Perkin and Kipping's Organic chemistry

ORGANIC CHEMISTRY NEW AND REVISED EDITION

BY

W.^H. PERKIN,

JUN., PH.D., F.R.S.

PROFESSOR OF ORGANIC CHEMISTRY IN THE OWENS COLLEGER MANCHESTER -

F.

AND

STANLEY KIPPING,

PH.D., D.Sc. (LOND.), F.R.S.

PROFESSOR OF CHEMISTRY IN UNIVERSITY COLLEGE, NOTTINGHAM

W. & E. CHAMBERS, LIMITED LONDON AND EDINBURGH 1904

Edinburgh R. Chambers, Limited. :

Printed by

W. &

PREFACE. OUR

original

intention was to write a small text-book

on

Organic Chemistry, based on the syllabus drawn up by the Science and Art Department, in the hope that it would be students

useful

to

classes

in the

as a

attending

subject,

handy book

the

of reference.

advanced

elementary or

and not without value As, however,

to

teachers

soon became

it

apparent that, by making comparatively few additions, the subject-matter might be made to include the facts usually dealt with in

a course of

work was enlarged same time to make it more of

the

about sixty lectures, the scope to

this

useful

extent, to

so

as

at

the

general students as

an introduction to Organic Chemistry. Part I., which deals with the fatty compounds, contains, in the

first

place, a general account of the

quently employed

of organic compounds,

weight.

methods most

in the separation, purification,

fre-

and analysis

and in the determination of molecular

The preparation and

properties

of

typical

com-

pounds are then described, attention being directed to those changes which come under the heading of general reactions rather than to isolated facts regarding particular substances.

Questions of constitution are also discussed at some length,

v

PREFACE.

and in the

case of most of the typical compounds, the facts on which the given constitutional formula is based are specificThis course was adopted, not only in order ally mentioned. to avoid the introduction of a long chapter earlier stage,

on structure

at

an

but also because, in our opinion, a constant

use of constitutional formula?, accompanied by a clear conception of their meaning, is one of the greatest helps, even to a beginner, in committing the facts to memory.

The opening chapters and

tar

its

treatment.

of Part II. contain

an account of

coal-

This leads naturally to a description of

the preparation and properties of benzene, and to a discussion of its constitution in the light of facts previously dealt with

the

student

is

thus

made acquainted with

characteristics of aromatic, as distinct

and

is

from

the

fatty,

;

principal

compounds,

then in a position to understand the classification of

organic substances into these two main divisions.

The more important classes of aromatic compounds are then somewhat different manner from that

described, but in a

adopted in Part L, inasmuch as a general account of the properties of each class of substances

is

given before, instead

after, the more detailed description of typical compounds ; this course is to a great extent free from the disadvantages

of

which are found

to attend its adoption at earlier stages, as the student has by this time acquired some experience of the more

systematic

Part

method from a study

of the

summaries given in

I.

Special attention has been given, as before, to questions of constitution, one of the objects- being to train the student to think out such matters, and to try and deduce a constitutional

formula for a given substance, by comparing its properties with those of others of known constitution ; with this end in view, it

has often been thought

desirable to withhold the

most

t

PREFACE.

important evidence in favour of the accepted constitutional formula until the subject had been discussed at some length.

The concluding chapters on dyes, alkaloids, and stereoisomerism will doubtless offer the greatest difficulties, but, considering the importance of the matters with which they their omission or curtailment

deal,

The account

was deemed inadvisable.

of the alkaloids should be useful, more particu-

on dyes deals with a variety of substances of even greater practical value, and indicates the methods employed in one of the most im-

larly to medical students, whilst the chapter

portant applications of organic chemistry.

The chapter on

stereo-isomerism was included because, owing to the import-

ance to which this theory has

now

attained, a text-book

organic chemistry would be incomplete without a cussion of the subject. The full directions which for the

use of models will,

on

brief disare given

hoped, lead to a clear con-

it is

ception of the views set forth.

A

considerable proportion of the text, dealing as a rule

either with matters of less importance or of a nature,

printed in small type,

is

more advanced

and should be

left

out of

consideration until the rest of the subject-matter has been

mastered,

or, at

any

rate, studied.

'summary and extension'

at

The

consideration of the

the conclusion of some of the

more important chapters, should also be postponed until the student has acquired some knowledge of the subject, as the

method here adopted

is

not well suited to the requirements

of a beginner.

