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GIFT OF
President's Office




EXPERIMENTAL ORGANIC
CHEMISTRY



NEW-WORLD SCIENCE SERIES

Edited by John W. Ritchie

SCIENCE FOR BEGINNERS

By Delos Fall
TREES, STARS, AND BIRDS

By Ed-win Lincoln Moseley
SCIENCE OF THE EVERYDAY WORLD

By Carleton W. Washbiirne
HUMAN PHYSIOLOGY

By /<?/* W. Ritchie
SANITATION AND PHYSIOLOGY

By John W. Ritchie

LABORATORY MANUAL FOR USE WITH
"HUMAN PHYSIOLOGY"

By Carl Hartman



EXERCISE AND REVIEW BOOK IN BIOLOGY

By/. G. Blaisdell
PERSONAL HYGIENE AND HOME NURSING

By Louisa C. Lippitt
SCIENCE OF PLANT LIFE

By Edgar Nelson Transeau



ZOOLOGY

By T. D. A. Cockerell
EXPERIMENTAL ORGANIC CHEMISTRY

By Augustus P. West



NEW-WORLD SCIENCE SERIES
Edited by John W. Ritchie

EXPERIMENTAL

ORGANIC
CHEMISTRY

by
Augustus P. IFest, Ph.D.

Professor of Chemistry, University of the Philippines

ILLUSTRATED WITH
DRAWINGS AND DIAGRAMS




Tonkers-on- Hudson, New Tork

WORLD BOOK COMPANY

1920



y

WORLD BOOK COMPANY A;

THE HOUSE OF APPLIED KNOWLEDGE (\^
Established, 1905, by Caspar W. Hodgson

YONKERS-ON-HUDSON, NEW YORK

2126 PRAIRIE AVENUE, CHICAGO

The World War has emphasized as nothing
else could have done the many and varied
relations of science to modern life, and the
imaginations of many persons have been
quickened by a realization of the possibili-
ties of the progress of science and its appli-
cations to human needs. In consequence,
we are doubtless at the beginning of a period
of great scientific development, and in this
period the fertile field of organic chemistry
is sure to receive even more attention than
it has had in the past. World Book Com-
pany has pleasure in offering at this time a
practical text in the subject. It is the out-
growth of a carefully worked-out method of
instruction that has given excellent results
where it has been used







NWSS : WEOC-I



Copyright, 1920, by World Book Company

Copyright in Great Britain

All rights reserved



PREFACE

IN several respects this book is somewhat different from similar
ones which are in general use at the present time. It is a combina-
tion of textbook and laboratory manual in which the theoretical
discussions and the laboratory experiments are blended together.
This arrangement encourages the student to consult the text while
he is doing the experiments in the laboratory, with the result that
he is more likely to perceive clearly the relation between the theory
and the practice.

Only the more important compounds are discussed, and thus the
student is not bewildered with a mass of information relating to a
large number of compounds of minor importance. Again, experi-
ments which are dangerous or very difficult for a beginner have been
purposely omitted.

The application of general reactions and the general relations
between the different groups of compounds have received special
attention; in fact, at frequent intervals review tables are given,
showing the relation between the principal members of various
groups of compounds. These review tables are very helpful in
enabling the student to review at a glance the chemistry of a number
of groups of compounds.

Special emphasis has been laid upon the exact preparation of
organic compounds, as this constitutes the most important feature
of a course in organic chemistry. In accordance with this view the
directions for performing the experiments have been written in a
most precise and accurate manner and will be found unusually free
from ambiguous statements; in fact, the student is usually told
exactly what to do and how to do it. This method has given ex-
cellent results in the University of the Philippines, where it has
been necessary to handle laboratory sections of more than one hun-
dred students. It trains a student to follow directions and to rely
upon himself rather than an instructor, it enables a teacher to handle
large laboratory classes in a satisfactory manner, with the result that
accidents and explosions seldom, if ever, occur.

Unlike many laboratory manuals, this book gives the equations
to explain the experiments, as it is considered desirable to give the
student ample opportunity to understand thoroughly his laboratory

v

417200



vi Preface

work. Questions relating to the experiments and other questions
which are supposed to give a certain amount of mental training are
placed at the end of the chapters.

