Semimicro and macro organic chemistry;: A laboratory manual

402 Pages·1942·3.94 MB·English

by  Nicholas Dimitrius Cheronis

SEMIMICRO
AND
MACRO
ORGANIC
CHEMISTRY
BY THE SAME AUTHOR
ORGANIC CHEMISTRY
SEMIMICRO AND MACRO ORGANIC CHEMISTRY
SEMIMICRO
AND
MACRO
ORGANIC
CHEMISTRY
A L A B O R A T O RY MANUAL BY
Nicholas D. Cneronis
CHICAGO CITY COLLEGES
NEW YORK • THOMAS Y. CROWELL COMPANY
COPYRIGHT, 1942, BY
THOMAS Y. CROWELL COMPANY
All rights reserved. No part of this book may be
reproduced in any form, by mimeograph or any
other means, without permission in writing from
the publisher.
FIRST PRINTING, SEPTEMBER 1942
MANUFACTURED IN THE UNITED STATES OF AMERICA
BY THE COLONIAL PRESS INC., CLINTON, MASS.
PREFACE
The present laboratory manual was developed primarily to pro-
vide suitable experiments in elementary laboratory practice for all
levels of students, both the average and the exceptional. Impressed
by the possibilities of the semimicro technic in connection with this
problem, the author began several years ago to experiment with it
in his classes. After mature consideration and six years of trial and
error with all types of students, he believes that it is possible to
attain all the objectives of laboratory practice in elementary or-
ganic chemistry using the semimicro technic. In addition, this
method offers the following advantages over the traditional
method: (1) it permits better adaptation of the laboratory work to
the varying needs of students; (2) it teaches students greater
care, cleanliness, and manipulation; (3) it is more economical; and
(4) it reduces substantially the seriousness of possible accidents
since the quantities of reagents and size of equipment are only
some 10 to 20 per cent as great as with macro methods.
It is realized, however, that a sudden and complete shift from
traditional macro methods is usually not practical or desirable.
For this reason, in practically all experiments, semimicro is par-
alleled with the macro method. In this manner teachers may ex-
periment as widely with semimicro technic and with whatever
students they wish.
The arrangement of the material in the manual is made accord-
ing to the following plan: In the first part an attempt is made to
introduce the students to the elementary technics, such as crystal-
lization of solids, distillation of liquids, determination of boiling
and melting points and of refractive indices, necessary for the
study of organic chemistry. This is followed by a study of the
preparation and properties of the simpler groups of organic com-
pounds. The preparation of one or more compounds from each
group serves to illustrate the general principles involved. This is
followed by a systematic study designed to illustrate important
group properties and variations of these among members of the
same group. Beginning each experiment there is a brief introduc-
tory explanation relating the material of the experiment to the
previous knowledge of the student and also orienting him to the
work to be done. For each group of organic compounds there are
vi PREFACE
usually listed several preparations. It should be emphasized that
this practice does not place a premium on the amount of work
done; it is rather the organization and understanding of the work
done that are of primary importance. It is believed, however, that
directions for several preparations will be an aid to the teacher in
providing suitable work for students of different abilities and in-
terests. A number of experiments are well adapted to discussion-
demonstrations to be given by the instructor, and are so marked.
The latter part of the manual is devoted to compounds of greater
complexity. Some of these require the preparation of several com-
pounds which are used in the subsequent work in order to obtain
the final product. Thus it is hoped that the manual achieves unity
and organization for teaching rather than being a mere collection
of unrelated preparations.
The author wishes to acknowledge his indebtedness to those who
have aided him in this work: for suggestions, reading, and com-
menting on parts of the manuscript, to Louis Sattler of Brooklyn
College, Joseph B. Niederl of New York University, Gordon
Pritham of the University of Scranton, Ernest R. Kline of the
University of Connecticut, Louise Wendt of Nebraska State
Teachers College, John Entrikin of Centenary College, and to his
colleagues, Sebastian Durban, James Parsons, and Conrad Ronne-
berg; to Joseph Drummond and Kurt Spitzmueller for many sug-
gestions on apparatus and methods; to Milton Cooper and Michael
Savoy for suggestions on the experiments for the determination of
melting points; to his former students, Peter Arvan, Herman
