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THE CHEMICAL SYNTHESIS

OF

VITAL PRODUCTS

THE CHEMICAL SYNTHESIS

OF

YITAL PRODUCTS

AND THE

INTER-RELATIONS BETWEEN ORGANIC
COMPOUNDS

RAPHAEL MELDOLA, F.R.S., V.P.C.S., F.I.C.

ETC,
PROFESSOR OF CHEMISTRY IN THE CITY AND GUILDS OF LONDON

TECHNICAL COLLEGE, FINSBURY

MEMBER OF THE FACULTY OF SCIENCE, UNIVERSITY OF LONDON,

AND OF THE teachers' REGISTRATION COUNCIL

VOL. I

HYDROCARBONS, ALCOHOLS AND PHENOLS, ALDEHYDES,
KETONES, CARBOHYDRATES AND GLUCOSIDES,
SULPHUR AND CYANOGEN COMPOUNDS,
CAMPHOR AND TERRENES, COLOURING-
MATTERS OF THE FLAVONE GROUP

LONDON

EDWARD ARNOLD

41 & 43 MADDOX STREET, BOND STREET, W.

1904

(All rights reserved)

f^'^lERAL

"V

Ki

f

\

PREFACE

The present work, the aim and objects of which are set forth in
the introductory chapter, originated in the year 1895, when, in the
course of preparing an address as President of the Chemical Section
of the British Association at Ipswich, I had occasion to take stock
of the present state of knowledge of synthetical chemistry \ I have
been encouraged from time to time by various chemical and bio-
logical friends, among whom I would especially mention Dr. Horace
Brown, Mr. Francis Darwin, Professors J. E. Green, "W. D. Halliburton,
Marshall Ward and "W. P. Wynne, to proceed with a compilation which,
in the midst of many other occupations and with very little leisure
time, has necessarily been a somewhat arduous task.

As it stands, this contribution to chemical literature represents the
result of fragmentary labour carried on at odd intervals during the last
nine years. From the nature of the conditions under which I have
been compelled to carry on the work, and in view of the wide domain
which it covers, it will, I am afraid, be found imperfect in many
respects, both with regard to omissions and inclusions. Encouraged,
however, by the belief that no similar work has hitherto been under-
taken, and that the time has arrived when a complete presentation of
the synthetical achievements of modern Organic Chemistry would be
of service to investigators here and abroad, I have decided to offer the
book in its present form for whatever value may be attached to it
as a work of reference. I am not without hope that it may be found
of service as a step towards the foundation of a more exact science of
Biochemistry.

Commencing in 1 895 with simply a tabular list of synthetical products,
it was soon found that the scope of the treatise would have to be con-
siderably enlarged in order to give an adequate account of the distribu-
tion in nature of the vital products and of the numerous synthetical
processes. Concurrently with the progress of the work a constant super-
vision over current literature had to be kept up in order that new
discoveries might be interpolated as they were announced. The rapid

* Rep. Brit. Assoc., Ipswich, 1895, p. 648.

145032

vi tREFACE

progress of discovery in this field must be held responsible for what
might be regarded as many anachronisms of treatment in the text
of the work.

It was my ambition at the outset to have kept pace with the
extension of our knowledge up to the completion of the whole work,
but the ever-increasing demands upon my time and energies have
compelled me to abandon this project and to consider the literature
as closed at the end of 1902. An Appendix comprises the more
important syntheses which have been effected during the printing
of this volume. In order to avoid unnecessary delay it has also
been ♦decided to issue the work in two volumes. The second of these
is in rough draft, and will be completed for publication as soon as
practicable.

If asked, as I frequently have been during the progress of the work,
what position synthetical chemistry occupies with respect to the
doctrines of Vitalism or Neovitalism, I think it advisable to place
upon record the opinion that the present achievements in the domain
of chemical synthesis famish no warrant for the belief that the
chemical processes of the living organism are in any sense transcen-
dental, or that they must be regarded as belonging to a class of special
material transformations which human science will never be able to
reproduce. Such an admission as the latter would be tantamount to
a proclamation of Neovitalism ; but the whole history of organic
synthesis, from the time when it was declared that organic com-
pounds could be obtained only by living agency, is opposed to any
such conclusion ^. But although the doctrine of a special ' vital
force ' has received its deathblow at the hands of modern science,
and although there is no warrant for the belief that the physics or
chemistry of animals and plants is ultra-scientific, yet it must not
be lost sight of that the S3nithetical possibilities of the living organism
have brought us face to face with modes of chemical action of which
we are as yet profoundly ignorant.

Those who consider that the triumphs of chemical synthesis have
finally disposed of Vitalism in any form will do well to bear in mind
that, until the chemist has shown that his synthetical methods are
identical with Nature's methods, there is just as much scope for
endeavouring to penetrate the chemical vital mysteries as there was
in the days when it was believed that every ' organic ' compound

* See on the otlier hand Dr. Lionel Si Beale's Introductory Lecture on 'The Founda-
tions of Medical Science,' delivered at King's College on Oct. 4, 1895. 'The Lancet,'
Oct. 19, 1895.

•Mt;'

PREFACE vii

required an animal or a plant for its production. If tliis is lost sight
of amidst the overwhelming mass of material accumulated by the
great army of workers in the field of Carbon Chemistry — if we have
produced thousands of compounds which do not and probably never
will be found to exist in living organisms ; if we have gone so far
beyond Nature as to make it appear unimportant whether an organic
compound is producible by vital chemistry or not, we are running the
risk of blockading whole regions of undiscovered modes of chemical
action by falling into the belief that known laboratory methods are
the equivalents of unknown vital methods.

The whole contents of this work will show how little warrant there
is for assuming such an attitude as the above. Eather than interpose
such a barrier to future investigation it would be better to return to
the initial position and to ask critically how far chemical synthesis
has as yet thrown light on the physiological processes of animals and
plants. It is evident that no synthetical process of a pyrogenic
character is of any particular biochemical interest. The fundamental
synthesis par excellence — the photosynthesis which plants are enabled
to accomplish, and in the course of which carbon dioxide is absorbed
by an organic compound and the product or products decomposed with
the liberation of oxygen — is as yet without a laboratory parallel. It
has also long been recognised that many hydroljrtic decompositions in
the living organism which result in the formation of definite products
are due to enzyme action. Such actions can generally be imitated by
laboratory methods, but the analogy between the natural and the
laboratory process disappears when it is considered that as yet no
organic nitrogenous hydrolysing agent of the nature of an enzyme
has ever been synthesised.

Still more recently has it been shown to be probable that certain
up-grade syntheses in the living organism, i. e. the coalescence of
simpler to more complex molecules, may also be the result of enzyme
action ^ Here again it may be said that the process might be imitated
by the use of chemical reagents, but the actual vital method has not
been reproduced in the laboratory. In emphasising these differences
between laboratory synthesis and synthesis in the living organism it
has appeared to me that some further stimulus might be given to bio-
chemical investigation, and this consideration has had much weight in

^ Croft Hill, Trans. Ch. Soc, 1898, 73, 634 ; Ber. Deutsch. ch. Gesell. 1901, 34, 1380 ;
Kastle and Loevenhart, Am. Ch. Journ. 1901, 26, 533 ; Hanriot, Comp. Rend. 1901, 132,
212; Emmerling, Ber. Deutsch. ch. Qesell. 1901, 34, 3810; Fischer and E. F. Arm-
strong, Sitzungsber. Pr. Akad. Berlin, 1901, 123 ; Ber. Deutsch. ch. Gesell. 1903,
35, 3144.

viii PREFACE

determining the completion of the task which was commenced nine
years ago.

The general survey of synthetical chemistry made possible by the
present work will help to bring into prominence the extreme im-
portance of the chemist and physiologist working hand in hand for
the future advancement of knowledge in this domain. Had time and
space permitted, I should have liked to discuss from the chemical point
of view the different hypotheses which have from time to time been
advanced by chemists and physiologists in explanation of the vital
synthesis of various compounds or groups of compounds. Such dis-
cussion, even had I possessed the necessary qualifications as a physiolo-
gist, would however have further delayed publication. This part of
the work may well be left over for future treatment, and will gain
rather than suffer in importance by allowing the facts to accumulate
and mature. I am not without hope that the present r4sum4 will
materially assist any fiiture discussion of the problems of Biochemistry.
As it stands, the work must be taken simply for what it professes to
be — a bare record of the synthetical achievements of generations of
workers arranged with a distinct biochemical bias.

At the outset I had also contemplated the interpolation of chemical
reactions and schemes, showing by the usual formulae the genetic
relationships between each vital product and its generators. This
likewise was abandoned when it was realised that such additions
would have expanded the work to an inordinate size, and^ further,
that the chemical mechanism of these transformations was often
imperfectly understood or had been explained only in a tentative
way. Here again, therefore, it has been thought better on the whole
to limit the work to statements of fact only, because, while the pro-
duction of one compound from another is an actual achievement, the
chemical explanation of the process must necessarily, with the develop-
ment of our theoretical notions, be subject to modification. As exer-
cises in chemical theory the pages of this compilation will be found to
furnish an overwhelming mass of material, and the original publica-
tions from which the facts have been gleaned can always be consulted
by those who wish to enter more ftilly into this aspect of the
subject.

In offering this book as a work of reference embodying only records
of facts, it must of course be understood that my task has been simply
that of a compiler, and that I do not hold myself responsible for any
of the statements made by investigators. It is not in any sense to be
regarded as a critical work, and my whole object has been simply to

PREFACE ix

bring practical workers, whether chemists, physiologists, or technolo-
gists, into communication with the various authorities quoted. For
this reason full references have been given for every record of the
natural occurrence of the compounds and of the methods employed
for their synthetical production. As it has been found impossible to
read every paper in full in the original, it is also necessary to caution
those who use this volume that many of the papers contained in diffi-
cultly accessible publications have been seen only in the abstracts
published in the ' Chemisches Central-Blatt,' the * Journal of the
Chemical Society,' the ' Journal of the Society of Chemical Industry,'
and in the ' Journal of the Federated Institutes of Brewing.' The
page given in the references must not therefore be quoted in all
cases without further verification as the actual page of the original
paper in which the statement occurs, but simply as a reference to
the page of the publication on which the original paper is to bo
found.

The vital products recognised in this volume are those compounds
of definite chemical composition which are known to be produced as
the result of the vital activities — for the most part normal — of animals
and plants, including of course the heterogeneous assemblage of micro-
organisms. As explained in the introductory chapter, considerable
latitude has been allowed in the interpretation of the term ' vital
product ' ; but it is to be understood that the syntheses of these
compounds as recorded are in every case comjalete in the chemical
sense. It is necessary to call attention to this point because in many
instances it may appear that where one vital product (Z) has been re-
corded as a generator of other vital products {A, B, &c.), the compound
X having originally been sjoithesised from A or B, that we have got
out of X nothing more than was originally put into it, and that there
has accordingly been presented a case of ' circular reasoning,' or, in
other wordsj an incomplete synthesis. In all such cases, however, it
will be found that X can be obtained from generators other than A or
B, and that the synthesis of X is therefore independently complete.
The importance of recording the inter-relations of Z", -4, and B is fully
explained in the subsequent pages.

A compilation such as the present would have been for me an im-
possible undertaking without the free use of the standard works of
reference, and I must in the first place acknowledge my indebtedness
to Beilstein's ' Handbuch der organischen Chemie ' and its Supple-
ments ; to Watts's ' Dictionary of Chemistry,' Morley and Muir ; to
Thorpe's ' Dictionary of Applied Chemistry ' ; and to Roscoe-Schor-

X PREFACE

lemmer's ' Lehrbuch der organisclien Chemie/ by Briihl and his
collaborators. In addition to these general works, many treatises
dealing with special branches of the subject have been found of
extreme value: —

For physiological chemistry, ' Lehrbuch der physiologischen Chemie,'
by Hammarsten, and the American translation by Mandel ; also ' The
Chemical Basis of the Animal Body,' by Sheridan Lea.

For enzymes, ' The Soluble Ferments and Fermentation,' by
J. Reynolds Green.

For fermentation, ' Die Mikroorganismen der Garungsindustrie,' by
Jorgensen ; also ' Technical Mycology/ by Franz Lafar, German and
English editions ; ' Die Garungsorganismen,' by Klocker ; ' Die Fer-
mente und ihre Wirkungen,' by Oppenheimer ; ' Die Zersetzung stick-
stofiffreier organischer Substanzen durch Bakterien,' by Emmerling.

For terpenes, ' The Chemistry of the Terpenes,'' by Heusler, trans-
lation by Pond.

For ethereal oils, ' Die aetherischen Oele,' by Gildemeister and
Hoffmann ; also ' Les Huiles essentielles,' by Charabot, Dupont, and
Pillet, and ' Odorographia,' by Sawer.

For carbohydrates, ' Die Chemie der Zuckerarten,' by E. 0. v. Lipp-
mann; * Kurzes Handbuch der Kohlenhydrate,' by Tollens ;. 'Les
Sucres et leurs principaux derives,' by Maquenne.

For glucosides, ' Die Glykoside,' by Van Rijn.

For colouring-matters, ' Die Chemie der natiirlichen Farbstoffe,' by
Hans Bupe.

For alkaloids, ' Ueber die Erforschung der Konstitution und die Ver-
suche zur Synthese wichtiger Pflanzenalkaloide,' by Julius Schmidt.

For ptomaines, ' Ueber Ptomaine,' by Brieger.

Some of the sections in the German edition of Roscoe and Schor-
lemmer's treatise above referred to are in themselves special mono-
graphs, and some of the lectures in the Stuttgart series, entitled
' Sammlung chemischer und chemisch-technischer Vortrage,' have
also been found of much value, and are quoted under their respective
titles.

Mr. E. M. Holmes, F.L.S., has been good enough to revise the lists
of plants referred to in the present volume, and I desire to express
my thanks to this well-known authority for the valuable assistance
thus given.

R. M.

Jillt/y 1904.

CONTENTS

PAGE

List of Synthetical Products , . . . . xiii

Abbreviated Titles of Publications quoted xv

INTRODUCTORY 1

I. Historical 1

II. Nature of the Compounds eegisteked as Vital Products ... 8

III. Organic Chemistry from the Biocehtric Standpoint .... 6

IV. Chemical Synthesis from the Biocentric Standpoint .... 9
V. Advantages of the Biocentric Treatment of Synthetical Csimistry 14

HYDROCARBONS 21

ALCOHOLS AND TERPENE ALCOHOLS • .... 40

KETONE ALCOHOLS 93

GLYCOLS AND POLYHYDRIC ALCOHOLS 95

AROMATIC ALCOHOLS AND PHENOLS ' . . .107

ALDEHYDES AND KETONES : FATTY GROUP 169

AROMATIC ALDEHYDES AND KETONES 205

CARBOHYDRATES AND GLUC03IDES 242

SULPHUR COMPOUNDS 251

CYANOGEN COMPOUNDS 262

APPENDIX

Camphor and Terpene Group 271

Flavonb Group 275

INDEX 295

ERRATA AND CORRIGENDA 339

LIST OF SYNTHETICAL PRODUCTS

Hydrocarbons.

1. Methane. 2. Normal Heptane.

3. Normal Pentadecane.

4. Normal Heptacosane.

5. Normal Hentriacontane.

6. Cymene. 7. Styrene.

8. Metastyrene.

9. Dipentene and Limonene.

10. Terpinene.

11. Laevo-isoterpene.

12. Naphthalene.

Alcohols and Terpene Alcohols.

13. Methyl Alcohol.

14. Ethyl Alcohol.

15. Normal Propyl Alcohol.

16. Isopropyl Alcohol.
IT. Normal Butyl Alcohol.

18. Isobutyl Alcohol.

19. Tertiary Butyl Alcohol.

20. Normal Primary Amyl Alcohol.

21. Normal Secondary Amyl Alcohol.

22. Isoamyl Alcohol.

23. Normal Hexyl Alcohol.

24. Isohexyl Alcohol.

25. Active Hexyl Alcohol.

26. Normal Heptyl Alcohol.

27. Isoheptyl Alcohol.

28. Normal Primary Octyl Alcohol.

29. Nonyl Alcohol.

30. Secondary Hendecatyl Alcohol.

31. Normal Primary Dodecyl Alcohol.

32. Normal Primary Tetradecyl Alcohol.

33.
34.
35.
36.
38.
40.
42.

Cetyl Alcohol.

Octadecyl Alcohol.

Dimethylheptenol.

Geraniol.

Citronellol.

Cineole.

Isopulegol.

37. Linalool.
39. Terpineol.
41. Menthol.

Ketone Alcohols.

43. Acetol or Acetyl Carbinol. 44. Methylacetyl Carbinol.

Glycols and Polyhydric Alcohols.

45. Ethylene Glycol. 49.

46. Trimethylene or Normal Propylene 50.

Glycol. 51.

47. Isobutylone Glycol. 52.

48. Glycerol. 53.

Glycerophosphoric Acid.

Erythritol.

Mannitol.

Sorbitol.

Mannoheptol or Perseitol.

Aromatic Alcohols and Phenols.

54. Benzyl Alcohol. 56. Saligenin.

56. Parahydroxybenzyl Alcohol.

57. Phenylethyl Alcohol.

58. Methylphenyl Carbinol.

59. Phenylpropyl Alcohol.

60. Phenol. 61. Orthocresol.
62. Metacresol. 63. Paracresol.

64. Phlorol.

65. Meta-ethylphenol. 66. Carvacrol.
67. Thymol. 68. Anethole.
69. Catechol. 70. Resorcinol.
71. Quinol. 72. Toluquinol.

73. Quinol Methyl Ether.

74. Quinol Ethyl Ether.

75. Orcinol. 76. Cresorcinol.
77. /3-Orcinol. 78. Mesorcinol.

79. Isoeugenol.

80. Methylisoeugenol.

81. Methyleugenol. 82. Thymoquinol.

83. Dimethylthymoquinol.

84. Pyrogallol. 85. Hydroxyquinol.
86. Phloroglucinol. 87. Antiarol.

88. Iretol. 89. Asarone.

90. Hydrojuglone.

XIV

LIST OF SYNTHETICAL PRODUCTS

Aldehydes and Ketones: Fatty Group.