This book may be used as a combination textbook and laboratory
manual, in which case material that has been omitted, such as cer-
tain groups of compounds and experiments, may be presented in
the lectures. Since the text itself is rather abbreviated, some teachers,
in giving a more extended course, may perhaps prefer to use the book
simply as a laboratory manual.

The author wishes to express his sincere thanks to Mr. J. I. Del
Rosario, Miss P. P. Herrera, and Miss Zoila Montes of the Univer-
sity of the Philippines, who have assisted him in reading the proof.



CONTENTS

PAGE

INTRODUCTION ' . . . . . xiii

ALIPHATIC COMPOUNDS

CHAPTER

1. PURIFICATION OF COMPOUNDS, SOLVENTS, AND DETERMINATION OF

FORMULAS % . . i

2. PARAFFIN HYDROCARBONS AND HALOGEN DERIVATIVES . . . 22

3. UNSATURATED HYDROCARBONS . . . . . . . . 56

4. ALCOHOLS: MONOHYDROXY DERIVATIVES OF THE HYDROCARBONS . 76

5. ETHERS AND SULFUR COMPOUNDS . . .'.,.,. . 89

6. ALDEHYDES AND KETONES ... . . . . .98

7. MONOBASIC ACIDS. . . * ' . .... ... 114

8. ESTERS . . . . , ........ .132

9. ACID CHLORIDES, ANHYDRIDES, AND AMIDES 139

10. AMINES . . . .... . . . . ... iS 1

11. CYANOGEN COMPOUNDS . -. . 160

12. SUBSTITUTED ACIDS . ^ . . ...-'..". .. . . .170

13. POLYHYDROXYL DERIVATIVES AND RELATED COMPOUNDS . . .183

14. DIBASIC ACIDS ... . . . 197

15. HYDROXY ACIDS AND STEREOCHEMISTRY . . . . . .212

16. CARBOHYDRATES . .... . . . . . . 243

AROMATIC COMPOUNDS

17. AROMATIC HYDROCARBONS 277

1 8. HALOGEN DERIVATIVES OF AROMATIC HYDROCARBONS . . . 304

19. NITRO COMPOUNDS . . . . . . . . . . 315

20. AMINO COMPOUNDS . . 323

21. DIAZONIUM COMPOUNDS . . . - 338

22. SULFONIC ACIDS 350

23. PHENOLS . * . * . . . . ... . . 361

24. ALCOHOLS, ETHERS, ALDEHYDES, KETONES, AND QUINONES v.- . 379

25. AROMATIC CARBOXYL ACIDS . . . ." . . . . . . 401

26. OTHER AROMATIC HYDROCARBONS AND DERIVATIVES . . . .421

vii



viii Contents

APPENDIX PAGE

I. General Laboratory Directions .451

II. Approximate Quantity of Materials Required for One Student . . 453

III. Apparatus Required for One Student 456

IV. Atomic Weights of the Common Elements 457

Reference Books 458

INDEX . 459



EXPERIMENTS

NUMBER PAGE

1. Fractional distillation 2

2. Crystallization 5

3. Determination of the melting point 5

4. Organic solvents 7

5. Test for carbon 8

6. Test for carbon and hydrogen 8

7. Test for halogens 9

8. Test for nitrogen 10

9. Methane 23

10. lodoform 26

11. Ethyl bromide 29

12. Ethyl potassium sulfate 57

13. Ethylene 59

A. Oxidation of ethylene . . 61

B. Decolorization of bromine water by ethylene 61

C. Decolorization of potassium permanganate solution by ethylene . . 61

D. Decolorization of bromine solution by amylene 62

14. Acetylene . . . . . . 68

A. Oxidation of acetylene 69

B. Decolorization of bromine water by acetylene 69

C. Precipitation of copper acetylide . 70

15. Absolute alcohol 79

A. Test for water in alcohol by copper sulfate . . ." .81

16. Reactions of ethyl alcohol 81

A. Sodium reaction 81

B. Oxidation with chromic acid 81

C. lodoform test 81

D. Acetyl chloride reaction . . . 82

17. Conversion of ethyl bromide into ethyl alcohol . . . . . .82

18. Ether . - . 91

19. Extraction with ether 93

20. Silver mirror test for formaldehyde ....... 100

21. Acetaldehyde ammonia 101

A. Acetaldehyde from acetaldehyde ammonia . . . .103

22. Acetone sodium hydrogen sulfite . . no

23. Formic acid from glycerol 116

24. Reactions of formic acid . . . . 117

A. Sodium formate 117

B. Interaction of sodium formate and sulfuric acid . . . .117