One

of the principal objects throughout has

been to treat

the subject from a practical point of view (as far as this could be done in a text-book on theoretical chemistry), because, unless

work accompanies the The progress can be made.

a thorough course of practical

theoretical,

no

really satisfactory

PREFACE.

VI

student should himself perform

involved in

the

many

of the simple exercises

and analysis of organic com-

purification

pounds, and should prepare typical substances in order to

become

practically acquainted

with their properties.

Such

general operations as oxidation, reduction, hydrolysis, nitration,

sulphonation,

&c.,

and

the

more important general

reactions for the identification of the several classes of com-

pounds, should also be included in the practical course. In many respects we have made free use of the excellent text-books of V. Beilstein's

Cliemie.

Meyer and Jacobson and von

Handbuch, and of

We

are also

much

Ost's

indebted to

help in revising the proof-sheets,

and

Richter, of

Lehrbuch der technischen

Dr

A. Harden for

in preparing the index.

Since this preface was written, a chapter dealing with some of the

more important constituents of plants and animals has in the form of an Appendix, with a separate

been added index.

We

hope that this new chapter will be found useful

by all readers, but especially by medical students, more particularly it has been written.

for

whom

PREFACE TO REVISED EDITION.

THE

favourable

accorded

reception

to

our

Text-book on

Organic Chemistry, and the constantly increasing support which it has received during recent years, have led us to

undertake already a complete revision of Parts

I.

and

II.

in order to bring the whole of the subject-matter thoroughly up-to-date.

Although, in doing

so,

in the

any noteworthy change we have found it necessary alterations

account into

of

of

the

considerable

new

facts

we have not introduced

general plan of to

the work,

make throughout many in

importance

order

to

take

and views which have come

prominence in the course of the rapid and continued

progress of

Certain chapters, indeed, Organic Chemistry. have been almost entirely rewritten and numerous additions have been made, but as it has also been possible to omit or condense

portions of the old text dealing with matters

of

diminishing importance, the been very materially increased

the revised edition will of students as those for

size ;

of the book

we

prove useful

whom

trust,

to

has not

therefore,

that

the same classes

the original one was intended.

Theoretical and Author of Mackay's Euclid.'

ARITHMETIC,

Practical.

By

J.

S.

MACKAY, M.A., LL.D.,

'

ALGEBRA FOR SCHOOLS. By

4/6.

WILLIAM THOMSON, M.A.,

B.Sc., Registrar,

University of the Cape of Good Hope, formerly Assistant-Professor of Mathematics and Mathematical Examiner, University of Edinburgh. 576 pages. Cloth, 4/6.

CHAMBERS'S ELEMENTARY ALGEBRA. By WILLIAM THOMSON, M.A., B.Sc. Up to and including Quadratic Equations. 288 pages. Cloth, 2/. With Answers,

2/6.

THE ELEMENTS OP EUCLID.

Books I. to VI., and parts of Books XI. and With Numerous Deductions, Appendices, and Historical Notes, by MACKAY, LL.D., Mathematical Master in the Edinburgh Academy. 412 pages. 392 diagrams. 3/6. Separately, Book I., I/; II., 6d. III., 9d. Books XL XII., 6d. Key, 3/6. JAMES TABLES. MATHEMATICAL By PRYDE, F.E.I.S. These comprehend XII.

J. S.

;

the most important Tables required in Trigonometry, Mensuration, LandSurveying, Navigation, Nautical Astronomy, &c. The tables of Logarithms to 108000), Logarithmic Sines, &c., are carried to seven decimal places. 496 pages. 4/6.

(1

;

CONTENTS. PAGE

CHAPTER I. COMPOSITION, PURIFICATION, AND ANALYSIS OF ORGANIC COMPOUNDS Origin and Present Meaning of the Word Organic

1

'

Composition of Organic Compounds General Principles of Organic Analysis Separation and Purification of Organic Compounds Tests of Purity

1

3 4

4 12

Qualitative Elementary Analysis

14

Quantitative Elementary Analysis Estimation of Carbon and Hydrogen

18 18

Quantitative Determination of Nitrogen

23

Quantitative Determination of Chlorine, Bromine, and Iodine

27

DEDUCTION OF A FORMULA FROM THE RESULTS OF ANALYSIS AND DETERMINATION OF MOLECULAR

CHAPTER

II.