91. Formic Aldehyde.

82. Acetic Aldehyde.

83. Acetal.

84. Butyric Aldehyde.

85. Valeric Aldehyde.

86. Hexoic Aldehyde.

87. Heptoic Aldehyde.

88. Octoic Aldehyde.

99. Ennoic or Nonoic Aldehyde.

100. Decoic Aldehyde,

101. Acrolein.

102. Crotonic Aldehyde.

103. Tiglic Aldehyde.

104. Citral. 105. Citronellal.

106. Acetone.

107. Methyl-n-amyl Ketone.

108. Methyl-n-heptyl Ketone.

109. Methyl-n-nonyl Ketone.

110. Methyl-n-decyl Ketone.

111. Methylheptenone.

112. Phorone.

113. Diacetyl.

Aromatic Aldehydes and Ketones.

114. Benzoic Aldehyde.

115. Hydrocinnamic Aldehyde.

116. Cumic Aldehyde.

117. Salicylic Aldehyde.

118. Metahydroxybenzoic Aldehyde.

119. Parahydroxybenzoic Aldehyde.

120. Anisic Aldehyde.

121. Vanillin. 122. Piperonal.

123. Cinnamic Aldehyde.

124. Orthocoumaric Aldehyde Methyl

Ether.

125. Asaryl Aldehyde.

126. Furfural. 127. Carvone.
128. Pulegone. 129. Menthone.
130. Orthohydroxyacetophenone.

131. Piceol or Parahydroxyacetophenone.

132. Ketocoumaran. 133. Poeonol.

134. Hydrocotoin.

135. Methylhydrocotoin.

136. Euxanthone. 137. Gentisin.
138. Chrysin. 139. Tectochrysin.
140. Apigenin. 141. Luteolin.

142. Quinone.

143. Thymoquinone.

144. Metahydroxyanthraquinone.

145. Alizarin.

146. Purpuroxanthin.

147. Hystazarin. 148. Anthragallol.

149. Purpurin.

150. Methylpurpuroxanthin.

Carbohydrates and Glucosides.

151.

Dihydroxyacetone.

156.

d-Mannose.

152.

d-Erythrulose.

157.

Salicin.

153.

d-Arabinose.

158.

Populin.

154.

Dextrose. 155. Lsevulose.

159.

Methylarbutin,

Sulphur Compounds.

160. Carbon Disulphide.

161. Methyl Mercaptan.

162. Normal Butyl Mercaptan.

163. Methyl Sulphide.

164. Ethyl Sulphide.

165. Secondary Butyl Isothiocyanate.

166. Allyl Isothiocyanate.

167. Crotonyl Isothiocyanate.

168. Angelyl Isothiocyanate.

169. Benzyl Isothiocyanate.

170. Phenylethyl Isothiocyanate.

171. Parahydroxybenzyl Isothiocyanate.

172. Hydrogen Cyanide.

Cyanogen Compounds.

173. Isocyanacetic Acid.

174. Thiocyanic Acid.

176. Camphor.

Camphor and Terpene Group.

176. Borneol. 177. Camphene.

178. Menthene.

179. FJsetin.

Flavone Group.

180. Quercetin.

181. Kampherol.

ABBREVIATED TITLES OF PUBLICATIONS QUOTED

Bel

American Chemical Journal

American Journal of Pharmacy

American Journal of Physiology

American Journal of Science

Annalen der Chemie (Liebig's)

Annalen der Physik, &c,, Gilbert

Annalen der Physik, &c., Poggendorff

Annales Agronomiques

Annales de Chimie et de Physique

Annales de I'lnstitut Pasteur .

Annales des Sciences Naturelles

Annals of Botany

Ai'chiv fiir experimentelle Pathologie und Pharmakologie

Archiv fiir die gesamte Phyaiologie des Menschen und der

Thiere

Ai'chiv fiir Hygiene

Archiv der Pharmazie

Atti della Reale Accademia dei Lincei : Rendiconti
Beitrage zur chemischen Physiol ogie und Pathologie
Berichte der Deutschen botanischen Gesellschaft .
Berichte der Deutschen chemischen Gesellschaft .
Berichte der Deutschen pharmazeutischen Gesellschaft
Biedermann's Centralblatt fiir Agrikulturchemie, &o.
Bollettino Chimico Farmaceutico
Botanische Zeitung ,
Bulletin de I'Academie Royale des Sciences, &c, de

gique

Bulletin de I'Association Beige des Chimistes .

Bulletin de la Soci6t6 Chimique de Paris

Bulletin de la Soci6t6 Mycologique de France .

Centralblatt der medizinischen Wissenschaften

Centralblatt fiir Bakteriologie und Parasitenkunde,

Centralblatt fiir Physiologie

Chemical News .

Chemiker-Zeitung

Chemische Industrie, Die .

Chemisches Central-Blatt

Chemist and Druggist, The

Comptes Rendus hebdomadaires des Stances de I'Academie

des Sciences

Dingler's polytechnisches Journal .

Electrical Review

Elektrochemische Zeitschrift ....
Gazzetta chimica Italiana ....

Geschaftsbericht von Schimmel & Co., Leipzig
Jahresbericht iiber die Fortschritte der Chemie, &c,

zelius) .

Jahresbericht iiber die Fortschritte der Chemie, &c
Journal of the American Chemical Society
Journal of the Chemical Society of London
Journal fiir Chemie und Physik, Gehlen .
Journal of the Federated Institutes of Brewing
Journal de Pharmacie et de Chimie .

&c.

(Ber

Am. Ch. Journ.
■■ Am. Journ. Pharm.
= Am. Journ. Physiol.
= Am. Journ. Sci.
= Ann.
= Gilb. Ann.

■ Pogg. Ann.

: Ann. Agronom.

: Ann. Chim.

: Ann. Inst. Past.

■ Ann. Sci, Nat.
: Ann. Bot.

Arch. exp. Path.

: Pfluger's Arch.
: Arch. Hyg.

Arch. Pharm.
■■ Atti Real. Accad.

Beit. ch. Physiol, u. Path,
■■ Ber. Deutsch. bot, Gesell.
= Ber.

Ber. Deutsch. pharm. Gesell.
' Bied, Centr.
= Boll. Ch. Farm.
= Bot. Zeit.

= Bull. Acad. Roy. Belg.

: Bull. Assoc. Belg.

: Bull. Soc.

= Bull, Soc, Mycol,

: Centr. med. Wiss.

= Centr. Bakter.

= Centr, Physiol.

= Ch. News.

= Ch. Zeit.

= Ch. Ind.

: Ch. Centr.

= Ch. Drug.

= Comp. Rend.

= Ding. poly. Journ.

= Elect. Rev.

= Elektro. Zeit.

= Gazz.

= Schimmel's Ber.

= Berz. Jahresber.
» Jahresber.
: Journ. Am. Ch. Soc.
= Journ. Ch. Soc.
: Gehlen's Journ.
: Journ. Fed. Inst.
: Journ. Pharm.

xvi ABBREVIATED TITLES OF PUBLICATIONS QUOTED

Journal fiir praktische Chemie

Journal of the Russian Physical and Chemical Society (in

Russian) ......

Journal of Physiology

Journal of the Society of Chemical Industry

Landwirtschaftlichen Versuchs-Stationen, Die

Monatshefte fiir Chemie .

Moniteur Scientifique

Pharmaceutical Archives .

Pharmaceutical Journal .

Pharmaceutical Review

Pharmaceutische Rundschau

Pharmazeutische Zeitung .

Philosophical Magazine

Philosophical Transactions of the Royal Society

Proceedings of the Chemical Society of London

Proceedings of the Physiological Society .

Proceedings of the Royal Society of London .

Recueil des Travaux Chimiques des Pays-Bas .

Revue de Chimie Industrielle ....

Revue g^n^rale de Chimie pure et appliqu^e .
Sitzungsberichte d. k. Preussischen Akademie der Wis

senschaften, Berlin

Stazioni sperimentali agrarie Italiane, Le

Transactions of the Chemical Society of London

Transactions of the Pathological Society

Wochenschrift fiir Brauerei

Zeitschrift fiir analytische Chemie

Zeitschrift fiir angewandte Chemie

Zeitschrift fiir anorganische Chemie

Zeitschrift fiir Biologie

Zeitschrift fur Chemie

Zeitschrift fiir die chemische Industxde

Zeitschrift fiir Elektrochemie .

Zeitschrift fiir das gesamte Brauwesen

Zeitschrift fiir physikalische Chemie

Zeitschrift fiir physiologische Chemie (Hoppe-Seyler's

and subsequently) ....
Zeitschrift fiir Zucker-Industrie in Bohmen

= Journ. pr. Ch.

= Journ. Russ. Soc.

= Journ. Physiol.

= Journ. Soc. Ch. Ind.

:^ Landw. Versuchs-Sta.

= Monats.

= Mon, Sci.

= Pharm. Arch.

= Pharm. Journ.

= Pharm. Rev.

= Pharm. Rund.

= Pharm. Zeit.

= Phil. Mag.

= Phil. Trans,

= Proc. Ch. Soc.

= Proc. Physiol. Soc.

= Proc. Roy. Soc.

= Rec. Tr. Ch.

= Rev. Ch. Ind.

= Rev. gdn. de Chim.

= Sitz. Pr. Akad.
= Staz. sper. agrar.
= Trans. Ch. Soc.
= Trans. Path. Soc.
= Woch. Brau.
= Zeit. anal. Ch.
= Zeit. angew. Ch.
= Zeit. an org. Ch.
= Zeit. Biol.
= Zeit. Ch.
= Zeit. ch. Ind.
= Zeit. Elektroch.
= Zeit. ges. Brau.
= Zeit. physik. Ch.

= Zeit. physiol. Ch.

= Zeit. Zucker-Ind. Bohm.

Of THt '^

VNIVER«rTY

INTRODUCTORY

I. HISTORICAL

The history of organic chemical synthesis has been so frequently
dealt with by previous writers that it is unnecessary to discuss the
subject in detail from this point of view. In so far as the existence of
a special ' vital force ' was considered necessary to explain the forma-
tion of organic compounds by the living organism, it is generally
conceded that Wohler, by his synthesis of urea from ammonium
cyanate in 1828, was the first to deliver a serious blow against the
doctrine in question. As a pioneer in the same field our own country-
man, Henry HenneU, must, as I ventured to plead in 1895 ^, be accorded
a place not inferior to that of Wohler as being among the first to
produce an organic compound independently of the living organism.
The English chemist succeeded in synthesising alcohol from olefiant
gas at practically the same time that his great German contemporary
had excited the interest of the whole chemical world by his synthesis
of urea.

Important as was the latter discovery, it must not be forgotten that
at the time of its announcement the synthesis was not what would now
be termed ' complete,' because the cyanide from which the cyanate was
prepared was then obtained by fusing nitrogenous organic matter with
an alkaline carbonate, so that it might have been said that the carbon
and nitrogen were both of vital origin. The synthesis of alcohol by
Hennell was equally incomplete, because the olefiant gas had been
obtained by the pyrogenic decomposition of organic material, viz. oil,
so that in this respect the two syntheses were on precisely the same
level.

Since alcohol was not in 1828 recognised as a vital product in the
same sense that urea was so regarded, it will be easily understood why
the synthesis of the former failed to arouse any particular interest at
the time ; the discovery did not clash with the current notions of
Vitalism. As Hennell's contribution to chemical synthesis had of late
years been allowed to fall into oblivion, I thought it desirable in 1 895
to remind chemists once again of his claim to take rank among the
early pioneers in this field. The plea has not, however, been allowed
to pass unchallenged, for no less an authority than M. Berthelot, one
of the most active and distinguished among the later workers at the
subject of chemical synthesis, has denied Hennell's claim to have been
the first to synthesise alcohol \ Under these circumstances it will be

^ Brit. Assoc. Rep. Ipswich, 1895, p. 649. * Comp. Rend. 1899, 128, 862.

B

2 ^ INTRODUCTORY

perhaps desirable to state more fully the facts upon which the English
chemist's claim is based : —

In 1826 Faraday published a paper entitled, ' On new Compounds
of Carbon and Hydrogen, and on the Products of the Decomposition of
Oil by Heat ^,' in the course of which he states : ' I find also that
sulphuric acid will condense and combine with defiant gas, no carbon
being separated, or sulphurous or carbonic acid being formed, and this
absorption has in the course of eighteen days amounted to 847 volumes
of defiant gas to one volume of sulphuric acid. The acid produced
combines with bases, &c., forming peculiar salts, which I have not yet
had time, but which it is my intention, to examine.'

The following year, on March 9, Brande communicated to the
Royal Society a paper by Hennell bearing the title : ' On the Mutual
Action of Sulphuric Acid and Alcohol, with Observations on the Com-
position and Properties of the resulting Compound ^.' In this paper
the author shows that he possessed very clear notions concerning the
nature of the sulphovinates, and he gives analyses of ' oil of wine ' as
well as of the potassium salt of sulphovinic acid. He refers to some
sulphuric acid which had been given to him by Faraday as having
absorbed eighty times its volume of defiant gas from oil gas, this being
no doubt the specimen mentioned by Faraday in the previous paper.
He identified sulphovinic acid in the foregoing preparation, and proved
it by a comparison of the potassium salt with potassium sulphovinate
obtained from 'oil of wine ^.' It is true that he gives no analysis of
the potassium salt from Faraday's acid, but he had already shown
evidence of his familiarity with this salt, and he declares the identity
of the salts from the two sources in most distinct terms.

It is impossible to arrive at any other conclusion than that Hennell
was aware that he had obtained sulphovinic acid from olefiant gas.
In 1828 a second paper was communicated to the Royal Society (read
June 1 9) under the title : ' On the Mutual Action of Sulphuric Acid
and Alcohol, and on the Nature of the Process hj which Ether is
formed ^.' In this second paper, among other experiments, he distilled
sulphovinic acid with water and a little sulphuric acid, and proved
that it was decomposed into sulphuric acid and alcohol : and not only
this, but he also showed that the whole of the alcohol and sulphuric
acid which originally entered into the composition of the sulphovinic
acid could be recovered by distillation with water. It is true that the
sulphovinic acid used in his second series of researches was not
obtained from olefiant gas, but this cumbersome mode of preparation
was obviously unnecessary in view of the circumstance that he had
already satisfied himself that the products were identical. There can
be no reasonable doubt that the claim advanced on behalf of Hennell
as the first to synthesise alcohol from olefiant gas must be admitted to

* Phil. Trans. 1825, P- 44^- ' Loc. cit. p. 245.

« Ibid. 1836, Part III, p. 240. * Ibid. 1828, p. 365.

HISTORICAL 3>

be fuUy borne out by the critical examination of the papers referred-
to, and this conclusion has recently been upheld by Fritzsche, who
also points out that these results were known to contemporary Con-
tinental chemists \

11. NATURE OF THE COMPOUNDS REGISTEEED AS
VITAL PRODUCTS

The term 'vital product' has been adopted in preference to the
designation ' natural product,' which first suggested itself because the
latter, strictly interpreted, includes also mineral or inorganic com-
pounds. In working out the details presented in the following pages
much consideration has had to be given to the question as to which
compounds should be regarded as of vital origin. In works dealing
with organic or physiological chemistry it is generally stated or implied
that such compounds are formed by the living plant or animal, as the
result of the physiological activities of its various organs or tissues.
It is also understood, in accordance with modern views, that the seat of
such physiological activity is the cell. Although this conception of the
nature of a vital product at first sight appears to bring the term within
easily definable limits, it soon became evident when the individual
products came under consideration that from the chemical point of
view, apart from the question of the physiological mechanism by which
the compounds are formed, some more precise understanding would
have to be arrived at. Thus in many cases it is necessary to register
a vital product not under one heading as a simple molecule, but under
two or more headings if the compound is obviously built up of, and is
easily resolvable into, two or more compounds of less molecular com-
plexity.

By way of illustration, it is doubtful whether either methyl alcohol
or salicylic acid occurs in nature in the free state ; but the ester,
methyl salicylate, is the chief constituent of the oil of wintergreen
(Gaultheria), and is contained in the ethereal oils of large numbers of
other plants. It is further probable that methyl salicylate does not
itself exist in the plants in the free state, but in the form of a glucoside,
gaultherin. The glucoside is therefore, strictly speaking, alone entitled
to registration. Similarly with respect to alizarin, which does not
exist as such in the plant, but in the form of the glucoside ruberythric
acid. In cases such as these, which are typical of a large class, the
product has been regarded as having been synthesised, and compounds
such as methyl alcohol, salicylic acid, and alizarin have been regarded

1 Journ. pr. Ch, [2] 65, 597. The references to * PoggendorfTs Annalen ' given are 9, 21 ;
14, 282. The latter, which relates to Hennell's second paper, is given also in Beilstein's
' Handbuch,' VoL I, p. 222, but, strangely enough, has been corrected in the Supplement
(Vol. I, p. 72) so as to make it appear as though M. Berthelot's reclamation had been
admitted.

B 2

4 INTRODUCTORY

as vital products, although the glucoside itself may not have been
hitherto synthesised in all cases.