C. Lead formate 118

D. Copper formate 118

E. Reduction of silver solution 118

F. Reduction of mercuric chloride 118

ix



x Experiments

NUMBER PAGE

25. Acetic acid from sodium acetate . 119

A. Test for acetic acid . . . . . . . . .120

26. Acetic acid from ethyl alcohol . ..'.'. . . .120

27. Salts of acetic acid . , . .125

A. Silver acetate 125

B. Copper acetate . . . 125

C. Ferric acetate . . . . 125

28. Ethyl acetate . . . . . . ...'.. . .132

29. Saponification of ethyl acetate . 137

30. Acetyl chloride ' 140

A. Reaction with ethyl alcohol . . -/'.'. . .142

B. Reaction with water . .".-.. . , . . .142

31. Acetic anhydride . . . . . . . . . . 144

A. Reaction with water 145

B. Reaction with ethyl alcohol . ' .145

32. Acetamide . . . . ". 147

A. Alkaline hydrolysis of acetamide . . . . . " . . 148

33. Methyl amine . . ... 152

A. Alkaline reaction . . ..";..". . . 155

B. Precipitation of aluminium hydroxide by ammonia . . . .155

C. Precipitation of aluminium hydroxide by amine solution . . .155

D. Decomposition of methyl ammonium chloride by sodium hydroxide . 156

E. Decomposition of methyl ammonium chloride by lime . . .156

F. Isocyanide test for primary amines . , . . . . .156

34. Cyanogen . ." . . . . . . . . . . 160

35. Reactions of cyanides . . . . ." . . . . . 163

A. Precipitation of silver cyanide . ... . . . .163

B. Potassium silver cyanide . . . 163

36. Test for ferrocyanides .... . . . . i .163

37. Test for ferricyanides . . 164

38. Methyl cyanide ,. ' . . 164

A. Hydrolysis of methyl cyanide . . . . .... . 165

39. Test for thiocyanates . . . .168

40. Amino acetic acid , . . . . .173

-A. Ferric chloride test . . . . . . . ... 175

41. Urea . . . . . 179

A. Urea nitrate . 179

42. Test for uric acid ." . . 181

43- Soap . . . .192

44. Reactions of oxalic acid . . . . ' . . . _ , J 99

A. Calcium oxalate 199

B. Interaction of oxalic and sulfuric acids 200

C. Oxidation of oxalic acid by acid permanganate . . . . 200



Experiments xi

NUMBER PAGE

D. Oxidation of oxalic acid by manganese dioxide and sulfuric acid . . 200

E. Calcium oxalate from sodium formate 200

45. Diethyl oxalate and oxamide ......... 201

A . Alkaline hydrolysis of oxamide 203

46. Malonic acid and calcium malonate . . . . ... * 204

A. Decomposition of malonic acid . . . . " . . ' .. . 205

47. Succinic acid separation of iron and zinc . . . . . . 208

48. Decomposition of inactive lactic acid . ar6

49. Tartaric acid and tartrates . . . . ' -. ' r . ..".'. . 230

A. Reaction of alkaline tartrate solution ... . . ." . 230

B. Silver mirror test . . ' .... - . . . . * . . 230

50. Tartar emetic . . . . . . ..-" >; . '. . " .. . 231

51. Calcium tartrate . . . . . . ' . . . - . . 232

52. Carbohydrate color test . . . . .... . . 244

53. Reduction of Fehling's solution by glucose . . 2 48

54. Behavior of sucrose with Fehling's solution . . . ' . . ' . . 260

55. Hydrolysis of sucrose . : . . ' . . . ' + . . . . 261

56. Test for invert sugar in bananas ... . . . . . 261

57. Polarization of cane sugar . . -. ..... . . 262

58. Preparation of starch solution . . ,' . .... . . 267

59. Test for starch . . .' . . 267

60. Test for starch in potatoes . .. . . . . . . .268

61. Hydrolysis of starch . . . '.'.'. . . . 268

62. Hydrolysis of cellulose . . . , . , ' 270

63. Coal tar and illuminating gas . . . . . . . .278

64. Reactions of benzene. . . . . ' . ' ^ . . . 282

A. Inflammability . . . , . ' . . .... 282

B. Crystallization . . . . , 282