WEIGHT

30

CHAPTER III. CONSTITUTION OR STRUCTURE OF ORGANIC COMPOUNDS CHAPTER IV. THE PARAFFINS, OR HYDROCARBONS OF THE

METHANE

SERIES

Methane, or Marsh-gas Ethane

48

53 53

58

Propane Butanes

60

Pentanes

63

61

Isomerism

Homologous

64 Series

General Formulae

Summary and Extension

66 66 67

X

CONTENTS. PAGE

CHAPTER V. UNSATURATED HYDROCARBONS THE OLEFINES, OR HYDROCARBONS OF THE ETHYLENE SERIES

71

Ethylene

71

Propylene

78

Summary and Extension of the

Hydrocarbons

79

Acetylene Series

80 81

Acetylene

87

Crotonylene and Extension

Allylene

Summary CHAPTER VI.

89

THE MONOHYDRIC ALCOHOLS

89

Methyl Alcohol

89

94 Ethyl Alcohol Production of Wines and Beers; Alcoholic Fermentation... 97 103 Homologues of Ethyl Alcohol

Propyl Alcohol Butyl Alcohols

Isopropyl Alcohol Alcohols

Amyl

Summary and Extension CHAPTER VII. THE ETHERS

105 106 107

,

Ill

Methyl Ether

Ill

Ethyl Ether

Ill

Summary and Ex tension

115

Radicles

116

CHAPTER

ALDEHYDES AND KETONES

VIII.

118

^

Formaldehyde

118

^

Polymerisation

121

122

--pA.cetaldehyde

Polymerisation of Acetaldehyde Acetal Chloral

Homologues

of

Acetaldehyde

Ketones

127

129 130

Acetone

130

Condensation of Acetone

133

Hydroximes and Hy d razones Summary and Extension

CHAPTER

^

126

IX.

THE FATTY ACIDS

1

34

136

145

Formic Acid

145

Acetic Acid

149

CONTENTS.

XI PACK

Homologues

of Acetic

Acid

156

Propionic Acid

158

Normal Butyric Acid Isobuty ric Acid

Iso valeric

Acid

Normal Heptylic Acid ^Palmitic Acid Stearic Acid Derivatives of the Fatty Acids

1

58

1

59

160 160

Acid Chlorides

161

Anhydrides

162

Acetic Anhydride

1 63

164

./Amides

Acetamide

1

Substitution Products of Acetic Acid

165

Chlor-, Dichlor-,

and Trichlor-acetic Acid

64

166

Summary and Extension

167

Fats, Oils, Soaps, Stearin, and Butter Composition of Fats and Oils

169 169

Soaps

171

Stearin and Glycerol

1

Butter

173

CHAPTER X.

ETHEREAL SALTS, OR ESTERS

Halogen Ethereal Salts and Halogen Derivatives Paraffins

Methyl Chloride

Methylene Dichloride Carbon Tetrachloride lodoform

Chloroform

72

174 of the

174

175 ....177

Ethyl Chloride

178

Ethyl Bromide

179

Ethyl Iodide

180

Ethereal Salts of Nitric Acid

Ethyl Nitrate Ethereal Salts of Nitrous Acid Ethyl Nitrite

182

Nitro-paraffins

184

183

Ethereal Salts of Sulphuric Acid

185

Ethyl Hydrogen Sulphate Mercaptans and Sulphides

185 1

Ethyl Sulphide Ethereal Salts of Organic Acids

Summary and Extension

86

187

Ethyl Mercaptan

188

Ethyl Acetate

188 190

CONTENTS.

Xll

PAGE

CHAPTER XL SYNTHESIS OF KETONES AND FATTY ACIDS WITH THE AID OF ETHYL ACETOACETATE AND ETHYL

MALONATE

193

Ethyl Acetoacetate Ketonic Acids

200

Ethyl Malonate

201

193

ALKYL COMPOUNDS OF NITROGEN, PHOSSILICON, ZINC, MERCURY, AND OTHER ELEMENTS

CHAPTER

XII.

PHORUS,

ARSENIC,

204

Ethylamine

205

Diethylamine

208

Triethylainine

209

Tetretliylammonium Hydroxide Preparation and Identification of Amines

210

Phosphines

214 215

Arsines Trie thy larsine

Tetrethylarsonium Iodide

Dimethylarsine Oxide

Tetramethyl

Silicon Tetrethyl

Organo- metallic Compounds Zinc Ethyl Mercuric Ethyl

CHAPTER

XIII.