The necessity for this treatment will be recognised when it is con-
sidered that the constituent atomic complexes of easily resolvable mole-
cules are very likely hereafter to be found in the free state in nature,
and in many instances are actually known, as in the case of glucose,
to exist as individual compounds. Thus, to mention another example,
hydroquinone (quinol) [7l] was at iirst entered as occurring only in
the form of the glucoside arbutin. "While this work was in course
of preparation it was announced by Hesse (Ann. 290, 3 17), that this
phenol occurs in the South African 'sugar bush,' Protea mellifera.
As the products from animals and plants are more and more investi-
gated it is certain that such instances will be multiplied.

On considering the published records as to the occurrence of vital
products it also became evident that in very large numbers of cases
it was extremely doubtful in what form the compound was actually
produced by the animal or plant. In other words, it is uncertain
whether many compounds isolated, identified, and recorded as of
natural occurrence may not have resulted from the resolution of more
complex and unstable molecules by the action of enzymes or of the
chemical reagents employed in their extraction — whether in fact they
may not have resulted from secondary changes or decompositions
taking place after removal from the organism. In view of this state
of affairs it must be admitted that a vital product is not so easily
definable as appears at first sight, and that in the present condition
of knowledge it is not always possible to say whether a particular
compound is of biochemical origin or whether it is a secondary
product. Under these circumstances it has been deemed advisable,
in order to make this work as comprehensive as possible, to assume
that the complex of atoms present in the molecule of the vital product
as isolated is of biochemical origin, even if the compound is not
directly synthesised as such by the animal or plant.

This view will no doubt commend itself to both chemists and
physiologists. From the chemical standpoint it is certainly justifiable
to believe that if a complex molecule is so unstable as to break down
readily into simpler molecules, the atomic groupings present in the
latter pre-exist in their generator. Moreover, molecular instability is
a phenomenon of degree, and it has been found practically impossible
to define the conception narrowly in terms of the agents necessary for
causing the resolution of the compounds. It is not possible, for
example, to draw a hard and fast line between, on the one hand, the
action of enzymes and of acids or alkalies at ordinary temperatures,
and, on the other hand, the action of acids or alkalies at high tempera-
tures, or even, in the case of the more stable cyclic compounds, the
action of fused alkali. For this reason the conception of a vital
product has been enlarged so as to include every atomic complex

NATURE OF THE COMPOUNDS 5

which, without unduly straining the facts, there is reason for believing
to be present in the products resulting from vital synthesis, the
other condition for ensuring inclusion in this work being of course
that the complex has been synthesised in the laboratory. The question
whether the agent which reveals the presence of the complex is a mild
or a violent one is for the purposes of the present treatment con-
sidered only as of subordinate importance.

The liberal extension of the term ' vital product ' thus claimed has,
it is hoped, been used judiciously, and not pushed to an unwarranted
degree. All that can be said is that in the present state of knowledge,
where so much doubt surrounds the chemical history of the antece-
dents of vital products, full advantage has been taken of this doubt on
behalf of this compilation. Should it be proved hereafter that any
particular compound is the result of secondary synthesis, and that its
atomic complex is not formed by the living organism, it can easily be
removed from the list.

The importance of including every possible complex, whether it is
obviously present in the vital product or whether its presence is
inferred only, will be more fully recognised if it is pointed out
that the inferred existence of any particular group of atoms in the
molecule becomes converted into a demonstrated fact, when, as in
many of the cases recorded, the compound has been produced syn-
thetically from a generator which is known to contain the group in
question. A few examples will serve more fully to illustrate the nature
of the difficulties which have had to be met, and will furnish further
justification for the mode of treatment adopted : —

Furfural [l26] has been found in the aqueous distillate from many
ethereal oils from plants as well as in some of the oils. It has been
detected also in certain fermented liquors, such as whisky, &c. It is
doubtful whether this compound is really a biochemical product, since
it may have been produced by the breaking down of more complex
antecedents (pentoses, &c.) during the process of distillation. This
question has been much discussed of late by technical chemists, and
the balance of opinion is against its being a product of alcoholic
fermentation. Nevertheless this aldehyde has been included because
it may be fairly said that the complex of atoms which so easily closes
up with the formation of this heterocyclic molecule pre-exists in the
vital compound or compounds which are its generators. Should any
of these generators be hereafter synthesised it is possible that furfural
may be made use of in their synthesis.

Again, orcinol [75] has not yet been found in the free state in any
plant, but many complex acids found in lichens yield this phenol with
varying degrees of facility, from simply boiling with water, alkaline
carbonates, or baryta water, to fusion with caustic alkali. It is there-
fore evident that the orcinol complex is contained in these lichen acids,
and should any of these compounds ever be synthesised it is certain

6 INTRODUCTORY

that orcinol or a derivative would have to be as it were built into the
structure of the molecule. This phenol, which has of course been
completely synthesised, has therefore been included among the vital
products, and it is not at all improbable — in view of the facility with
which some of the lichen acids furnish the compound by chemical
treatment and even by bacterial action — that it may yet be found in
the vegetable kingdom.

Resorcinol [70] presents a similar case, only the evidence that the
complex is contained in vital products such as pseonol [133], euxan-
thone [136], &c., has been in the first place obtained by the more
violent method of fusing with alkali. It is hardly likely that this
phenol will be ever found in the free state in plants, but it must
nevertheless be regarded as a vital product, since it has been proved by
synthesis as well as by the action of heated alkali that resorcinol is one
of the generators of both pseonol and euxanthone.

For similar reasons the pyrogallol [84] complex is regarded as
being present in gallic acid, &c., the phloroglucinol [86] complex in
many colouring-matters of the pyrone group, and so forth. Another
instructive example is furnished by hydrojuglone [90] from the
walnut, Juglans regia. This compound is known to be a derivative
of naphthalene, and as it contains the naphthalene complex the
syntheses of this hydrocarbon are given in connexion with the phenol.
While these pages were undergoing final revision it was announced
by V. Soden and E-ojahn (Pharm. Zeit. 47, 779) that the hydrocarbon
itself had been found in certain vegetable ethereal oils.

III. ORGANIC CHEMISTRY FROM THE BIOCENTRIC

STANDPOINT

The general tendency of the present work is to bring Carbon
Chemistry back to the point from which it departed three-quarters
of a century ago, when the leading discovery of the synthesis of urea
by Wohler showed that organic compounds could be formed without
vital intervention. Without desiring to reopen the question of the
existence of a special ' vital force,' it may be well to call the attention
of those physiologists who appeal to the achievements of synthetical
chemistry as conclusive evidence against the existence of such a force
to the fact — so distinctly brought out by the summary of experimental
results herein recorded — that the testimony of pure chemistry cannot,
as it at present stands, be legitimately interpreted into a direct nega-
tion of Vitalism in any form. This negation may, and probably will,
be made possible in the future when our chemical methods have been
made to approximate more closely to the vital methods.

In the meantime it must not be forgotten that there is at present
but little reason for believing that our laboratory methods have much
analogy with the processes which go on in the living organism. All

ORGANIC CHEMISTRY 7

that can be said is that the chemist has realised that which vital
chemistry had been realising long before his entry into the field — that
such and such atomic groupings are stable and capable of free and
definite existence, and to this knowledge he has added the fact that
vast numbers of other atomic groupings are also capable of free and
definite existence. An impartial survey of the facts will, however,
serve to show how far we still are from realising vital chemical pro-
cesses in the laboratory. The fact that alcohol can be synthesised
from carbon and hydrogen through acetylene, &c., has no direct
bearing on the formation of alcohol from sugar by the zymase of the
yeast-plant. When we can transform sugar into alcohol in the
laboratory at ordinary temperatures by the action of a synthesised
nitrogenous organic compound ; when we can convert glucose into
citric acid in the same way that Citi^omyces can effect this transforma-
tion ; when we can build up heptane, or cymene, or styrene, or when
we can produce the naphthalene or anthracene complex in the labora-
tory by the interaction of organic compounds at ordinary temperatures,
then may the chemist proclaim with confidence that there is no longer
any mystery in vital chemistry.

It is clear that if chemistry be regarded from what may be called
the biocentric point of view, the complete synthesis of an organic
compound by pyrogenic methods or by the action of violent reagents
is of comparatively little importance. On the other hand, the trans-
formation of one vital product into another by laboratory processes —
even if these are at present not actually analogous to the physiological
processes — may furnish information of the highest biochemical signifi-
cance. The treatment of organic chemistry in this work has accord-
ingly been entirely subordinated to the biocentric view of the subject.
The book is not to be regarded simply as a catalogue of synthetical
products and processes ; neither does it profess to be a practical
laboratory guide to the preparation of organic compounds, although,
by virtue of its contents, it necessarily comprises both kinds of
information. Physiologists will find herein a record of the achieve-
ments of synthetical chemistry, chemists will be enabled to ascertain
the natural mode of occurrence of organic compounds, and technologists
will no doubt find it useful to have the chemical generators of such
products as are of industrial value brought conspicuously under notice.

The importance of emphasising the relationships between the vital
products themselves will be realised when it is pointed out that the
future development of our knowledge of the chemistry of the living
organism must depend largely upon the detection of the chemical
antecedents of these products. The discussion of the results of
chemical synthesis from this point of view does not come within the
scope of the present work, but belongs — at any rate in the present
state of knowledge — rather to the province of physiology. It is for
this reason that the necessity for the chemist and physiologist working

8 INTRODUCTORY

hand in hand has been insisted upon so frequently and so emphatically
of late years by both classes of workers ^. The publication of this
volume may possibly contribute towards this much-desired rajjprocTie-
ment between the sciences.

So far as modern science has been enabled to deal with the question
of the mode of origin of these vital products in the living organism, it
must be confessed that hitherto but little progress has been made.
The chemist at the present time may be said to be far in advance of
the physiologist in his contributions to biochemistry. "While large
numbers of definite vital products have been isolated, identified, and
synthesised in the laboratory, the course of development of these com-
pounds in the organism can hardly yet be said to have been satis-
factorily traced in any instance. The practical difficulties associated
with this kind of investigation are confessedly very great, but it must
be apparent to chemists that the study of the evolution of organic
compounds in the animal or plant has the most pressing claims upon
the attention of physiologists. With the solution of the problems
furnished by such studies our knowledge of vital chemistry, and
through this of vital processes generally, is certain to advance by great
strides. Perhaps it is not going too far to say that the whole future
development of physiological chemistry lies in this direction.

The chemical evolution in the living organism of one definite
compound of known constitution, if successfully traced, might lead to
the discovery of fundamental principles. It certainly must strike
chemists as being somewhat remarkable, in view of the importance of
the investigation of such problems, that more systematic efforts have
not been concentrated upon them by physiologists. The difficulties
surrounding the determination of the origin of such a comparatively
simple product as urea in the animal body or oxalic acid in plants,
or, again, the study of the origin and fate of amino-acids in the
growing plant, which has received so much attention of late years
from Schulze and others, will only serve to emphasise the necessity
for the vigorous prosecution of research in this field. The evolution
of definite products in the growing plant would appear to offer special
facilities for investigation, because the course of development of the •
compounds might be followed by collecting and investigating such
well-characterised substances as are contained in many ethereal oils at
different stages in the life-history of the plant or of the part of the
plant which yields the oil. Some progress in this direction has been
made in France by Charabot, whose views concerning the development
of the terpene alcohols and ketones, which are referred to under these
respective groups, are worthy of special notice as examples of the
results of a kind of pioneering work which is much required. Such
research constitutes the common meeting ground of chemistry and

' See, for instance, Prof. W. D. Halliburton's address to the Section of Physiology at
the Belfast meeting of the British Association in 1902. Brit. Assoc. Kep. 1902, p. 771.

ORGANIC CHEMISTRY 9

physiology, and if the publication of this work should give an impetus
to further activity in this region one of its main objects will have been
achieved.

The development of physiology along chemical lines is bound to
take place at an increasing rate with the progress of discovery, and in
the future the two sciences must necessarily become more and more
interdependent. If, some decades hence, a work on similar lines to
the present should ever be compiled, it may be anticipated with confi-
dence that the laboratory methods for synthesising vital products will
have approximated more closely to the physiological processes. It
may further be predicted with equal confidence that as greater chemical
mastery is acquired over the biochemical processes the number of
syntheses of vital products effected in the laboratory will go on increas-
ing at a much greater rate. Molecules of greater and greater com-
plexity will be built up independently of the animal or plant, and the
final triumph of synthetical chemistry may be expected to culminate
in the synthesis of those complex proteids which constitute such
a large proportion of the materials composing the living organism.
The complicated nitrogenous colloidal substances which play such an
important part in vital chemistry will at that time be no longer
subject to the reproach, now frequently aimed by organic chemists
who recognise nothing that is not crystalline, of being ' messes,' but
will take rank among the definite synthesised vital products. In the
meantime the recasting of the data of organic chemistry in this
biological mould may help to convince physiologists that considerable
progress has been made by chemists towards placing their science
on a more exact foundation, since all the vital products registered in
this work are perfectly definite and well-characterised compounds of
known chemical constitution.

IV. CHEMICAL SYNTHESIS FROM THE BIOCENTRIC

STANDPOINT

The consideration of the achievements of synthetical chemistry
from the present point of view has necessarily resulted in a mode of
treatment differing essentially from that adopted in the current
treatises. The term ' synthesis ' as used in organic chemistry is
generally assumed, if not explicitly stated, to mean the building up
of a carbon compound from compounds of lesser complexity. If the
simpler molecule is capable of being produced directly from its
elements the synthesis is said to be complete. It is evident, however,
that in the living organism two kinds of chemical change are going
on — an up-grade or building-up process from simpler to more complex
molecules, and a down-grade or breaking-down process from complex
to simpler molecules. From the chemical as well as from the physio-
logical point of view it appears that a large proportion, if not a large

^ or TWi
( VNIVER8ITY

10 INTRODUCTORY

majority, of the vital products hitherto synthesised are of the nature of
down-grade materials, or, in other words, waste products resulting
from the degradation of more complex antecedent compounds. It is
probable that in many cases the waste material is a final product of the
breaking down of several different antecedent compounds.

For the foregoing reasons the term synthesis as used in this work
has been given a wider meaning so as to comprise both up-grade and
down-grade products. From the established point of view, for example,
the formation of acetic acid from methane via methyl chloride and
cyanide, &c., is regarded as a true synthesis, the simpler molecule
having given rise to the more complex. But from the present point
of view the formation of methane from acetic acid by heating acetates
with alkali is just as much a true and complete synthesis of methane
as is the formation of this hydrocarbon by the direct union of its
elements. The methane of vital origin is a bacterial product resulting
from the breaking down of an extremely complex molecule, cellulose.
The latter has not yet been synthesised, but if this synthesis should
ever be effected the synthesis of methane via cellulose would be as
complete as the synthesis of the hydrocarbon via acetic acid.

The enlarged view of chemical synthesis thus rendered necessary
by a contemplation of the facts from the biological standpoint has
resulted in a mode of treatment which may at first seem strange and
unfamiliar, but it will be found that the method on closer acquaintance
is one that cannot but be helpful to chemists as well as to technologists.
Not only is prominence given thereby to the actual generators of the
various synthesised products, but the inter-relations between the
organic compounds themselves is also brought out as a special feature
to which, in view of the importance of the subject, emphasis is given
by means of the sub-title of the book.

The interest of the present work will, it is anticipated, be found
to centre not only in the records that particular compounds can be
obtained from such or such generators, but, as already pointed out,
more particularly in the information that such compounds are geneti-
cally related among themselves. Thus, to take a simple illustration, the
relationship of alcohol to aldehyde and acetic acid is of more .than
purely chemical interest in this work ; it is a fact also of biochemical
interest, because aldehyde and acetic acid are both vital products, and
the relationship is further of technological interest because the acid is
industrially producible from the alcohol by biochemical processes. In
general terms the genetic relationship of an organic compound to
a product sometimes of greater and sometimes of less complexity is
a fact which the present mode of treatment is well adapted to reveal,
and the essential feature of this treatment is to bring out all such
inter-relations within the limits of a reasonably sized work. In many
cases, such, for example, as the relationship of alcohol to certain sugars,
the living organism may be said to have discovered methods of break-

CHEMICAL SYNTHESIS 11

ing down complex into simpler molecules, which the chemist cannot
imitate at present by laboratory methods. In other cases, again, the
chemist has discovered relationships in the laboratory which the living
organism has long been realising in the vital laboratory. It must be
left to the judgement of physiological chemists to decide whether in
the case of any particular relationship herein recorded the chemical
mechanism of the transformation is similar in the organism and in the
laboratory — whether there is any analogy between the processes or
whether absolute ignorance must be declared. The consideration of
such problems cannot but give an impetus to further inquiry into the
chemical activities of animals and plants.

Certain details of treatment which follow from the foregoing con-
siderations may now be dealt with. "While following the main divi-
sions, such as hydrocarbons, alcohols, aldehydes, ketones, &c., under
which organic compounds are generally grouped, the information
which from the present standpoint is considered of the greatest impor-
tance is the particular generator which serves as a starting-point in
each synthesis. Since the generators under the present scheme are for
the most part themselves vital products, the relationships which from
the biochemical point of view are of the greatest interest are thus
brought into prominence. It was hoped at the outset of this under-
taking that it would have been possible to keep to the systematic
classification of the generators in the order of the above main divisions,
but the rapid progress of discovery made interpolations and rearrange-
ments so frequently necessary that this plan was found to be impracti-
cable in the time available and it had to be abandoned. This departure
from what may be considered the logical sequence will not, however,
be found of any practical disadvantage in using the work. The
systematic sequence has been observed as far as possible, and the
synthetical processes have been arranged under lettered paragraphs
with the name of the generator printed in italics so as to catch the
eye at once in running down the page. Each synthetical product has
also a registration number, so that cross-references are easily found
when necessary, the registration numbers which serve for such refer-
ences being printed in thick type in square brackets. The system of
cross-references, although throwing some additional trouble on the
reader, has been unavoidable in view of the fact that many synthetical
products serve as generators for numbers of other products. The
repetition of the sjnithetical processes every time a synthesised com-
pound is mentioned would have added enormously to the labour of
compilation, and would moreover have increased the size of the book
to an inordinate extent. In order to facilitate reference the registra-
tion number of the compound and the initial letters of the paragraphs
containing the descriptions of the synthetical processes are also printed
at the top of each page.