C. Reaction with alkaline permanganate . . . . ... 282

D. Reaction with bromine solution . . . . ... . 282

65. Brom benzene and para dibrom benzene - . . . . . . 305

66. Nitrobenzene . . . . . . 316

67. Meta dinitro benzene . . . , ....". . . 318

68. Aniline . . * ; . . . . . . . . . 323

69. Aniline hydrochloride . . . . . . . . ^- ". 326

70. Acetanilide ............ 328

71. Meta nitraniline . . . ... 332

72. Azoxy benzene . .... 345

73. Azo benzene . . . . ... . . . . . 346

74. Sodium salt of para toluene sulfonic acid . " . . . * . 354

75. Sulfanilic acid . . V . . . . . . i > . 358

76. Phenol . . . , . " . . * . . 362

A. Tribrom phenol . , . . , - . . . . . . . 363

B. Ferric chloride test . . . , , . . . 363



xii Experiments

NUMBER PAGE

77. Nitro phenol 366

78. Potassium ortho nitro phenolate ... .... 368

79. Para cresol 370

A. Ferric chloride test 371

80. Color reactions of dihydroxy phenols . 375

A. Catechol ferric chloride test 376

B. Ferric chloride test for resorcinol 376

C. Quinol ferric chloride test 376

81. Benzyl alcohol 380

A. Reaction with hydrogen chloride ... . . . . 380

B. Oxidation with nitric acid 380

82. Anisol . . . . .'''. . . .... 384

83. Benzaldehyde reactions . . . . ... . . . 389

A. Benzaldehyde sodium hydrogen sulfite . . . . ' . 389

B. Oxidation of benzaldehyde to benzoic acid 390

84. Benzoin . . . 395

85. Ferric benzoate . . . . , . .... . 403

86. Ethyl benzoate . . . . . . .... . . 403

87. Benzamide . . . . . . . . . . . 405

A. Alkaline hydrolysis of benzamide . . . . . . . 405

88. Cinnamic acid . . . . . . . . . . 409

89. Barium salt of meta nitro benzoic acid . . . . ' -4 . .412

90. Salicylic acid . . . 415

91. Phthalic anhydride .' ;".' .418

92. Sodium salt of beta naphthalene sulfonic acid . . . . . 424

93. Anthraquinone . . . . . . . . . . 428

94. Malachite green 435

A. Dyeing with malachite green . . . ? - 437

95. Dyeing by precipitation . . . . . , . . 441

96. Dyeing with a substantive dye . . ...._.' . . . 442

97. Dyeing with an adjective dye . . 443



INTRODUCTION

PRIOR to the nineteenth century chemistry was divided into two
branches, inorganic and organic. Compounds which could be ob-
tained from living matter such as animal and vegetable substances
were called organic compounds, and those obtained from inert or
mineral matter were known as inorganic compounds. For many
years it had seemed impossible to prepare organic compounds by
artificial methods, and consequently it was believed that organic
substances were formed only in a living organism under the influence
of a peculiar " vital force." Wohler in 1828 prepared the organic
compound urea, CO(NH 2 )2, which is a typical secretion of the animal
organism, from the inorganic substance ammonium cyanate, NH 4 OCN.
Some years later other organic substances which occur naturally in
plants and animals were prepared artificially, and gradually it came
to be generally recognized that the influence of a living organism is
not necessary for the production of organic compounds.

In recent years the development of organic chemistry has made
enormous strides. Theories have been developed which have enabled
us to discover a large number of new compounds, many of which
are of considerable practical importance. Thus there has been
opened up gradually the great field of synthetic organic chemistry;
that is, the laboratory preparation of compounds, many of which
occur naturally in plants and animals. Since all these compounds
contain carbon, organic chemistry is the chemistry of carbon compounds.