216 217

Organic Silicon Compounds Silicon

211

218 219 220

220 222

THE GLYCOLS AND THEIR OXIDATION PRO-

DUCTS Ethy lene Glycol Oxidation Products of the Glycols Glyoxal Hydroxycarboxylic Acids Glycollic Acid Lactic Ac^d

223 224 229 229 231

Hydracrylic Acid Dicarboxylic Acids

233

Oxalic Acid

235

Oxamide

239

234

Malonic Acid

239

SuccinicAcid

240

Succinic Anhydride

241

CONTENTS.

Xlll

PAGE

Hydroxydicarboxy lie Acids Tartaric Acid

Hyd roxy tricarboxylic Acids

Malic Acid

245 247

Citric

Acid

251

TKIHYDRIC AND POLYHYDRIC ALCOHOLS

CHAPTER XIV.

253

254

Glycerol

Chlorohydrins

257

Nitro-glycerin

258

Unsaturated Compounds related to Glycerol Allyl Alcohol Allyl Bromide

Allyl Sulphide

Acrylic Acid Polyhydric Alcohols

Monoses

Acrole'in

262 263

Ery thritol - Mannitol

THE CARBOHYDRATES

264 266

Glucose

Mannose

260 261

Allyl Iodide

CHAPTER XV.

260

267

Galactose

269

Fructose

270

Action of Phenylhydrazine on Glucose and Fructose Bioses Sucrose

272

274

Maltose

276

Lactose

277

Polyoses

Starch

Gluten

278

Dextrin

280

Cellulose

281

Gun-cotton

Cordite

Collodion

282

Summary and Extension CHAPTER XVI.

CYANOGEN COMPOUNDS

283 :

285

285

Cyanogen Hydrogen Cyanide

287

Potassium Ferrocyanide Potassium Ferricyanide

293

292

Nitriles

293

Cyanic Acid Thiocyanic Acid

295 296

Allyl Isothiocyanate

298

CONTENTS.

XIV

PAGE

CHAPTER XVII.

AMIDO- ACIDS

GLYCINE

299

^^rea,

301

Uric Acid

303

MANUFACTURE, PURIFICATION, AND PRO-

CHAPTER XVIII.

PERTIES OF BENZENE

305

CONSTITUTION OF BENZENE, AND ISOMERISM

CHAPTER XIX. OF BENZENE DERIVATIVES

313

GENERAL PROPERTIES

CHAPTER XX. POUNDS

.OF

AROMATIC COM331

Classification of Organic

331

Compounds

General Character of Aromatic Compounds

334

CHAPTER XXL HOMOLOGUES OF BENZENE AND OTHER HYDROCARBONS 339 Toluene Xyleiies Mesitylene Cumene Cymene 344-349 Diphenyl

Diphenyl methane

350

Triphenylmethane

CHAPTER XXII. HALOGEN DERIVATIVES OF BENZENE AND ITS HOMOLOGUES Chlorobenzene

benzene

Bromobenzene lodoxybenzene

lodobenzene

lodoso-

Chlorotoluene

Benzyl

Chloride

357-361

CHAPTER XXIII. Nitrobenzene

CHAPTER XXIV. Aniline and

352

its

NITRO-COMPOUNDS Meta-dinitrobenzene

362

Nitrotoluenes

AMIDO-COMPOUNDS AND AMINES

367

Derivatives

Homologues of Aniline Alkylanilines.... Diphenyl amine and Triphenylamine Aromatic Amines Benzylamine

CHAPTER XXV.

365-367

373 376, 377

379

380

DIAZO-COMPOUNDS AND THEIR DERIVA-

TIVES

381

Diazoamido- and Amidoazo-compounds

386

Phenylhydrazine Azo- and Azoxy-compounds

388

CHAPTER XXVI. TIVES...,

390

SULPHONIC ACIDS AND THEIR DERIVA...392

XV

CONTENTS.

PAGE

PHENOLS

CHAPTER XXVII.

Monohydric Phenols

398

Phenol

Picric

Acid

404-409

Cresols

Dihydric Phenols Gatechol, Resorcinol, Hydroquinone..410,411 412 Trihydric Phenols

CHAPTER XXVIII. AROMATIC KETONES, AND QUINONES