Among other consequences which follow from this biochemical

U INTRODUCTORY

treatment of organic synthesis is a complete departure from the usual
practice of classifying carbon compounds under types representing
certain atomic configurations of molecules. According to this method,
with which most students of organic chemistry are familiar, the
parent-compound or type is naturally looked upon as the generator of
all its derivatives, and is accordingly given the first rank in the order
of treatment. According to the present scheme each vital product is
in itself a biochemical type quite independently of the chemical type
to which it may be referred, and the synthesis of each product, instead
of being mentioned incidentally in connexion with the group to which
it belongs as a point of minor interest, is here brought into the first
rank of importance. In other words, the chemical type is in this work
subordinated to the individual compound — a mode of treatment for
which every justification will be conceded when it is pointed out
that in vital syntheses there are unquestionable genetic relationships
between compounds of quite different types.

In fact, a general survey of the present state of synthetical chemistry
makes it perfectly clear that the transformations in the living organism
have little or no relations to the chemical type, and it is equally certain
that the parent-compound or type, which is often the actual generator
in the laboratory synthesis, is not the generator in the vital synthesis.
Genetic relationships between vital products are thus to the student of
biochemistry all-important, because they maybe indicative of the actual
course of the vital chemical transition from one compound to another,
while relationships due to the possession of a common type of molecular
structure are of subsidiary importance. Whole groups of phenols,
aldehydes, acids, &c., are, for example, derivatives of benzene, and this
hydrocarbon is their actual laboratory generator. It may be confidently
asserted that the synthesis of these phenols, aldehydes, acids, &c., is not
effected by the animal or plant via benzene any more than that the
formation of alizarin in the madder plant proceeds from anthracene,
or that the production of hydrojuglone in the walnut-tree is preceded
by the synthesis of naphthalene.

On the other hand, the genetic relationships between compounds
of such different types as acetoacetic ester and quinol [7l], as di-
acetyl [113] and quinol, or as y-acetobutyric ester (from acetoacetic
ester and glycerol) and resorcinol [70] are of special interest from our
present standpoint, and may prove hereafter to be of real biochemical
significance. The subordination of the type to the individual vital
product has for the foregoing reasons been consistently carried out, so
that benzene, for example, is treated of, as it were incidentally, in
connexion with the first compound in the work in which the benzene
nucleus occurs, viz. cymene [e], anthracene in connexion with meta-
hydroxyanthraquinone [144], &c.

Another result which may be said to be accidental to the present
mode of treatment is the disproportionate amount of space allotted to

CHEMICAL SYNTHESIS 13

some compounds as compared with others. As long, however, as it is
borne in mind that the importance of a compound is not measurable
by the number of pages occupied by records of its mode of occurrence
or of its synthetical production but little harm is likely to arise from
this circumstance. It will be evident that such discrepancy is due to
the fact that some compounds have lent themselves more readily to
chemical investigation than others — that some have been found only
in a limited number of animal or vegetable products, while others are
widely distributed, or again, that some compounds are synthesisable
from a few generators only, while others can be synthesised from
a multiplicity of generators. Thus cymene [6] and benzyl alcohol [54]
occupy the large amount of space that has been devoted to them
because they happen to offer the first opportunity for dealing with the
syntheses of benzene and toluene respectively, these hydrocarbons
being required in many subsequent syntheses. Chemists will, of course,
regard such cases in true perspective, although the caution herein
conveyed may perhaps be necessary for physiologists who have no
special knowledge of organic chemistry. Had benzene and toluene
occurred as such in the free state in nature they would of course have
been given place among the vital products and had their syntheses
recorded in the usual way.

In view of the improbability of the derivatives of such hydrocarbons
as benzene or toluene being synthesised from the hydrocarbon by the
living organism it has not been even considered justifiable to include
their atomic complexes among the vital products. In fact, in the
present state of knowledge, it would be impossible to draw up a satis-
factory scale showing the importance to the vital economy of the
various synthetical products — the more especially since, as already
stated, the majority of these are of the nature of down-grade materials.
The compounds of fundamental importance in vital chemistry, such as
enzymes and albuminoid substances, have not yet been produced in the
laboratory, so that chemical synthesis from the biochemical point of
view may be said to have been hitherto confined to the lower orders
of combination. Even the classification into the main groups of
hydrocarbons, alcohols, &c., although convenient for practical purposes,
is from the biocentric standpoint purely artificial, and must be taken
rather as an expression of imperfect knowledge than of biochemical
reality. "When with the progress of discovery it becomes possible to
construct schemes showing the genetic or evolutional inter-relations
among vital products, then will the time be ripe for discussing on
a scientific basis the order of importance of the various organic com-
pounds in the cycle of vital operations. When our knowledge has
reached this level it may be confidently asserted that the biochemical
relationships will be found to be quite different from those at present
indicated by the ordinary chemical classification.

14 INTRODUCTORY

V. ADVANTAGES OF THE BIOCENTRIC TREATMENT
OF SYNTHETICAL CHEMISTRY

In one sense every definite organic compound known to science
may be said to have relationsliips with every other organic compound.
These inter-relations are necessarily extremely complex, being some-
times hypothetical — as in relationships of chemical type — and in other
cases real or genetic with few or many intermediate stages. The
progress of discovery in this department of chemistry consists largely
in substituting genetic for hypothetical relationships, and among the
advantages incidental to the mode of treatment adopted in this work
may be claimed the bringing into prominence, not only of the rela-
tionships between the vital products themselves, but likewise the
inter-relations among the intermediate compounds which are transition
stages between one synthetical product and another. The relations
between the vital products are, as frequently dwelt upon, of special
biochemical interest ; the relations between the intermediate com-
pounds are of more purely chemical interest. The intermediate stages
may or may not turn out to be of biochemical significance ; in the
present state of knowledge it is desirable that all inter-relationships
should be borne in mind, and in view of the ever-increasing complexity
of the connexions between organic compounds revealed by chemical
discovery it has been felt that some such work as the present would
furnish an opportunity of presenting this aspect of the subject in
a manner that cannot but be helpful to students from whatever point
of view they may be approaching the science.

As already explained, the time is not yet ripe for discriminating
precisely between biochemical and purely chemical relationships j the
work could not therefore be cast either in a purely physiological mould
or in a purely chemical mould, and its present arrangement appeals to
both classes of students. In the future it may be possible, when our
synthetical methods have come more into line with the biochemical
methods, to prepare a treatise on synthetical chemistry in which every
vital product shall be genetically connected with every compound to
which it gives rise by intermediate compounds, each one of which is
also a vital product. In other words, the ideal biochemical treatise of
the future may be cast on similar lines to the present work, but for
non-vital intermediate stages there will be substituted, by the dis-
covery of new and perhaps quite unsuspected synthetical methods,
series, more or less numerous, of vital intermediate compounds. The
fact that the intermediate stages are now so largely represented by
non-vital compounds is a measure of our ignorance of biochemical
processes. In the other direction the ideal treatise on pure chemical
sjmthesis — towards which considerably greater progress has already
been made— will contain records of genetic relationships starting, let

SYNTHETICAL CHEMISTRY 15

us say, from carbon and hydrogen or from calcium carbide and water,
and every known organic compound. At present the two modes of
treatment have perforce been combined, and it must be left to the
judgement of chemists and physiologists respectively to attach the
proper weight to such data as they may gather from these pages for
the purposes of any particular inquiry.

It may perhaps be considered presumptuous on the part of a writer
who lays no claim to be considered a physiologist to caution students
of this science that the work now offered does really contain in spirit,
if not in the text, the two distinct lines of treatment above indicated,
and that there is a danger in making too free use of laboratory rela-
tionships between organic compounds as evidence of physiological
relationship without direct physiological evidence in confirmation.
The extreme difficulty of obtaining such confirmation has already been
conceded ; nevertheless any chemist who considers some of the physio-
logical speculations which have been advanced of late years cannot
but come to the conclusion that genetic relationships established
experimentally by chemists have been overstrained in the service of
physiology. The ordinary chemical equation representing the genetic
relationship of one vital compound to another is apt to delude those
who are not experts in chemistry into the belief that it is all-sufficient
and that it ' explains ' the biochemical process : as a matter of fact the
sign connecting the two sides of the equation stands for the whole
unexplored region of biochemical transmutation.

It may perhaps be urged as a countercharge against chemists that
many of the highest authorities have advanced purely chemical
explanations of biochemical transformations without sufficient physio-
logical evidence. This must be frankly admitted, but it may be
pleaded in excuse that the physiological evidence has not been avail-
able— partly owing to the practical difficulties of obtaining it, and
partly owing to want of co-operation between the two departments of
science. Such speculative advances, however, if taken at their true
scientific value and not exalted to the rank of proved theories, can
do no harm, and may do much good in advancing biochemical science
by acting as suggestions stimulating further observation and experi-
ment in this all-important field.

Not the least difficult task in connexion with the present compila-
tion has been the restriction of the series of intermediate compounds
within reasonable limits. Although much judgement has been exer-
cised, it may appear even now that many of the genetic relationships
are extremely far-fetched — that the number of intermediate com-
pounds has been multiplied to an unnecessary extent, and that stages
have been interpolated which would certainly never be passed through
in the course of any practical series of laboratory operations for the
synthesis of one compound from another. Again, therefore, it may be
necessary to insist that this work is not a practical laboratory guide,

16 INTRODUCTORY

but that its object is to furnish material for evolutional schemes of
genetic relationships which are chemically real, however far-fetched
they may appear from a laboratory or technical point of view.

Thus, to state the case in an abstract form, a vital product, X, is
capable of being produced from a certain generator, A, by the action
of heat or chemical reagents. But A by treatment with certain other
reagents can be transformed into the compounds P, Q, R, &c., each one
of which, or only the last one, say R, can by appropriate treatment be
converted into X It may be urged against the system adopted in this
work that since X can be directly obtained from A, the intermediate
compounds P, Q, R, &c., have been interpolated unnecessarily. This
objection is valid from a practical point of view, but if the fact that X
is obtainable from P, Q, and R were for this reason omitted the genetic
relationships between A, P, Q, R, and X would be lost sight of. More-
over it is possible — and in fact during the preparation of this work
numbers of actual cases have occurred — that one or all of the inter-
mediate compounds P, Q, R may be at present, or may be found sub-
sequently to be, synthesisable from some generator other than A, let us
say B, so that B then becomes a generator of X— a fact that would
have been ignored if P, Q, R had not been interpolated between A and
X. It is further possible that some natural source of one of the inter-
mediate compounds, say R, might be discovered hereafter, in which
case the genetic relationship of the vital product i? to 4 at one end
and X at the other would then be deducible from this work. Provision
is accordingly made by this treatment not only for the possible
development of further chemical relationships through the discovery of
new modes of synthesising compounds which are now non-vital inter-
mediate stages, but likewise for the possibility of some non-vital pro-
ducts, at present only used as stepping-stones in the laboratory series
of operations, being hereafter found in nature.

In illustration of the advantages of this system — a system in which
directness and simplicity of transformation cannot be allowed to deter-
mine which synthetical processes shall be included and which excluded
— the case of diacetyl [113] may be quoted. When the section dealing
with quinol [7l] was first written the generators of diacetyl had to be
included among the generators of this phenol. It was afterwards
found in the laboratory of Sohimmel & Co. that diacetyl is a consti-
tuent of certain ethereal oils, so that this compound, at first introduced
only on account of its genetic relationship to quinol, thereupon had to
be enrolled among the vital products and so, as it were, to have its
importance enhanced by having biochemical interest added to its
purely chemical interest as an indirect generator of quinol. Had
diacetyl been excluded because its connexion with quinol is only of
an indirect character an interesting relationship between two vital
products would have been lost sight of. The cases in which new
synthetical processes for the production of non-vital intermediate

SYNTHETICAL CHEMISTRY 17

compounds have been discovered during the compilation of this work
are too numerous to select special illustrations from ; constant interpo-
lations have, as already stated, been necessary to keep pace with the
progress of discovery.

In pursuance of the scheme of recording the inter-relations between
organic compounds on biochemical rather than on purely chemical
lines it has also been found necessary, not only to interpolate whole
series of intermediate stages irrespective of practical considerations,
but also to record synthetical processes which in many cases yield only
a small quantity, or even only a trace, of the final product. In other
words, the question of yield, like the question of directness of method,
cannot be allowed any weight in presenting the subject of chemical
synthesis from the present point of view. It is clear that we are
following the natural method in this, because it is tolerably certain
that a large number, if not a large majority, of the vital products at
present isolated and synthesised are of the nature of by-products,
having no quantitative relationship to their generators that could be
stated — even if we knew what these generators were — in the form of
chemical equations which could be said to express the whole truth.
No less is it certain that many of the vital compounds herein dealt
with arise from the breaking down of many antecedent generators,
and the final product results from the accumulation of traces of the
compound derived from several sources.

It may fairly be urged that the inclusion of processes which result
only in a trace of the final product diminishes the value of this work
from the technological point of view. Even here, however, it is
claimed that the biochemical method, if properly used, may be of great
service in chemical technology. In using this as a work of reference
in which all the generators of any particular compound are recorded
in a systematic manner, the chemist, the physiologist, and the techno-
logist will no doubt each use his judgement in assigning due weight
to any particular process. The mere statement of the fact that there
is any genetic relationship between one compound and another of
industrial importance may furnish a suggestive clue for future in-
vestigation. As our knowledge of biochemical processes advances and
as our chemical processes are brought more and more into line there-
with, it is certain that the manufacture of vital products will derive
just as much advantage as will the laboratory methods for synthesising
organic compounds which are of no industrial use.

To state the case another way, the fact that a particular generator
gives rise to only a trace of some compound of industrial use is a hint
given by Nature that the future technologist might work upon to
increase the yield and, as it were, to improve upon Nature's own
method. The history of the development of industrial organic
chemistry furnishes many examples which justify this inclusion of
all processes, irrespective of yield. In modern times the synthesis of

c

18 INTRODUCTORY

indigo, first from benzene and acetic acid via phenylglycin, then from
naphthalene and acetic acid via anthranilic acid (a vital product) and
phenylglycin-orthocarboxylic acid, may be quoted as a most instruc-
tive illustration. The yield from the first of these generators was
insufficient for technological success ; the yield from anthranilic acid
is sufficient to enable the synthetical to compete successfully with the
natural product. In fact, most laboratory syntheses are at first accom-
plished without any consideration of the question of yield ; it is not
till the process is taken over by the technologist that this question
becomes of importance. The conversion of a laboratory compound
into a technological product often reacts also upon the scientific
investigation of the compound, leading not only to improvements in
methods of production, but likewise to the discovery of new synthetical
processes.

The study of synthetical chemistry from the present point of view
will furnish numerous examples illustrative of the interdependence of
science and technology, and, in fact, many of the syntheses of vital
products effected of late years are the direct outcome of the techno-
logical value of such products. In view of the relationships between
biochemistry and chemical technology, the revelation of which, it is
claimed, is intimately associated with the present mode of treatment,
it is obvious that patented processes have had to be included in the
literature. It is of course beyond the scope of this work to discuss
such processes critically, and they have all been included, when having
any bearing upon any particular synthesis, for whatever they may be
worth industrially. The inclusion of patented processes cannot, how-
ever, but contribute towards the utility of the work from the point of
view of the chemical technologist.

In one direction a certain latitude has been allowed in dealing with
synthesised vital products, to which special attention must be directed
in conclusion. In the case of optically active compounds the synthesis
is not logically complete till the optical isomeride has been isolated in
the laboratory by one or another of the known methods. Nevertheless
the synthesis of such optically active compounds has been recorded as
an accomplished fact, although the laboratory product is, as is well
known, always optically inactive through ' external compensation '
(racemism, &c.). In going beyond the facts to this extent it is claimed
that the course adopted is, however, but a reasonable anticipation of
future discovery. The optically active vital product is actually present
in the racemic compound or mixture produced in the laboratory, and
it may confidently be expected that some method will hereafter be
devised for separating the optical isomerides in the case of synthesised
compounds which, being neither acid nor basic nor attackable by
biological methods, have thus far remained as unresolved. To illustrate
this point by a hypothetical case, dextrotartaric and racemic acids are
natural products, the latter alone being, strictly speaking, a synthetical

SYNTHETICAL CHEMISTRY 19

product. Nevertheless, had racemic acid never been resolved, both
dextro- and IsBVotartaric acids, according to the above principle, would
have been claimed as synthetical products in anticipation of the dis-
covery of methods of resolution. To take another actual example,
dipentene and dextro- and IsBvolimonene [9] are all natural products.
Dipentene is racemic limonene, and as this compound has been
synthesised it is claimed that the limonenes are also synthetical
products, although no method for resolving dipentene has yet been
devised.

c2

n

HYDROCARBONS.

1. Methane; Marsh Gas.
CH,

Natural Sources.

A PRODUCT of the bacterial fermenta-
tion of calcium acetate and lactate, of
milk-sugar, glycuronic acid, choline,
cellulose, albumin, &c.