Although there is no essential difference between organic and inor-
ganic substances, the carbon compounds are still, for various reasons,
considered as a separate branch of chemistry. The carbon compounds
differ somewhat from the inorganic compounds in their general prop-
erties and chemical behavior, and since the number of these compounds
is exceedingly large, it is convenient to treat them separately.

The two fields of chemistry, inorganic and organic, overlap to some
extent, since certain classes of compounds which contain carbon, such
as the cyanogen compounds, may be considered from the standpoint of
either branch of chemistry. A more exact name for organic chemistry
would be, perhaps, the chemistry of the hydrocarbons and their deriv-
atives, since a large number of organic compounds may be regarded
as derived from certain fundamental substances called hydrocarbons.



ALIPHATIC COMPOUNDS



EXPERIMENTAL ORGANIC
CHEMISTRY

CHAPTER ONE

PURIFICATION OF COMPOUNDS, SOLVENTS, AND
DETERMINATION OF FORMULAS

A LARGE proportion of the compounds of carbon are prepared
in the laboratory, from certain substances which occur naturally.
The laboratory methods which are used to prepare these com-
pounds have been worked out by careful experimentation.

Sources of carbon compounds. In certain parts of the world
an oil called petroleum is obtained either from natural springs or
from wells. This oil is composed chiefly of the paraffin hydro-
carbons. By means of the proper methods of purification and
preparation, a number of organic compounds can be obtained
which are derivatives of these hydrocarbons. When coal is
heated for the purpose of manufacturing illuminating gas, a
mixture of substances, which is called coal tar, is obtained as a
by-product. Coal tar yields a number of important carbon com-
pounds. A number of trees and plants also contain organic
compounds which are of great value for their medicinal prop-
erties. They, therefore, also form a natural source of carbon
compounds.

Purification of compounds. In order to study the chemical
behavior of compounds we must first obtain them in pure condi-
tion. The usual methods of purification are the following :



Purification

of
compounds



{ ^ \ Determine boiling point

Liquids Distillation ,

[ for purity



Solids



Crystallization

and
sublimation



Determine melting
point for purity



2 Experimental ^ Organic Chemistry

*. t t L^*.i-*.^*fcfc* * A

>.'tt* p t*'* 1 ' \ * *V * *

If the substance is 1 a* liquid* It is purified by distillation, but in

the cas'e of a mixture of liquid compounds it is often very difficult
to obtain these compounds in pure condition. However, we can
subject the mixture to fractional distillation and obtain portions
which have an amount of a particular ingredient greater than the
original mixture. The laboratory method of manipulation is
illustrated in the following experiment :

EXPERIMENT 1
Fractional distillation of a mixture of ethyl alcohol and water




Figure i
S CC " *& ak ho1 (9S per C6nt)



Materials

[ ioo cc. water

NOTE. Before performing any of the experiments the student should read the
general laboratory directions which are given in the Appendix.

Procedure. Connect a 300 cc. distilling flask to a Liebig condenser
as shown in the figure and place a wire gauze under the distilling flask.
The side tube of the distillation flask and the inner tube of the
condenser should project a short distance so that the distillate will
not touch the stoppers and become contaminated.



Purification of Compounds and Solvents



Prepare in a beaker a mixture consisting of 50 cc. of ethyl alcohol
(95 per cent) and 100 cc. of water. Will the mixture ignite when a
flame is applied to it ? The mixture is poured through a funnel into
the 300 cc. distilling flask. A thermometer is passed through a cork
stopper and placed in the neck of the flask at such a height that the
mercury bulb stands at the same level as the side exit tube of the flask.
A moderately slow stream of tap water is allowed to enter the condenser
at A and flow out at B.