Teifeld, Alford Anderson, Richard Erhardt, and Carl Anderson
for their patience and work in adapting the various preparations
of organic compounds to the semimicro technic; to Walter Bur-
fischer of Wilkens-Anderson Company for the many suggestions
and help in the development of the semimicro apparatus; and, for
assistance in the preparation of the manuscript, to Harold Wood-
son, Helen Karagianes, and Denver Cummings.
NICHOLAS D. CHERONIS
CONTENTS
BXPEBIMENT FAQS
General Information 1
PART I
INTRODUCTION TO LABORATORY METHODS
1. The Sources of Organic Compounds 21
2. The Purification of Solid Organic Compounds by Crys-
tallization 24
3. Determination of Melting Points 41
4. Determination of Melting Points of Mixtures . .. 53
5. The Purification of Organic Compounds by Distillation 57
6. Purification by Fractional Distillation 65
7. Micro Determination of Boiling Points 78
8. Determination of Refractive Indices 82
9. Identification of Elements in Carbon Compounds . . 87
PART II
PREPARATION AND PROPERTIES OF
SIMPLE ORGANIC COMPOUNDS
10. Preparation of n-Decane and n-Octane 97
11. Preparation of Ethylbenzene 103
12. Preparation of a Hydrocarbon by Decarboxylation of an
Organic Acid 106
13. Unsaturated Hydrocarbons: Preparation of Cyclohexene
and Amylene 108
14. The Preparation of Acetylene 118
15. The Study of Aromatic Hydrocarbons 121
16. Preparation of Hydrocarbons by the Use of the Grignard
Reagent 123
17. The Reactions of Hydrocarbons 127
18. Preparation of Butyl Chlorides . 131
19. Preparation of Butyl Bromides 135
20. Preparation of Alkyl Iodides 138
21. Preparation of Bromobenzene 140
22. The Properties and Reactions of Halogen Compounds . 144
23. Grignard Synthesis of Carbinols 146
24. The Reactions of Hydroxy Compounds 150
vii
viii CONTENTS
EXPERIMENT PAGE
25. Preparation of Ethers 153
26. Preparation of Amines by Ammonolysis 160
27. Preparation of Aniline 163
28. Reactions of Amines 174
29. Preparation of Nitro Compounds 178
30. Important Reactions of Nitro Compounds . . .. 181
31. Oxidation of Alcohols to Aldehydes and Ketones . . 183
32. Preparation of Acetaldehyde 187
33. The Preparation of Cyclopentanone 189
34. Reactions of Aldehydes and Ketones 191
35. The Polyhalogen Compounds 196
36. Preparation of Acids by Oxidation of Alcohols . . . 199
37. Preparation of Acids by Carboxylation of the Grignard
Reagent 201
38. Reactions of Carboxylic Acids 204
39. Preparation and Properties of Esters 207
40. Preparation and Properties of Acyl Chlorides . . . 211
41. Preparation and Properties of Amides 216
42. Preparation of Acid Anhydrides 219
PART III
PREPARATION AND PROPERTIES OF COMPOUNDS
OF GREATER COMPLEXITY
43. Preparation of Chloroacetic Acid 223
44. Preparation of a-Bromopropionic Acid 230
45. Distillation under Reduced Pressure 232
46. Determination of Optical Rotation 244
47. Esters of Polyhydroxy Compounds 248
48. Properties of Carbohydrates 252
49. Preparation and Properties of Urea 257
50. Preparation and Properties of a-Amino Acids . . . 260
51. Properties of Proteins 263
52. Preparation of Substituted Anilines 266
53. Preparation of Diazonium Salts 271
54. Replacement of the Diazo Group by Iodine . . .. 275
55. Replacement of the Diazo Group by Chlorine . . . 277
56. Replacement of the Diazo Group by a Hydroxyl Group 280
57. Reduction of the Diazo Group 282
58. Preparation of Azo and Diazoamino Compounds . . 285
59. Preparation of Sulfonic Acids 289
60. Preparation and Properties of Quinones 293
61. Preparation of Aromatic Hydrocarbons by the Friedel-
Craf ts Reaction 296
62. Preparation of Ketones by the Friedel-Crafts Reaction 300
CONTENTS ix
EXPEBIMENT PAGE
63. Preparation of o-Benzoylbenzoic Acid 303
64. Preparation of Anthraquinone by Ring Closure . . . 305
65. Condensations of Carbonyl Compounds 307
66. The Benzidine Rearrangement 311
67. Preparation of Heterocyclic Compounds 314
68. Physiologically Active Compounds 317
69. Preparation of Dyes and Indicators 328
70. Synthetic Polymers 343
Appendix
I. Laboratory Accidents and First Aid . . .. 347
II. Suggested List of Apparatus for Elementary Or-
ganic Chemistry (Macro and Semimicro) . . 350
III. List of Chemicals and Reagents 352
IV. Calibration of Thermometers 355
V. Freezing Mixtures 357
VI. Drying Agents for Organic Liquids . . .. 357
VII. Cleaning Solutions 358
VIII. Preparation of Pipettes and Pipette Droppers . 359
IX. Preparation and Sealing of a Bomb Tube . . 360
X. Densities and Percentage Compositions of Vari-
ous Solutions 362
XL Vapor Pressures of Various Organic Substances . 367
XII. Reference Books for Beginners in Practical Or-
ganic Chemistry and Laboratory Methods . 368
XIII. Write-Up of a Typical Experiment . . .. 369
Index 371