Methane fermentation is produced by
micro-organisms from the stomach of
ruminants and by bacteria occurring in
sewage mud. (For methane fermenta-
tion of calcium acetate and lactate see
Hoppe-Seyler, Zeit. physiol. Ch. 11, ^6 1 ;
of milk-sugar, Baginsky, ibid. 12, 457 ;
of albumin, Nencki and Sieber, Monats.
10, S"^^ j of choline, Hasebroek, Zeit.
physiol. Ch. 12, 148 ; of cellulose, Mit-
scherlich, Monats. d. k. Akad. d. Wis-
sensch. Berlin, 1850, 104 ; Popoff,
PflUger's Arch. 10, 113 ; Tappeiner,
Ber. 16, 1734-) The methane fermenta-
tion of cellulose has been erroneously
attributed to TrecuPs Amylohacter (Van
Tieghem, Comp. Rend. 88, 205 ; 89,
5 ; Hoppe-Seyler, Zeit. physiol. Ch. 10,
201 ; 401 ; 409 ; Ber. 16, 122).

The gases of the intestinal canal,
which are evolved especially after a
pulse diet, contain methane, possibly re-
sulting from the bacterial fermentation
of cellulose (Tappeiner, Ber. 15, 999 ; 16,
1734; 1740 ; Zeit. Biol. 20, 52; 215;
24, 105), of albumin (Ruge, Wien. Sit-
zungsber. 44, 739), and of lecithin
(Hasebroek, Zeit. physiol. Ch. 12, 148).

The intestinal gases of man and
dogs fed on purely flesh diet also contain
methane (Ruge and Planer, quoted by
Lafar, ^ Technical Mycology,' I, p. 196).
Methane is said to have been detected
in the breath of calves and of sheep
(Reiset, Jahresber. 1863, 638).

According to Omeliansky (Comp.
Rend. 125, 1131; Ch. Centr. 1900, 1,
918, from Arch. Sci. Biol. St. Pet. 7,
411) the cellulose ferment is Bacillus
fermentationis celluloscB, but this does

not give rise to methane. The latter
is produced towards the end of the
fermentation by another Bacillus, which
is not Amylohacter. (See also Centr.
Bakter. 8, 193 et seq.) Chalk is
essential for the production of methane
from cellulose (Omeliansky).

The methane fermentation of milk-
sugar is caused by Bacterium lactis a'ero-
genes of Escherich = Bad. aceticum of
Baginsky (Zeit. physiol. Ch. 12, 461 ;
Emmerling, Ber. 33, 2477). The de-
velopment of gases, including methane,
by Bacillus coli communis cultivated in
different media has been studied by
Mary E. Pennington and Geo. Kiisel
(Am. Ch. Journ. 22, 556).

Methane is among the gases evolved
during the 'sauerkraut' fermentation
of vegetables and of nutrient saccharine
solutions hj Bacterium brassier acidce. of
Lehmann and Conrad (Ch. Centr. 1897,
1, 1098). Also among the gases evolved
during the putrefaction of elastin (pre-
pared from the ligamentnm nuchtB of the
ox) by anaerobic microbes (Zoja, Zeit.
physiol. Ch. 23, 236). Methane is
evolved during the putrefaction of com-
pressed manure (Deherain and Dupont,
Ann. Agronom. 26, 273 ; also Deherain,
Comp. Rend. 99, 45 ; and for evolution
of methane by anaerobic fermentation
of straw, Ibid. Ann. Agronom. 10, 385),
and is among the gases given off during
the fermentation which takes place in
indigo vats and in sugar diffusers (for
latter see Lafar's ' Technical Mycology,'
I. p. 196). Methane is among the gases
evolved during the putrefaction of barley
(Lermer, Journ. Fed. Inst. 8, 509, from
Zeit. ges. Brau. 25, 165).

Synthetical Processes.

[A.] Methane is produced by the direct
union of carbon with hydrogen at iaoo°
(Bone and Jordan, Trans. Ch. Soc. 71,
41 ; 79, 1042). The carbides of the
metals aluminium, beryllium, cerium,

22

HYDROCARBONS

[1 A-D.

manganese, lanthanum, yttrium, ura-
nium, and thorium, praseo- and neo-
didymium produced in the electric fur-
nace give methane (in most cases mixed
with other gases) when acted upon by
water (Moissan, Proc. Roy. Soc. 60,
156; Bull. Soc. [3] 11, 1012 ; 15, 1285 ;
17, 15 ; Comp. Rend. 122, 362 ; 423 ;
1462 ; Ann. Chim. [7] 9, 302 ; Moissan
and Etard, Ann. Chim. [7] 12, 429;
Lebeau, Comp. Rend. 121,498 ; Moissan,
Comp. Rend. 131, 595; Berthelot, Comp.
Rend. 182, 281).

Carbon and hydrogen combine directly
to form acetylene when the electric arc
passes between carbon poles in an at-
mosphere of hydrogen (Berthelot, Ann.
Chim. [4] 13, 143; Comp. Rend. 54,
640 ; Bone and Jerdan, Trans. Ch. Soc.
71, 41 ; 79, 1042). Or certain metallic
carbides, such as those of barium, cal-
cium, strontium, and lithium prepared in
the electric furnace, give acetylene when
acted upon by water (Moissan, Bull. Soc.
[3] 15, 1285 ; the production of acety-
lene from calcium carbide and water was
first observed by Wohler, Ann. 124, 220 :
the technical production of calcium car-
bide is due to Willson, 1894. Wohler
prepared calcium carbide by strongly
heating an alloy of zinc and calcium with
charcoal : Maquenne prepares barium
carbide by heating barium carbonate
with magnesium powder and carbon ;
Ann. Chim. [6] 28, 266). Acetylene
gives methane when passed over finely
divided nickel heated to 300° (Sabatier
and Senderens, Comp. Rend. 124, 617)
or when heated ^^r se to 1 150° (Bone and
Jerdan, Proc. Ch. Soc. 17, 164). Or
acetylene forms a compound with mer-
curic chloride (see under acetaldehyde
[92; A]), and this on treatment with
iodine and alkali gives iodoform (Le
Comte, Journ. Pharm. 16, 297). From
iodoform as under D below.

Carbon monoxide and hydrogen give
methane under the influence of the silent
electric discharge (Brodie, Proc. Roy.
Soc. 21, 245 ; Ann. 169, 270). So also
(probably) does a mixture of carbon di-
oxide and hydrogen (Collie, Trans. Ch.
Soc. 79, 1067). Methane is produced
by the catalytic action of finely divided
heated nickel or cobalt on a mixture of

hydrogen with carbon dioxide or mon-
oxide (Sabatier and Senderens, Comp.
Rend. 134, 514; 689).

[B.] Heptane [2] gives methane among
the gases produced by heating the hydro-
carbon to 900° (Worstall and Burwell,
Am. Ch. Journ. 19, 815).

[C] From methyl alcohol [13] through
methyl iodide and the action of sodium
on the moist ethereal solution or of the
copper-zinc couple or aluminium amal-
gam on the alcoholic solution of the
iodide (Gladstone and Tribe, Trans. Ch.
Soc. 45, 154; "W right, Ibid. 47, 200;
Bone and Wheeler,7d?V/. 81,541). Magne-
sium amalgam reduces the alkyl iodides
more readily than the copper-zinc couple
(Meunier, Comp. Rend. 134, 47 2). Me-
thyl iodide (or chloride) gives methane
by heating with potassium hydride
(Moissan, Comp. Rend. 134, 389). Or
from methyl iodide through zinc methyl
(Frankland, Ann. 85, 346 ; 111, 62) and
decomposition of the latter by water
{Ibid. Phil. Trans. 1852, 2, 417 ; Laden-
burg and Kriigel, Ber. 32, 1821), or by
alcohol in an atmosphere of nitrogen or
hydrogen (Tolkatscheff, Journ. Russ.
Soc. 33, 469). Magnesium methiodide
gives methane on decomposition by water
(Grignard, Ann. Chim. [7] 24, 433 ;
Tschugaeff, Ber. 35, 3912).

From methyl alcohol by passing the
vapour over heated magnesium (Keiser
and Breed, Ch. News, 71, 118), or by
passing the electric arc through the va-
pour (Lob, Ber. 34, 917), or by pyro-
genic contact decomposition (Ipatieff,
Ber. 35, 1055; 1060). From methyl
alcohol through methyl ether (Dumas
and Peligot, Ann. 15, 12 ; Kane, Ann.
19, 166 ; Ebelmen, Ann. 57, 328 ;
Erlenmeyer and Kriechbaumer, Ber. 7,
699 ; Tellier, Arch. Pharm. 10, 57).
The latter gives methane on passing
through a hot tube (Tischtschenko, Ch.
Centr. 1900, 1, 586, from Journ. Russ.
Soc. 31, 784).

[D.] From ethi/l alcohol [l4] through
chloroform (Liebig, Ann. 1, 198 ; Sou-
beiran, Ann. Chim. [2] 48, 131; Sou-
beiran and Mialhe, Ann. 71, 225;
Kessler, Journ. Pharm. 13, 162; Belo-
houbek, Ann. 165, 349 ; Goldberg,
Journ. pr. Ch. [2] 24, 114 ; for electro-

ID.]

METHANE

23

lytic production of chloroform from
potassium chloride and alcohol see
Chem. Fab. auf Aktien, Germ. Pat.
29771 of 1884 ; Ber. 17, Ref. 624. See
also Dony-Henault, Zeit. Elektroch. 7,
57). Chloroform gives methane on reduc-
tion with zinc dust in alcoholic solution
(Sabanejeff, Ber. 9, 1810; Perkin, Ch.
News, 18, 106) or by potassium amal-
gam (Regnault, Gerhardt's ' Traits/
1, 603). Or by passing chloroform
vapour and hydrogen through a hot
tube, or by heating chloroform with
copper or with potassium iodide and
water in a sealed tube (Berthelot,
Jahresber. 1857, 267).

Or from ethyl alcohol through bromo-
form (Lowig, Ann. 3, 295 ; Dumas,
Ann. Chim. [2] 56, 120; Giinther,
Arch. Pharm. [3] 25, 373), which is
reduced to methane by heating with
potassium iodide, water, and copper or
zinc (Berthelot, Ann. Chim. [3] 51, 48),
or by the copper-zinc couple (Gladstone
and Tribe, Journ. Ch. Soc. 28, 510).
Bromoform yields methane by passing
the vapour over heated copper (in an
atmosphere of carbon dioxide) or by
heating with zinc dust in alcoholic
solution (Nef, Ann. 308, 329).

Or from ethyl alcohol through iodo-
form (Serullas, Ann. Chim. [2] 22, 172 ;
25, 314; Giinther, Arch. Pharm. [3]
25, '^y^ ; Rother, Pharm. Journ. [3] 4,
593 ; for electrolytic preparation of iodo-
form see Chem. Fab. auf Aktien, Germ.
Pat. 29771 of 1884; Ber. 17, Ref. 624;
Forster and Meves, Journ. pr. Ch. [2]
56, 354; Elbs and Herz, Zeit. Elektroch.
4, 113; also Dony- Renault, /^ia'. 7, 57;
Bull. Assoc. Belg. [6] 14, 247; for
production from potassium iodide and
alcohol by the action of ozone see Otto,
Germ. Pat. IC9013 of 1898; Ch. Centr.
1900, 2, 304). Iodoform gives methane
by the action of the copper-zinc couple
(Gladstone and Tribe, Journ. Ch. Soc.
28, 508), or by heating with finely
divided silver in an atmosphere of
carbon dioxide (Nef, Ann. 308, 329).

Or from ethyl alcohol through ethyl
chloride (Robiquet and Colin, Ann.
Chim. [2] 1, 343 ; Regnault, Ibid. 71,
355; Kuhlmann, Ann. 33, 108; Lowig,
Pogg. Ann. 45, 346; Groves, Journ.

Ch. Soc. 27, 637; Kriiger, Journ. pr.
Ch. [2] 14, 195; Geuther, Zeit. [2] 7,
147). The latter gives methane (and
acetic acid) when passed over red-hot
lime (L. Meyer, Ann. 139, 282 ; see
also Dumas and Stas, Ann. Chim. [2]
73, 154, and Nef, Ann. 318, 1).

Or from alcohol through chloral by
chlorination (Liebig, Ann. 1, 189); also
under formic acid [Vol. II]). Chloral
in aqueous solution gives methane on
heating with zinc or iron dust (Cotton,
Bull. Soc. [2] 42, 622).

Methane is among the gases produced
by passing the vapour of ethyl alcohol
over heated magnesium (Keiser and
Breed, Ch. News, 71, 118). Ethyl
alcohol by the action of aluminium
in presence of stannic chloride gives
aluminium ethylate(Hillyer and Crocker,
Am. Ch. Journ. 19, 41). The latter
gives methane among the products of its
decomposition by heat (Tischtschenko,
Ch. Centr. 1900, 1, 585, from Journ.
Russ. Soc. 31, 784).

From ethyl alcohol through ethyl
ether (Valentin Rose, Scherer's, Journ.
d. Ch. 4, 253 ; Saussure, Ann. Chim.
89, 273 ; Dumas and BoiiUay, Ibid. [2]
36, 294; Williamson, Journ. Ch. Soc.
4, 106; Boullay, Journ. Pharm. 1, 97;
Soubeiran, Ibid. [3] 16, 321). The
latter gives methane among the pro-
ducts of photochemical oxidation in pre-
sence of hydrogen peroxide (Berthelot,
Comp. Rend. 129, 627).

From ethyl alcohol through ethylene
by heating with dehydrating agents
(Mitscherlich, Ann. Chim. [3] 7, 12;
Ebelmen, Ibid. 16, ^^6; Erlenmeyer
and Bunte, Ann. 168, 64 ; 192, 244 ;
Villard, Ann. Chim. [7] 10,389; Newth,
Proc. Ch. Soc. 17, J 47). Methane is
among the products formed by passing
ethylene over finely divided nickel heated
in a tube (Sabatier and Senderens,Comp.
Rend. 124, 1358 ; 131, 267), by passing
a mixture of ethylene and hydrogen
over heated freshly reduced cobalt [Ibid.
130, 1 761), or by passing through a hot
tube (Day, Am. Ch. Journ. 8, 153).

Note : — Ethylene and acetylene are among
the products formed when the vapours of
primary alcohols such as methyl [13], ethyl [14],
isobutyl [18], and amyl alcohol [22] are passed
over calcium carbide heated to 500° (Lefebvre,

24

HYDROCARBONS

[1 D-J.

Comp. Rend. 132, 1221). Ethylene or methane
or both gases are among the products formed
by passing the vapour of ethyl alcohol through
hot tubes of glass, platinum, or iron, or over
heated metals such as zinc, brass, &c., or certain
metallic oxides such as those of zinc, tin, &c.
(Jahn, Ber. 13, 987 ; Ipatieff, Ber. 34, 3579 ;
35, 1047 ; also over heated plumbago crucible
material, Ibid. 1058). Ethylene and acetylene
are among the products of the pyrogenic de-
composition of the vapour of amyl alcohol [22]
(Wurtz, Ann. 104, 243). Ethylene is among
the products formed by passing n-hexane [23 ;
A, &c. J or isobutyl alcohol vapour [18] mixed with
air over heated platinum (v. Stepski, Monats.
23, 773).

[E.] Propyl alcohol [15] gives me-
thane among the products formed by
passing the vapour over heated mag-
nesium (Keiser and Breed, Ch. News, 71,
118), or over heated plumbago crucible
material (Ipatieff, Ber. 35, 1059). ^^"
n-propyl alcohol gives iodoform by the
action of iodine and alkali (Lieben, Ann.
Suppl. 7, 318; 377), and this can be
reduced to methane as above under D.

Or from n-propyl alcohol through
the aldehyde (propanal) by oxidation
(Chancel, Ann. 151, 301 ; Przybytek,
journ. Russ. Soc. 8, 335 ; Lieben and
Zeisel, Monats. 4, 14). Propanal gives
methane among the products of de-
composition of its vapour at a high
temperature (Tischtschenko, Ch. Centr.
1900, 1, 586; Journ. Russ. Soc. 31,

7«4).

Or from n-propyl alcohol through
n-propyl chloride (see under isopropyl
alcohol [16; B]). The latter gives
carbon tetrachloride (with the hexa-
chloride) when heated with iodine
chloride to 200° (Krafft and Merz, Ber.
8, 1296). The tetrachloride gives me-
thane as below under L.

Or from inopropi/l alcohol [16], being
among the products of pyrogenic contact
decomposition (Ipatieff, Ber. 35, 1056).

[P.] Normal butyl alcohol [17] gives
iodoform by the action of iodine and
alkali (Lieben ; see above under E).
Subsequent treatment as under D.

Or isobutyl alcohol [18] gives iso-
butyl chloride or bromide, and these
haloids passed over soda-lime heated
to 600° give methane among other
products (Nef, Ann. 318, 22, &c.).
Methane is among the gases produced
by the pyrogenic contact decomposition

of the vapour of isobutyl alcohol by
certain metals (Ipatieff, Ber. 35, 1052 ;
also Noyes, Beilstein, I, 115) or by
plumbago crucible material (Ipatieff,
Ber. 35, 1060).

[G.] From octyl alcohol [28] through
iodoform (Lieben, loc. cif.) and then as
above under D.

[H.] Glycerol [48] gives a small
quantity of methane among the products
of the dry distillation of the barium
compound (Destrem, Ann. Chim. [5]
27, 17; 44; Comp. Rend. 90, 1313).

Or from glycerol through allyl alcohol
(see under ethyl alcohol [14 ; G]), which
gives methane among the products of
pyrogenic contact decomposition bypass-
ing the vapour over certain heated metals
(Ipatieff, Ber. 35, 1054). Or from
glycerol through acrolein [lOl] as under
HH below.

