to an Amine . .188
3. Reaction: (a) Reduction of a Nitro-Compound to a Hydroxylamine
Derivative. (&) Oxidation of a Hydroxylamine Derivative to a
Nitroso-Compound 196
4. Reaction: Reduction of a Nitro-Compound to an Azoxy-, Azo-, or
Hydrazo-Compound . 199
5. Reaction: Preparation of a Thiourea and a Mustard Oil from Car-
bon Disulphide and a Primary Amine 205
6. Reaction: Sulphonation of an Amine 208
7. Reaction: Replacement of the Amido- and Diazo-Groups by Hy-
drogen . 210
CONTENTS xiii
PAGE
8. Reaction: Replacement of the Diazo-Group by Hydroxyl . .216
9. Reaction: Replacement of a Diazo-Group by Iodine . . .217
10. Reaction: Replacement of a Diazo-Group by Chlorine, Bromine, or
Cyanogen . . . .. 221
11. Reaction: (a) Reduction of a Diazo-Compound to a Hydrazine.
(l>) Replacement of the Hydrazine-Radical by Hydrogen . . 223
12. Reaction: (a) Preparation of an Azo-Dye from a Diazo-Compound
and an Amine. (l>) Reduction of the Azo-Compound . . 229
13. Reaction: Preparation of a Diazoamido-Compound . . . 235
14. Reaction: The Molecular Transformation of a Diazoamido-Com-
pound into an Amidoazo-Compound . . . . .. 238
15. Reaction: Oxidation of an Amine to a Quinone . . .. 239
16. Reaction: Reduction of a Quinone to a Hydroquinone . . . 243
17. Reaction: Bromination of an Aromatic Compound . . . 244
18. Reaction: Fittig's Synthesis of a Hydrocarbon . . .. 249
19. Reaction: Sulphonation of an Aromatic Hydrocarbon (I) . . 253
20. Reaction: Reduction of a Sulphonchloride to a Sulphinic Acid
or to a Thiophenol 258
21. Reaction: Sulphonation of an Aromatic Hydrocarbon (II) . . 261
22. Reaction: Conversion of a Sulphonic Acid into a Phenol . . 264
23. Reaction: Nitration of a Phenol 267
24. Reaction: (a) Chlorination of a Side-Chain of a Hydrocarbon.
(£) Conversion of a Dichloride into an Aldehyde . . . 269
25. Reaction: Simultaneous Oxidation and Reduction of an Aldehyde
under the Influence of Concentrated Potassium Hydroxide . . 274
26. Reaction: Condensation of an Aldehyde by Potassium Cyanide to a
Benzoin 276
27. Reaction: Oxidation of a Benzoin to a Bcnzil 278
28. Reaction: Addition of Hydrocyanic Acid to an Aldehyde . . 279
29. Reaction: Perkin's Synthesis of Cinnamic Acid . . .. 285
30. Reaction: Addition of Hydrogen to an Ethylene Derivative . . 288
31. Reaction: Preparation of an Aromatic Acid-Chloride from the Acid
and Phosphorus Pentachloride 289
32. Reaction: The Schotten-Baumann Reaction for the Recognition of
Compounds containing the Amido-, Imido-, or Hydroxyl-Group . 290