Select four clean, dry flasks of about 100 cc. capacity to serve as
receivers for the distillate, which is the liquid that distils through the
condenser. Number the flasks i, 2, 3, and 4. The mixture is now
distilled and the distillate collected in fractions in the following
manner : Flask No. i is placed at the exit end of the condenser. The
mixture is now heated by a moderate flame which allows it to distil
gradually. When the temperature indicated by the thermometer
begins to rise above 85, the distillation is continued but the receiving
flask No. i is removed and replaced by flask No. 2. When the tem-
perature begins to rise above 89, flask No. 2 is removed and replaced
by flask No. 3, and as the temperature rises above 96 the distillation
is discontinued. The liquid remaining in the distilling flask is now
poured into flask No. 4 and allowed to cool. The distillate obtained
from the original mixture of alcohol and water is thus separated into
four fractions :

Room temperature to 85 inclusive.

Above 85 to 89 inclusive.

Above 89 to 96 inclusive.

Above 96.



I.

;IL

in.

IV.



Measure each fraction and tabulate the results as follows :





FRACTION


i


II


III


IV


Temperature


Room
Temperature
to 85


Above 85
to 89


Above 89
to 96


Above 96


First distilla-
tion .


Volume










Second distil-
lation . .


Volume











4 Experimental Organic Chemistry

The constituents of the original mixture may be further separated
by a second fractional distillation. This is carried out in the follow-
ing manner: The first fraction is placed in a clean distilling flask
which is connected to a condenser. Distil until the thermometer
indicates a temperature of 85. When the temperature begins to rise
above 85, temporarily discontinue the distillation, pour the second
fraction into the flask, and continue the distillation without changing
the receiving flask. A small amount will distil over before the tem-
perature reaches 85 ; when this temperature is obtained stop dis-
tilling, and add fraction III and proceed as before. Fraction IV is
treated in the same manner, except that when the thermometer be-
gins to rise above 85 the flask No. i is removed and flask No. 2 is put
in its place. At 89 the receiver No. 2 is removed and flask No. 3
put in its place. At 96 the distillation is discontinued and the residue
(fraction IV) remaining in the flask is cooled. The four fractions
obtained in the second distillation are measured and the results re-
corded in a table as represented above. By continued fractional
distillation the two end fractions (in this case Nos. I and IV) will
increase in volume, while the intermediate fractions will diminish.
Having twice fractioned the mixture of ethyl alcohol and water, ascertain
if fraction No. i is now sufficiently rich in alcohol to ignite when a lighted
match is applied to it.

Ethyl alcohol boils at 78 and water at 100. A mixture con-
sisting of 2 volumes of water and i volume of alcohol will begin
to boil at about 78, but only a very small amount of the distil-
late passes over at that temperature ; gradually, as the distilla-
tion proceeds, the temperature indicated by the thermometer
becomes higher and higher until at last 100 is reached and all
distils over. The distillates obtained at different temperatures
differ from each other in composition. Those obtained at the
lower temperatures have a larger amount of alcohol than those
obtained at the higher temperatures.

Boiling point. In determining the purity of compounds which
are liquids, the most important physical property utilized is the
boiling temperature, or boiling point. The temperature in-
dicated by the thermometer when the liquid is distilling is called



Purification of Compounds and Solvents 5

the boiling point. In the case of pure compounds the boiling
point does not rise during the distillation, but remains constant.
For accurate observations the boiling point must be corrected
in accordance with the barometric pressure observed at the time
of the experiment, since the boiling point varies with the baro-
metric pressure. A correction should also be made for the part
of the thermometer which is not inclosed by the flask. Tables
for making the necessary corrections may be found in larger
laboratory manuals.

The purification of compounds which are solids is effected by
crystallizing them.

EXPERIMENT 2

Crystallization of urea

Procedure. Place about 10 grams of urea in an evaporating dish
and add a sufficient amount of hot water to dissolve it. Evaporate
the solution on a water bath until a slight residue of the solid is de-
posited on the side of the dish. Allow the solution to cool and crystal-
lize. Filter, and wash with a few cubic centimeters of water. Then
place several thicknesses of filter paper on a watch glass, and on this
lay the filter paper containing the urea. The ^atch glass is used to
prevent the moist filter paper from coming in contact with the desk,
which may not be thoroughly clean. Place the watch glass contain-
ing the urea in your desk and allow it to remain some hours until
thoroughly dry, after which determine the melting point.

Another method which is used for purifying solids is called
sublimation. This procedure will be described later, in the direc-



Online LibraryAugustus Price WestExperimental organic chemistry → online text (page 1 of 32)