[I.] From aldehyde [92] throngli
iodoform (Lieben, loc. cit.) and then as
above under D. Or aldehyde gives
chloral on chlorination (Pinner, Ber. 4,
256 ; Wurtz and Vogt, Zeit. [2] 7, 679),
and this is decomposed by alkali with
the formation of chloroform (Liebig,
Ann. 1, 199). The latter, or chloral
itself, can be reduced to methane as
above under D.

Aldehyde gives methane among the
products of the decomposition of its
vapour by heat (Tischtschenko, Ch.
Centr. 1900, 1, 586; see also Ipatieff,
Ber. 34, 3579) or by pyrogenic contact
decomposition by the action of certain
metals (Ipatieff, Ber. 35, 1049). Me-
thane is among the products of the
action of strong aqueous hydriodic acid
on aldehyde and many other compounds
at a high temperature (Berthelot, Bull.
Soc. [2] 7,60; 9,8; 91; 178; 265;
Jahresber. 1867, 342).

Or aldehyde-ammonia gives methane
among the products of its decomposition
when heated with a hypochlorite (De
Coninck, Comp. Rend. 126, 1042).

[J.] From acetone [IO6] through
chloroform or iodoform (Liebig, Ann. 1,
198 ; Lieben, as above under E ; Rother,
Jahresber. 1874, 317; Curtman, Beil-
stein^s 'Handbueh,'' I, 189 ; Suilliot and
Raynaud, Bull. Soc. [2] 51, 4 ; Orndorff
and Jessel, Am. Ch. Journ. 10, "^d^, and

1 J-T.]

METHANE

25

subsequent reduction as above under D.
According to Berthelot (see above under
I) methane is among the gases produced
by the reduction of acetone by heating
to a high temperature with strong
aqueous hydriodic acid.

Acetone also gives bromoform by
electrolysis in presence of potassium
bromide and carbonate (Coughlin, Am.
Ch. Journ. 27, 63 : compare Elbs and
Herz, Zeit. Elektroch. 4, 113).

[K.] Butyric aldehyde [94] gives
iodoform by the action of iodine and
alkali (Lieben, as above under E).

[L.] From carbon disidphide [160]
by passing the vapour mixed with
sulphuretted hydrogen over heated
copper (Berthelot, Comp. Rend. 43, 236 ;
Ann. Chim. [3] 63, 69). Or from
carbon disulphide by heating with phos-
phonium iodide to I20°-140° (Jahn,
13er. 13, 127).

Or carbon disulphide on chlorination
in the presence of iron and iodine and
Bubsequent treatment of the product
with bleaching powder gives carbon
tetrachloride (Serra, Gazz. 29, ^S3)' ^^
carbon disulphide can be converted into
the tetrachloride by chlorination (Kolbe,
Ann. 45,41 ; 64, 146 ; Hofmann, Ann.
115, 264; Klason, Ber. 20, 2376;
Mouneyrat, Bull. Soc. [3] 19, 262 :
for references to technical processes see
Conroy, Journ. Soc. Ch. Ind. 21, 309 ;
Urbain, Eng. Pat. 13733 ^^ 1901J
Journ. Soc. Ch. Ind. 21, 926). Carbon
tetrachloride can be reduced to methane
in the same way as chloroform (Berthe-
lot, Jahresber. 1857, 267).

[M.] Phenol [6O] gives methane
among the products of pyrogenic de-
composition (Miiller, Journ. pr. Ch. 58,
i). Orphenol by the action of potassium
chlorate and hydrochloric acid gives tri-
chlor-aa-glyceric acid, which is decom-
posed by cold alkaline solutions into
oxalic acid and chloroform (Schreder,
Ann. 177, 282).

[N.] From cresol [61; 62; 63] by
pyrogenic decomposition (Miiller, as
above under M).

[O.j From/brwzc acid [Vol. II], being
among the products of the dry distilla-
tion of the barium salt (Berthelot,
Jahresber. 1857, 426) and of the action

of heated zinc dust on the vapour of the
acid (Jahn, Ber. 13, 2109).

Or methyl formate on extreme chlo-
rination gives perchlormethyl formate
(Hentschel, Journ. pr. Ch. [2] 36, 100 ;
214; 305), which is decomposed by
aluminium chloride with the formation
of carbon tetrachloride {Ibid. 308). Sub-
sequent steps as above under L.

[P.] From acetic acid [Vol. II] by
heating acetates with barium oxide, with
potash-lime or soda-lime (Dumas, Ann.
Chim. [2] 73, 92; Ann. 33, 181 ; Von
Schlegel, Ann. 226, 140; Schorlemmer,
Ch. News, 29, 7 : compare Ladenburg
and Kriigel, Ber. 32, 1820). Also from
acetic acid by photochemical decom-
position in the presence of uranium
salts (Fay, Am. Ch. Journ. 18, 287).
Also by the electrolysis of fused potas-
sium acetate (Lassar-Cohn, Ann. 251,

Or indirectly from acetic acid through
the trichloro-acid by chlorination (Du-
mas, Ann. 32, loi). The trichloro-acid
gives chloroform on heating with
aqueous alkali [Ibid. 113; Ann. Chim.
[2] 56, 115).

[Q.j Glycollic acid [Vol. II] gives
methane on distillation with lime (Han-
riot, Bull. Soc. [2] 45, 80; Comp. Rend.
101, 1 156).

[B.] Lactic acid [Vol. II] gives iodo-
form by the action of iodine and alkali
(Lieben, as above under E). Subsequent
reduction as before. Or lactic acid gives
chloroform on treatment with bleaching
powder (Eberhard, Journ. Ch. Soc. 80,
I, Abst. 357). Subsequent reduction as
above under D.

[S.] From malonic acid [Vol. II],
ethylene being among the products of
the electrolysis of the acid potassium
salt (Petersen, Ch. Centr. 1897, 2,
519). Ethylene gives methane as above
under D.

[T.] From succinic acid [Vol. II],
methane being among the products of
electrolysis of an alcoholic solution in
presence of sodium hydroxide (Clark and
Smith, Journ. Am. Ch. Soc. 21, 967).

Or indirectly through ethylene by
the electrolysis of a strong solution of
the sodium salt (Kekule, Ann. 131, 79 ;
Clark and Smith, loc. cit. ; also from

26

HYDROCARBONS

[l T-HH.

the acid potassium salt, Petersen, Ch.
Centr. 1897, 2, 519; 1900, 2, 171),
and then as above under D.

Or succinic acid gives a dibromo-acid
on bromination (Kekule, Ann. 117, 123 ;
Ann. Suppl. 1, 352; Bourgoin, Bull.
Soc. [2] 19, 148 ; Gorodetzky and
Hell, Bar. 21, 1731), and this by treat-
ment with alcoholic potash gives acetyl-
enedicarboxylic acid (Bandrowsky, Ber.
10, 838 ; Baeyer, Ber. 18, 677 ; 2269),
the sodium salt of which gives, on the
addition of silver nitrate, silver acetylide
(Lessen, Ann. 272, 140). Acetylene
liberated from the latter gives methane
as above under A.

[U.] Fumaric acid [Vol. II] combines
with bromine to form dibromsuccinic
acid (Kekule, Ann. Suppl. 1, 131 ;
Baeyer, loc. cit. ; Kirchhoff, Ann. 280,
209 J Michael, Journ. pr. Ch. [2] 52,
395). Subsequent steps as above
under T.

Or fumaric (or maleic) acid gives
acetylene on electrolysis of a strong
solution of the sodium salt (Kekule,
Ann. 131, 85).

Or maleic acid (anhydride) on com-
bination with bromine gives isodibrom-
succinic acid (Kirchhoff, Ann. 280, 207),
and this on heating with strong hydro-
bromic acid gives dibromsuccinic acid
(Michael, Journ. pr. Ch. [a] 52, 324).
Subsequent steps as above under T.
Isodibromsuccinic acid also on treatment
with alcoholic potash gives acetyl ene-
dicarboxylic acid (Bandrowsky, Ber. 10,
838), which gives acetylene and methane
as above under T.

[v.] Azeldic acid [Vol. II] gives
a small quantity of ethylene among
the products of its distillation with
Boda-lime (Miller and Tschitschkin, Ch.
Centr. 1899, 2, 182). Ethylene gives
methane as above under D.

[W.] Salicylic acid [Vol. II] by the
action of potassium chlorate and hydro-
chloric acid gives trichlor-aa-glyceric
acid, from which chloroform can be
obtained (see under M above).

[X.] From gallic acid [Vol. II]
through trichlor-aa-glyceric acid by the
action of potassium chlorate and hydro-
chloric acid and chloroform, &c., as
before (see under M above).

[Y.] Metliylamine [Vol. II] gives
methane among the products of its re-
duction by strong aqueous hydriodic
acid at a high temperature (Berthelot,
as above under I).

[Z.] Trimethylamine [Vol. II] on
heating the hydrochloride to 326 de-
composes with the formation of methyl
chloride (Vincent, Journ. Pharm. [4]
30, 132; Jahresber. 1878, 1 1 35). Me-
thyl chloride gives methane among the
products of pyrogenic decomposition
(Perrot, Ann. 101, 375), or a solution
of the chloride "might be reduced as
above under C.

[AA.] Benzene (see under cymene
[e ; I, &c.]) by the action of sulphuric
acid and potassium chlorate gives tri-
chlorphenomalic acid, CCI3 . CO . CH :
CH.COOH (Carius, Ann. 142, 129;
Kekule and Strecker, Ann. 223, 170;
Anschiitz, Ann. 254, 152), and this
decomposes into chloroform (and maleic
acid) on heating with barium hydroxide
solution. For reduction of chloroform
to methane see above under D.

[BB.] From malic acid [Vol. II],
which gives bromoform by the action
of bromine and alkali (Cahours, Ann. 64,
351). S ubsequent steps as above under D.

[CO.] From citric acid [Vol. II],
which gives bromoform as above.

[DD.] Ethylamine [Vol. II] gives
methane among the products of pyro-
genic decomposition (Miiller, Bull. Soc.
[2] 45, 43«)-

[EE.] Glucose [154] gives an oxime
which on reduction yields the base
glucamine. The latter gives iodoform
with iodine (Maquenne and .Roux,
Com p. Rend. 132, 980). From iodoform
to methane as above under D.

[FF.] From isovaleric acid. [Vol. II],
methane being among the products of
the dry distillation of the calcium salt
(Dilthey, Ber. 34, 21 15).

[GO.] Isoamyl alcohol [22] gives
methane among the products of pyro-
genic decomposition by the contact
action of certain heated metals on the
vapour (Ipatieff, Ber. 35, 1053).

[HH.] From acrolein [lOl] through
propinal and acetylene (see under
cymene [6 ; XVIII]), and then as
under A above.

2-4.]

NORMAL HEPTANE

27

2. Normal Heptane.

CH3. [CHgJg.CHg

Natural Soukcb.

Occurs in the exudation of the Cali-
fornian nut pine^ Finns sabiniana
(Thorpe, Trans. Ch. Soc. 35, 296 ;
37, 313). Also in the resin of Finns
jeff're^i (Blasdale, Journ. Am. Ch. Soc.
23, 163).

[Vol. II], a mixture of the potassium
salts giving a heptane on electrolysis
which is probably normal heptane
(Wurtz, Ann. 96, 372).

Note : — Many synthetical products belonging
to the aromatic series are said by Berthelot to
give heptane on heating to a high temperature
with strong aqueous hydriodic acid, but the
constitution of the heptanes thus obtained has
not been determined. (See for references under
methane [1 ; I] and under isoheptyl alcohol
[27].)

Synthetical Processes.

[A.] From methyl and n-hexyl alcohols
[13 J 23] by conversion into the corre-
sponding alkyl iodides and combination
of the alkyls by the action of sodium
on the iodides in ethereal solution
(general method of Wurtz, Ann. Chim.
[3] 44, 2"]^ ; see also Frankland, Ann.
71, 171; 74,41).

[B.] From ethyl and n-amyl alcohols
[14 ; 20] as above.

[C] From n-jpropyl and n-butyl alco-
hols [15 ; 17] as above.

[D,] (Enanthol [97] on reduction
with sodium amalgam or zinc dust and
acetic acid gives normal heptyl alcohol
(Bouis and Carlet, Ann. 124, '>,^1',
Schorlemmer, Ann. 177, 303 ; Cross,
Ann. 189, 2; Jourdan, Ann. 200, 102 ;
Krafft, Ber. 16, 1723). The alcohol
gives n-heptyl iodide on heating with
aqueous hydriodic acid (Jourdan, loc. cit.
104), and this might be reduced to
n-heptane by the usual methods (see
under methane [l ; C]).

Or cenanthol by the action of phos-
phorus pentachloride gives i : i-di-
chlorheptane = oenanthylidene chloride
(Limpricht, Ann. 103, 81), which by
the action of alcoholic potash gives
6-(a)-heptine = cenanthylidene {Ibid. ;
Rubien, Ann. 142, 294). The latter
combines with hydrogen by the ' con-
tact ' action of hot finely divided nickel
to form heptane (Sabatier and Sen-
derens, Comp. Rend. 135, 87).

[E.] From azela'ic acid [Vol. II]
through heptane by heating the barium
salt with barium oxide (Dale, Journ.
Ch. Soc. 17, 258).

[F.] From acetic and n-hepioic acids

3. Normal Fentadecane.
CH3 [CHJ13 . CH3

Natural Source.

Possibly a constituent of the essential
oil of Kaempferia galanga (P. van Rom-
burgh, Proc. K. Akad. Wetensch.
Amsterdam, 4, 618 ; Journ. Ch. Soc.
82, I, Abst. do,-^.

Synthetical Processes.

[A.] From palmitic acid [Vol. II]
and methyl alcohol [13] by distilling
the barium salt of the acid in a vacuum
with sodium meth oxide (Mai, Ber. 22,

2^34).

Or palmitic and acetic acids on dis-
tilling a mixture of the barium salts
give 2-heptadecanone (Krafft, Ber.
12, 1671), and this on oxidation with
chromic acid mixture gives pentadecylic
acid {Ibid.). The latter on heating
with hydriodic acid and phosphorus
to 240° gives n-pentadecane {Ibid. 15,
1700).

4. Normal Eeptacosane.

CH3[CH2]26.CH3

Natural Sources.

Occurs in beeswax (Schwalb, Ann.
235, 117) and in tobacco leaf (Thorpe
and Holmes, Trans. Ch. Soc. 79, 982 ;
see also Kissling, Ber. 16, 2432).

28

HYDROCARBONS

[4 A-6.

Synthetical Process.

[A.] From myrxstic acid [Vol. II]
through myristone jby distilling the
calcium or barium salt (Overbeck,
Pogg. Ann. 86, 591; Ann. 84, 290 ;
Krafft, Ber. 15, 17 13); the dichloride
by distilling with phosphorus penta-
chloride, and reduction of the dichloride
by heating with aqueous hydriodic acid
and phosphorus (Krafft, loc. cit.).

Note : — A heptacosane may occur in n6roli
oil (E. and H. Erdmann, Ber. 32, 12 14), but the
constitution of this hydrocarbon is at present
unknown.

5. XTormal Hentriacontane.

CH3[CH2]29 . CHg

Natural Sources.

Occurs with the preceding in bees-
wax (Schwalb, loc. cit.) and tobacco leaf
(Thorpe and Holmes, loc. cit.).

Synthetical Process.

[A.] From palmitic acid [Vol. II]
through palmitone by distilling the
barium salt (Piria, Ann. 82, 249) ; the
dichloride as above, and reduction of
latter as before (Krafft, loc. cit. 17 14).

6. Cymeue;

Faraisopropyltolnene ;

Faramethylisopropylbenzene ;

l-Methyl-4-Methoethylbenzene.

CH,

CHo . Cxi . CHj

Natural Sources.

In Roman cumin oil from the seeds
of Cuminmn cyminum (Gerhardt and
Cahours, Ann. 38, 70; loi ; 345); in
oil from the seeds of water-hemlock,
Cicuta virosa (Trapp, Journ. pr. Ch. 74,

428; Arch. Pharm. 231, 212; Ann.
108, 386) ; in oil of pepperwort, Satureia
hortensis (Jahns, Ber. 15, 816), and of
Satureia thymbra (SchimmeFs Ber. Oct.
1889).

Cymene occurs in oil of true bishop's
weed, Ptychotis ajowdn (Haines, Journ.
Ch. Soc. 8, 28; Miiller, Ber. 2,
130 ; Landolph, Ber. 6, 936) ; in oil
of thyme from Thymus vulgaris and
T. serpyllum (Lallemand, Journ. Pharm.
24, 274 ; Comp. Rend. 37, 498 ; Ann.
102, 119; Febve, Comp. Rend. 92,
1290); in oil of wild bergamot from
Monarda jistulosa (Kremers, Pharm.
Rund. 13, 207 ; Melzner and Kremers,
Pharm. Rev. 14, 198); and in oil of
American horsemint from Monarda
piinctata (Kremers and Hendricks,
Pharm. Arch. 2, 73 ; Schumann and
Kremers, Pharm. Rev. 14, 223).

According to Faust and Homeyer
(Ber. 7, 1429) cymene occurs in the oil
of Eucalyptus globulus, but according to
Gildemeister and Hoffmann (p. 691)
the oil investigated by these chemists
could not have been from that species.
Cymene occurs in oil of Eucalyptus
heBmastoma (Gildemeister and Hoff-
mann, p. 161), in oil of Thymus
capitatus from S. Spain (Schimmel's
Ber. Oct. 1889), in oil of Trieste and
Smyrna origanum from Origanum hirtum
and 0. smyrnaum (Jahns, Arch. Pharm.
215, I; Gildemeister, Ibid. 231, 182),
and in Ceylon oil of cinnamon (Schim-
meFs Ber. April, 1902; Walbaum and
Hiithig, Journ. pr. Ch. [2I 66, 47).

According to Tardy (pull. Soc. [3]
17, 580 ; 660) cymene is contained in
the oil of French bitter-fennel, but it
more probably resulted from the action
of hydrogen chloride on some other
constituent of the oil (Gildemeister
and Hoffmann, p. 740). According to
Klason the oil extracted from pine-
wood during the sulphite cellulose pro-
cess is cymene (Bied. Centr. 27, 137;
Ber. 33, 2343)-

Cymene is contained in the steam
distillate from lemon-grass oil from the
Indian Andropogon citratus (Dodge, Am.
Ch. Journ. 12, ^^'i, ; Stiehl, Journ. pr.
Ch. [2] 58, 51). Cascarilla oil from the
bark of Croton eluteria contains cymene

e.]

CYMENE

29

(Fendler, Arch. Pharm. 238, 671 : see
also Ch. Centr. 1900, 2, 574).

Note : — The cymene said in the older works
to be a constituent of so many plant oils is no
doubt some other hydrocarbon and was re-
corded before the discovery of dependable
chemical methods for identifying cymene. It
is probable also in many cases that the cymene
was produced by the action of the reagents
employed upon some constituent of the oil and
was not pre-existent as such.

Cymene is found in the urine of
dogs after repeated doses of sabinol
(Hildebrandt, Ch. Centr. 1901, 1, ^^).

Synthetical Processes.

One of the generators of cymene in
some of the synthetical processes is
benzencj and as this hydrocarbon is also
the generator of large numbers of other
synthetical products its syntheses are
here introduced : —

Sjintheses of Benzene.

[I.] From acetylene (see under meth-
ane [1; A]). The latter polymerises
under the influence of heat with the
formation of benzene (Berthelot, Comp.
Rend. 63, 479 ; Bull. Soc. [3] 7, 303 ;
Ann. Chim. [4] 9, 469).

Note : — Generators of acetylene (see under
methane [1 ; T ; U ; &c.]) thus become generators
of benzene.

Carbon monoxide combines with
potassium at 80° to form a salt of
hexahydroxybenzene, the latter being
liberated on treatment of the salt with
hydrochloric acid (Brodie, Journ. Ch.
Soc. [a] 12, 369 ; Ann. 113, 358 ;
Nietzki and Benckiser, Ber. 18, 1834).
Hexahydroxybenzene gives benzene
(and diphenyl) on distillation with zinc
dust.

Mellitic acid= benzenehexacarboxylic
acid can be obtained by oxidising char-
coal or other forms of carbon by alkaline
permanganate (Schulze, Ber. 4, 80a ;
806), by fuming nitric acid (Dickson
and Easterfield, Proc. Ch. Soc. 14, 163),
by the electrolysis of dilute acid or
alkali with carbon electrodes (Bartoli
and Papasogli, Gazz. 11, 468; Ch.
Centr. 1881, 327), by alkaline hypo-
chlorite {Ibid. Gazz. 15, 446), or by

heating with strong sulphuric acid
(Verneuil, Bull. Soc. [3] 11, 121;
Comp. Rend. 132, 1340). Mellitic
acid gives benzene when distilled with
soda-lime (Baeyer, Ann. Suppl. 7, 5).

Certain metallic carbides, e. g. of
barium, give benzene when heated to
600-800° with an equimolecular weight
of the metallic hydroxide (Bradley and
Jacobs, Germ. Pat. 125936 of 1898;
Ch. Centr. 1902, 1, 77).

[II.] Methane [l] and heptane [2]
give benzene among the products
formed by passing through a hot tube
(for heptane see Worstall and Burwell,
Am. Ch. Journ. 19, 815).

[III.] From ethyl alcohol [14] through
ethylene (see under methane [l; Dl).
The latter gives benzene among the
products formed by passing through
a hot tube (Berthelot, Bull. Soc. [a]
9, 456 ; Norton and Noyes, Am. Ch.
Journ. 8, 362).

Note : — Generators of ethylene thus become
generators of benzene. (See under methane
[1 ; S ; T ; V, &c.]).

Or from ethyl alcohol through chloro-
form, bromoform, or iodoform (see under
methane [l ; D]). ChloBoform gives
acetylene by passing the vapour over
heated copper (Berthelot, Comp. Rend.
50, 805) or by the action of potassium
or sodium amalgam (Kletzinsky, Zeit.
[2] 2, 127 ; Fittig, Ibid.). Iodoform
gives acetylene by the action of finely
divided silver, zinc, or the copper-zinc
couple (Cazeneuve, Comp. Rend. 97,
1371 ; Bull. Soc. [2] 41, 106). Bromo-
form gives acetylene by similar treat-
ment {Ibid. [3] 7, 70; see also Nef,
Ann. 308, 329). Acetylene gives ben-
zene by polymerisation as under I
above.

Note : — Generators of chloroform and iodo-
form given under methane thus become through
acetylene generators of benzene.

Or from ethylene through ethylene
bromide and acetylene by the action of
alcoholic potash on the latter (Miasni-
kofE, Ann. 118, 330 ; Sawitsch, Comp.
Rend. 52, 157; Ann. 119, 184; Sa-
banejeff, Ann. 178, iii), or by the
action of potassium isobutylate on the
bromide (Forcrand, Ann. Chim. [6] 11,

30

HYDROCARBONS

[6.

477), or by passing ethylene chloride
over hot soda-lime (Wilde, Ber. 1, ^$2).
[IV.] From normal or isopropyl alco-
hol [15 ; 16] through propylene and
allylene (see under benzyl alcohol [54 ;
E]). The latter gives mesitylene when
treated with sulphuric acid (Schrohe,
Ber. 8, 17). Mesitylene oxidises to
trimesic =1:3: 5-benzenetricarboxylic
acid (Fittig, Ann. 141, 153), and this
gives benzene on distillation with lime.

Note : —Generators of allylene (see under
benzyl alcohol [54 ; F, G, &c.]) thus become
generators of benzene. Generators of propylene
are given under glycerol [48].

[V.] From hutyl alcohols normal or
iso- [17; 18] through normal or iso-
butylene or pseudobutylene (see under
isobutyl alcohol [I8 ; A] ; tertiary butyl
alcohol [19 ; B] ; and secondary butyl
isothiocyanate [165 ; A and B]). Butyl-
ene or pseudobutylene bromide gives
crotonylene on treatment with alcoholic
potash (Caventou, Ann. 127, 347 ; Al-
medingen, Journ. Russ. Soc. 13, 392 ;
J. Wislicenus and Schmidt, Ann. 313,
ail), and this by the action of sulphuric
acid gives hexamethylbenzene (Alme-
dingen, loc. cit.). The latter on oxida-
tion with permanganate gives mellitic
acid (Friedel and Crafts, Ann. Chim.
[6] 1, 470), which gives benzene as
above under I.

Benzene is a product of pyrogenic
synthesis from isobutylene (Noyes ;
Beilstein, I, 115).

[VI.] Methyl alcohol [13] is said to
give a small quantity of hexamethyl-
benzene by the action of zinc chloride
(Greene and LeBel, Jahresber. 1878,
388).

A passage from methyl alcohol to
benzene is also possible through methyl
chloride and the further chlorination of
the latter to chloroform (Damoiseau,
Comp. Rend. 92,4a). From chloroform
through acetylene as above under III.

[VII.] From carhon dmdphide [I60]
through carbon tetrachloride (see under
methane [l ; L]). The latter is reduced
by zinc and dilute sulphuric acid to
chloroform (Geuther, Ann. 107, aia).

[VIII.] From acetone [IO6] through
mesitylene (see under benzyl alcohol
[54 ; D]), and then as above under IV.

Or from acetone through phorone
and pseudocumene (see under ortho-
cresol [61 ; B]). The latter oxidises to
a-xylic = methylterephthalic acid and
finally to trimellitic = i : 2 : 4-benzene-
triearboxylic acid (Fittig and Laubin-
ger, Ann. 151, 276; Krinos, Ber. 10,
1494), which gives benzene on fusion
with alkali (Barth and Schreder, Ber.

12, 1257)-

Or acetone and formic acid [Vol. II]
condense when the ethyl ester of the
latter and the ketone are acted upon
by sodium ethoxide. The product is
hydroxymethylene-acetone, and this
undergoes further condensation to tri-
acetylbenzene, which is oxidised to
trimesic acid by nitric acid (Claisen
and Stylos, Ber. 21, 1144).

[IX.] From formic and acetic acids
[Vol. II]. A mixture of the esters
when acted upon by sodium gives
^-hydroxyacrylic = hydroxymethylene-
acetic = f ormylacetic acid, which readily
condenses to trimesic ester (Piutti, Ber.
20, 537 ; Claisen and Stylos, Ber. 21,
1 146; see also Wislicenus and Binde-
mann, Ann. 316, 18).

Or a mixture of monochlor- or (better)
monobromacetic acid and ethyl formate
when acted upon by zinc condenses to
trimesic ester, from which the acid can
be obtained by hydrolysis (Reformatsky,
Journ. Russ. Soc. 30, a8o).

Or acetic acid on boiling potassium
dichloracetate with potassium acetate
solution gives the potassium salt of
diacetyldihydroxyacetic = diacetylgly-
oxylic acid (Doebner, Ann. 311, ia9).
The latter (salt) condenses with pyro-
racemic acid (see below under XIV) in
presence of alkali to phthalidetricarb-
oxylic acid, the aqueous solution of which
gives phthalidedicarboxylic acid on boil-
ing. The dicarboxylic acid gives toluene
when the barium salt is heated with
barium oxide (Doebner, loc. cit. 132).
Toluene can be oxidised to benzoic acid
[Vol. II], which gives benzene on dis-
tillation with lime.

Note : — Generators of toluene are given under
benzyl alcohol [54] passim.

[X.] From isohutyric dind. formic acid
[ V ol. II]. Isobutyric acid is brominated

e.]

CYMENE

31

(Markownikoff, Ann. 153, 239; Hell
and Waldbauer, Ber. 10, 448) and
a mixture of bromisobutyric ester and
formic ester acted upon by zinc. Tri-
mesic (with tetramethyloxyglutaric)
ester is formed (Blaise, Comp. Rend.
126, 1808).

[XI.] From succcinic acid [Vol. II]
through acetylenedicarboxylic acid (see
under methane [1; T]). The acid
potassium salt of the latter gives pro-
piolic = propargylic acid on boiling with
water (Bandrowski, Ber. 13, 2340), and
this on long exposure to light out of
contact with air partially condenses to
trimesic acid (Baeyer, Ber. 19, 3185).

Or from succinic acid through ethyl-
ene by electrolysis (see under methane
[l; T]), ethylene bromide and acetylene
as above under III, and polymerisation
as under I.

[XII.] From fumaric or maleic acid
[Vol. II] through acetylene by electro-
lysis (see under methane [l ; IJ]).

[XIII.] Isovaleric acid [Vol. II] gives
mesitylenic acid among other products
when the dry sodium salt is mixed with
sodium ethoxide and heated to 160° in
an atmosphere of carbon monoxide
(Loos, Ann. 202, 321). Mesitylenic
acid oxidises to trimesic acid (Fittig,
Ann. 141, 153).

[XIV.] From tartaric acid [Vol. II]
through pyroracemic acid (see under
benzyl alcohol [54; N]). The latter
gives uvitic acid (54 ; I), and this oxi-
dises to trimesic acid (Baeyer, Zeit. [2]
4, 119; Fittig and Furtenbach, Ann.
147, 301).

Pyroracemic acid condenses also with
acetaldehyde [92] or homologues (by
heating the mixture with baryta water)
to form uvitic = methylisophthalic acid
and homologues (Doebner, Ber. 23,
2377; 24, 1746). These alkyliso-
phthalic acids all oxidise to trimesic acid.

Note : — Generators of pyroracemic acid are
given under benzyl alcohol [54].

[XV.] From malonic acid [Vol. II]
and acetal [93]. The latter is con-
verted into monobromacetal (Pinner,
Ber. 5, 149; Fischer and Landsteiner,
Ber. 25, 2551), and this by interaction
with sodio-malonic ester gives acetal-

malonic ester (W. H. Perkin, junr., and
Sprankling, Trans. Ch. Soc. 75, 13),
which by hydrolysis to acetalmalonic
acid and the action of water at 180-
190° gives ^-aldehydopropionic acid
[Tbid. 16). The latter on heating with
sodium hydroxide solution gives tere-
phthalic acid {Ibid. 18), and this gives
benzene on distillation with lime.

Or from malonic acid and ethyl alcohol
[14] and chloroform through dicarboxy-
glutaconic ester by the interaction of
chloroform and sodio-malonic ester in
alcoholic solution (Conrad and Guthzeit,
Ann. 222, 250 ; Guthzeit and Dressel,
Ber. 22, 1414). The sodium deriva-
tive of dicarboxyglutaconic tetraethyl
ester on heating with alcohol at 150°
gives the triethyl ester of trimesic acid
(Lawrence and W. H. Perkin, junr.,
Proc. Ch. Soc. 17, 47).

Note : — Dicarboxyglutaconic ester can also be
obtained from sodio-malonic ester and etboxy-
methylenemalonic ester (Claisen and Haase,
Ann. 207, 86), or from sodio-malonic ester and
trichloracetic ester (Ruhemann, Ber. 29, 1017),
or from sodio-malonic ester and carbon tetra-
chloride (Dimroth, Ber. 35, 2881).

[XVL] Malic acid [Vol. II] by the
action of fuming sulphuric acid gives
coumalic acid = formylglutaconic anhy-
dride (v. Pechmann, Ber. 17, 936 j Ann.
264, 272). The methyl ester of the
latter is converted into trimesic mono-
methyl ester by dilute alkali [Ibid, Ann.
264, 294), and this can be hydrolysed
and converted into benzene as before.

Note: — Formylglutaconic = hydroxymetbyl-
eneglutaconic ester can also be obtained
by the action of dilute sulphuric acid on
sodium-ethylformylacetate (see above under
IX). The ester condenses to trimesic ester on
standing (oily form) or on distillation under
reduced pressure (Wislicenus and Bindemann,
Ann. 316, 18).

[XVII.] Tiglic acid [Vol. II] com-
bines with bromine to form a dibromide
which by the action of alcoholic potash
is converted into j8-bromangelic acid.
By the extreme action of alkali the
latter gives crotonylene (Wislicenus and
Henze, Ann. 313, 243). Subsequent
steps through hexamethylbenzene and
mellitic acid as above under V.

[XVIIL] From glycerol [48] through
acrolein [lOl] by dehydration (Redten-

32

HYDROCARBONS

[e A-P.

bacher, Ann. 47, I30 ; Van Romburg-h,
Bull. Soc. 36, 550 ; Griner, Ann. Chim.
[6] 26, 367 ; Aronstein, Ann. Suppl. 3,
180; Wag-ner, Journ. Russ. Soc. 16,
31 7 ; Wohl and Neuberg", Ber. 32, 1352),
dibromacrolein = dibrompropionic alde-
hyde by combination with bromine
(Aronstein, loe. cit. 185 ; Henry, Ber. 7,
1 1 12; Linnemann and Penl, Ber. 8,
1097), and the ethyl diacetal by con-
densing" the aldehyde with formimino-
ether (Claisen, Ber. 31, 1015). The
diacetal on treatment with alcoholic
potash gives the diacetal of propargyl-
aldehyde = propinal, the latter being
obtained by the action of dilute sul-
phuric acid on the diacetal (Claisen, loc.
cit. 1022). Propinal is decomposed by
aqueous alkali into acetylene and formic
acid (Claisen, loc. cit.). From acetylene
to benzene as above.

The synthetical processes for the pro-
duction of cymene are the following : —

[A.] From benzene, methyl [13], and
normal or isopropyl alcohol [15 ; 16].
Benzene and normal or isopropyl bromide
or the corresponding chloi-ides condense
in the presence of aluminium bromide
or chloride respectively to form isopropyl-
benzene = cumene (Gustavson, Ber. 11,
1 251 ; R. Meyer, Journ. pr. Ch. [2] 34,
98; Silva, Bull. Soc. [2] 43, 317;
Claus and Schulte im Hof, Ber. 19,
3012 : see also Kekule and Schrotter,
Ber. 12, 2280; Konowaloff, Journ.
Russ. Soc. 27, 457 ; Radziewanowski,
Ber. 28, 1137).

Or monobrombenzene and isopropyl
iodide condense to isopropylbenzene on
treatment with sodium (Jacobsen, Ber.
8, 1260).

Isopropylbenzene on bromination in
presence of iodine gives parabromiso-
propylbenzene (R, Meyer, loc. cit. 101),
and this condenses with methyl iodide
under the influence of sodium to form
cymene (Widman, Ber. 24, 439 j 1362 ;
see also Jacobsen, Ber. 12, 430).

Or toluene (see above under IX) and
isopropyl chloride condense to cymene
in contact with aluminium chloride
(Silva, loc. cit. 321).

Note : — Isopropylbenzene may also be syn-
thesised from toluene through benzal chloride

bychlorination (Beilstein, Ann. 116, 3.^6 ; Beil-
stein and Kuhlberg, Ann. 146, 322) and interac-
tion of the latter with zinc methyl (Liebmann,
Ber. 13, 46). Or from aimic acid [Vol. II] by
distillation with lime or baryta (Gerhardt and
Cahoura, Ann. Chim. [3] 1, 87 ; 372 ; 14, 107;
Ann. 38, 88). Or from isobuiyric aldehyde [84] and
pyroracemic acid (see above under XIV) through
isopropylisophthalic acid, which gives isopro-
pylbenzene on distillation with lime (Doebner,
Ber. 24, 1748). Orfromphenyldimethylcarbinol
through /3-allylbenzene = methovinylbenzene
by dehydration ; the hydrocarbon gives isopro-
pylbenzene by reduction (Tififeneau, Comp.
Rend. 134, 845). Also from acetophenone and
magnesium methiodide through methovinyl-
benzene and reduction (Klages, Ber. 35, 2640 ;
3507 ; 36, 620). See also under benzoic alde-
hyde (114 ; A).

[B.] From dipe?ite?ie [9] which gives
cymene on heating with phosphorus
pentoxide or cymenesulphonic acid by
the action of sulphuric acid. Or dipen-
tene (limonene) is combined with hydro-
gen bromide, the dihydrobromide further
brominated and the product debromi-
nated by reduction with zinc dust and
hydrochloric acid followed by sodium in
alcoholic solution (Baeyer and Villiger,
Ber. 31, 1401).

[C] From amyl alcohol [22] (crude
fusel oil) through the pentine or va-
lerylene obtained by the action of
alcoholic potash on the amylene bromide
(Reboul, Ann. 131, 238). This pentine
on heating to 250-260° gives a diva-
lerylene which is said to yield cymene
by the action of bromine (Bouchardat,
Comp. Rend. 90, 1560).

[D.] Geraniol [36] gives terpin hy-
drate [CjoHi8(OH)2 . H2O] by the
action of dilute mineral acids (Tiemann
and Schmidt, Ber. 28, 2137), and this
on dehydration over sulphuric acid
gives terpin [C,oHi8(OH)2]. The
latter gives a dibromide on heating
with bromine (Cj^HjgBrg), and this
gives cymene on heating with aniline
(Barbier, Bull. Soc. [2] 17, 17; Comp.
Rend. 74, 194).

[E.] Linalool [37] gives terpin hy-
drate under the same conditions as
geraniol (Tiemann and Schmidt, loc.
cit.).

[F.] Terpineol [39] combines with
bromine to form a dibromide which
gives cymene on heating with zinc
dust. Or terpineol on standing in con-
tact with dilute sulphuric acid gives

6 P-7 A.] CYMENE

terpin hydrate (Tiemann and Schmidt,
Ber. 28, 1781), which can be converted
into cymene as above under D.

[G.] Cineole [40] (eucalyptol) gives
cymene on distillation with phosphorus
pentasulphide (Faust and Homeyer,
Ber. 7, 438).

[H.] Menthol [4l] gives cymene on
heating with copper sulphate solution
at 260° (Briihl, Ber. 24, '>,'>,']S). Also
(with hexahydrocymene and other pro-
ducts) on treatment with strong sul-
phuric acid (Wagner, Ber. 27, 1638).

[I.] From thymol [67] by distilling
with phosphorus pentasulphide (Pott,
Ber. 2, 121). Or by the action of
phosphorus pentachloride on thymol and
reduction of the chloride (CjoHjoCl)
with sodium amalgam (Carstanjen,
Jahresber. 1871, 456).

[J.] Citral [104] gives cymene on
heating with aqueous hydrochloric acid
(Dodge, Am. Ch. Journ. 12, 561 ;
see also Tiemann, Ber. 32, 108), with
acid potassium sulphate at 170° (Semm-
ler, Ber. 24, 204), with acetic acid
(Barbier and Bouveault, Comp. Rend.
118, 1 051), or on treatment with zinc
chloride solution, with hydriodic or
sulphuric acid (Verley, Bull. Soc. [3]
21, 408).

[K.] Citronellal [105] combines with
bromine to form a dibromide which
gives cymene on heating (Beilstein's
' Handbuch,' III, 475).

[L.] From cumic aldehyde [II6]
through cumic alcohol (Kraut, Ann.
82, 66 ; 192, 324 ; Fileti, Gazz. 14,
498). The latter gives cymene on
boiling with zinc dust (Kraut, loc. cit, ;
Jacobsen, Ber. 12, 434)-

[M.] Carvone [127] gives cymene by
the action of the sulphides of phos-
phorus (Kekul6 and Fleischer, Ber. 6,
1088) and among the products formed
by passing the vapour over heated zinc
dust (Arndt, Ber. 1, 204).

[N.] From terpinene [lO], which forms
a nitrite which on reduction with
sodium in alcohol gives cymene among
other products (Wallach, Ann. 313, 361 j
Semmler, Ber. 34, 715).

33

7. Styrene; Styrolene; Fhenyl-
ethylene ; Cinnamene.

CH : CH,

Natural Sources.

Occurs in liquid storax, a balsam
from the Liquidambar orientalis of Asia
Minor and N. Syria (Bonastre, Journ.
Pharm. 17, 338 ; Simon, Ann. 31, 265 ;
Blyth and Hofmann, Ann. 53, 293 ;
325). Also in American storax from
Liquidambar styraciflua (W. v. Miller,
Arch. Pharm. 220, 648) and in the
oil from the yellow resin of Xanthorrhcea
hastilis of Australia (SchimmeFs Ber.
Oct. 1897 ; Ch. Centr. 1898, 1, 258).

Styrene exists as such in storax and
is not a product of distillation (Van
Itallie, Ch. Centr. 1901, 2, 856 : see
also Tschirch and Van Itallie, Arch.
Pharm. 239, 506 ; 532).

Synthetical Processes.

[A.] Among the products formed by
the action of Tieat on acetylene [l; A,
&c.] (Berthelot, Comp. Rend. 62, 905;
947 ; Ann. 141, 181). Also among the
products formed by passing acetylene
over finely divided nickel at 200° (Saba-
tier and Senderens, Comp. Rend. 134,
1 1 85). Also by passing ethylene [l ; D,
&c.] or ethylene and benzene vapour [6 ;
I, &c.] through a hot tube (Berthelot,
Bull. Soc. [2] 9, 456 ; Zeit. [2] 4, 384 ;
Ann. 142, 257 ; Ferko, Ber. 20, 660).

Toluene vapour, alone or mixed with
ethylene, gives styrene by pyrogenic
synthesis (Ferko, loc. cit.). Acetylene
passed through benzene in presence of
aluminium chloride gives styrene (Varet
and Vienne, Bull. Soc. [2] 47, 918;
Comp. Rend. 104, 1375)-

Or from ethylene through the brom-
ide and monobromethylene (vinyl brom-
ide) by the action of alcoholic potash
(Regnault, Ann. Chim. [2] 59, 358;
Beilstein, Jahresber. 1861, 609 ; Glock-

34

HYDROCARBONS

[7 A-C.

ner, Ann. Suppl. 1, 109 ; Semenoff,
Jaliresber. 1864, 480). Vinyl bromide
and benzene condense in the presence
of aluminium chloride to form styrene
(Hanriot and Gilbert^ Jahresber. 1884,
561 : see also Anschiitz, Ann. 235^

Note : — Vinyl bromide is formed also by the
combination of acetylene with hydrogen brom-
ide (.Reboul, Comp. Rend. 74, 947).

Or from ethyl alcohol [14] and benzene
through ethylbenzene by the condensa-
tion of ethyl bromide or iodide with ben-
zene in presence of aluminiiim chloride
(Friedel and Crafts, Ann. Chim. [6] 1,
457). Ethylbenzene g-ives styrene when
the vapour is passed through a hot tube
(Berthelot, Zeit. [2] 4, 589; Ferko,
Ber. 20, 663).

Or ethylbenzene on bromination at
its boiling-point or in presence of light
gives i^ - bromethylbenzene, CgHg .
CHBr . CH3 (Berthelot, Bull. Soc. 10,
343; Comp. Rend. 67, 338; Radzis-
zewski, Ber. 6, 492 ; 7, 141 ; Anschiitz,
Ann.235,328 ; Schramm, Ber. 18, 351),
and this gives styrene by the action of
heat or of alcoholic potash (Thorpe,
Proc. Roy. Soc. 18, 123 ; Radziszewski,
Ber. 7, 140). Or ethylbenzene on
bromination with two molecules of
bromine gives i^ : i^-dibromethylben-
zene = styrene bromide (Radziszewski,
Ber. 6, 493 ; also Friedel and Balsohn,
Bull. Soc. [2] 35, SS)} and this on
heating with strong alcoholic potash at
1 ao° gives phenylacetylene (Glaser, Ann.
154, 155 ; Zeit. [2] 5, 97 ; Friedel and
Balsohn, loc. cit.; Holleman, Ber. 20,
3080 ; see also Moureu and Delange,
Bull. Soc. [3] 25, 302). The latter
can be reduced to styrene by zinc and
acetic acid (Aronstein and Holleman,
Ber. 22, 11 84).

Or ethylbenzene can be converted
into phenylacetaldehyde = a-toluic alde-
hyde and co-phenylethylamine (see under
phenylethyl mustard oil [l70 ; A]).
The hydrochloride of the latter gives
styrene on distillation (Fileti and Piccini,
Ber. 12, 1308).

Note :— Generators of ethylbenzene are given
under phlorol as follows : — Tartaric or racemic
acid [Vol. II] and n-propyl alcohol [15] through
ethyBsophthalic acid (see under phlorol [64 ;

J]). Benzoic and acetic acids [Vol. II] through
acetophenone (see belowunder D) and dypnone
(see under phlorol [64 ; K]). Full references
to syntheses of ethylbenzene from benzene are
given under phlorol [64 ; A].

Benzene can be converted into aceto-
phenone by various processes (see under
benzoic aldehyde [114; A]). The ketone
reduces to methylphenyl carhinol [58]
(Emmerling and Engler, Ber. 6, 1006 ;
Klages and Allendorff, Ber. 31, 1003),
and this gives styrene on heating with
zinc chloride or by distilling the acetate
(E. and E. Ber. 4, 147 ; Radziszewski,
Ber. 7, 140), or by heating with syrupy
phosphoric acid (Klages and Allendorff,
Ber. 31, 1298).

Or methylethyl carbinol by the action
of hydrobromic acid gives i ^-brom-
ethylbenzene (Engler and Bethge, Ber.
7, 1 1 26), which gives styrene as above.

Or acetophenone and hydrogen sul-
phide combine in presence of hydrogen
chloride to form a trithio-derivative
(C24H24S3) which gives styrene on
heating (Baumann and Fromm, Ber. 28,
901).

By the action of phosphorus penta-
chloride acetophenone is converted into
the dichloride = i^ : i^-dichlorethyl-
benzene, and this gives phenylacetylene
by the action of alcoholic potash or hot
lime (Friedel, Comp. Rend. 67, 1192;
Morgan, Journ. Ch. Soc. 29, 164;
Peratoner, Gazz. 22, 67 ; Nef, Ch.
Centr. 1899, 2, 933). Phenylacetylene
can be reduced to styrene as above.

Toluene gives benzyl chloride on
chlorination at its boiling-point (see
under benzyl alcohol [54 ; A]), and this
by interaction with potassium cyanide
[172] and reduction of the product gives
phenylethylamine (see under phenyl-
ethyl mustard oil [l70; A]), which gives
styrene as above under A.

[B.] Cymene [6] gives cumic aldehyde
and acid, and isopropylbenzene (see under
benzoic aldehyde [ll4 j K]). The latter
gives acetophenone among the products
of the action of chromium oxychloride
(Miller and Rohde, Ber. 24, 1358).
Acetophenone gives styrene as above
under A.

[C] From benzoic aldehyde [ll4] and
acetic acid [Vol. II] and alcohol [14]
through phenylglycidic acid, a-toluic

7 C-I.]

STYRENE

35

aldehyde, and oo-phenylethylamine (see
under phenylethyl mustard oil [l70;
D]).

Or from benzoic aldehyde ^Miihyclrogen
cyanide [172] through mandelonitrile
and phenylethylamine (references as
before).

Or from benzoic aldehyde and chloro-
form [l ; D, &c.], which condense in
the presence of alkali to form trichlor-
methylphenyl carbinol (Jocitsch, Journ.
Russ. Soc. 29, 97). The latter by the
action of zinc dust on the alcoholic
solution gives styrene (Jocitsch and
Faworsky, Ibid. 30, 920).

[D.] From benzoic and acetic acids
[Vol.11] through acetophenone (Friedel,
Ann. 108, 122). Or from benzoic acid
and methyl alcohol [13] through benzoyl
chloride and zinc methyl, which yield
acetophenone by interaction (Popoff,
Ber. 4, 720; Ann. 161, 296) ; or benzoyl
chloride and sodio-acetoacetic ester [Vol.
II] give benzoylacetoacetic ester, which
yields acetophenone among other pro-
ducts on hydrolysis (Bonne, Ann. 187,
I ; Nef, Ann. 266, 99). Acetophenone
gives styrene as above under A.

Note : — Since ethylbenzene gives a-toluic
aldehyde and the latter phenylethylamine,
which is a generator of styrene (see above
under A), generators of a-toluic aldehyde be-
come generators of styrene (see below and
under phenylethyl mustard oil [170]).

[E.] From phenylacetic and formic
acids [Vol. II] through a-toluic aldehyde
[170; H].

[F.J From ^-})henylpropionic acid
[Vol. II] through co-phenylethylamine
[170; I].

[G.] From phenylalanine [Vol. II]
through co-phenylethylamine [170 ; J].

[H.] From cinnamic acid [Vol. 11],
which gives styrene by heating per se
or with lime or baryta or by heating
the copper salt (Gerhardt and Cahours,
Ann. Chim. [3] 1, 96 ; Ann. 38, 96 ;
Kopp, Comp. Rend. ^^, 634 ; Simon,
Ann. 31, 265 ; Howard, Journ. Ch. Soc.
13, 135; Hempel, Ann. 59, 318 ; Miller,
Ann. 189, 338 ; Kramer, Spilker, and
Eberhardt, Ber. 23, 3269).

Or cinnamic acid on combination
with hydrogen iodide gives iodhydro-
cinnamic = phenyliodopropionic acid.

d2

and this gives styrene on boiling with
sodium carbonate solution (Fittig and
Binder, Ann. 195, 137).

Cinnamic acid (or ester) combines
with bromine to form phenyldibrom-
propionic acid, which by the action of
alcoholic potash is converted into a-
brom- = i^-bromcinnamic acid and
finally into phenylpropiolic acid (Glaser,
Ann. 143, 32,5; 330; Barisch, Journ.
pr. Ch. [a] 20, 182; Kinnicutt, Am.
Ch. Journ. 4, 26; Stockmeier, Inaug.
Diss. 1 883, 52 j Glaser, Zeit [2] 4, 328 ;
Ann. 154, 140; W. H. Perkin, junr..
Trans. Ch. Soc. 45, 173; Weger, Ann.
221,70; Roser,Ann.247, 138; Michael,
Ber. 34, 3648 : see also Liebermann
and Sachse, Ber. 24, 41 13, note).
Phenylpropiolic acid on heating with
water at 120° or by distilling the barium
salt gives phenylacetylene (Glaser, Ann.
154, 155; Weger, loc. cit.: see also
Holleman, Ber. 20, 3081).

Or phenylbrompropionic acid on boil-
ing with sodium carbonate solution gives
co-bromstyrene, which, on heating with
alcoholic potash, gives phenylacetylene
(Nef, Ch. Centr. 1899, 2, 933, from
Ann. 308, 264, &c. : for conversion of
jQ-bromcinnamic acid into phenylacety-
lene see Michael, Ber. 34, 4226).

Cinnamic acid by the action of iodine
in presence of pyridine gives pyridine
/3-iodocinnamate, which, by the action of
sulphurous acid on the sodium hydroxide
solution, gives /3-iodocinnamic acid. The
silver salt of the latter gives phenyl-
acetylene on heating (Ortoleva, Gazz.
29, 503). Phenylacetylene can be re-
duced to styrene as above under A.

From cinnamic acid through phenyl-
a-chlorlactic acid, a-toluic aldehyde,
and a)-phenylethylamine (phenylethyl
mustard oil [170 ; A and E] and above
under A) ; or through a-oxyphenyl-
propionic lactone and a-toluic alde-
hyde [170 ; E] ; or through phenyl-
glyceric acid (benzaldehyde [114 ; E]),
phenyl-^-chlor- or bromlactic acid, and
a-toluic aldehyde (phenylethyl mustard
oil [170 ; E]).

[I.] Benzoylacetic eder [Vol. II] gives
phenyl-;3-lactic acid on reduction with
sodium amalgam (W. H. Perkin, junr.,
Trans. Ch. Soc. 47, 254). This acid

36

HYDROCARBONS

[7 19.

on heating with dilute sulphuric acid
gives, among other products, a small
quantity of styrene (Erlenmeyer, Ber.
13, 304).

[J.] From meihylphenyl carlinol [58]
by conversion into the chloride and
heating the latter with pyridine at 130°
(Klages and Keil, Ber. 36, 1632).

8. Metastyrene.
(C6H5.CH:CH2)x

Natural Sources.

Occurs in liquid storax (Kowalewsky,
Ann. 120, 66), and in Siegburgite, a
fossil resin found in sandy concretions
over deposits of brown coal at Troisdorf
and Siegburg (Klinger and Pitschki,
Ber. 17, 2742).

Synthetical Process.

[A.] From styrene [7] by polymerisa-
tion through heat (Blyth and Hofmann,
Ann. 53, 311 ; Lemoine, Comp. Rend.
125,530; Kronstein, Ber. 35, 4153)
or light (Lemoine, Ibid. 129, 719), by
the action of a hot solution of acid
sodium sulphite (Miller, Ann. 189, 341)
or of strong sulphuric acid (Berthelot,
Bull. Soc. 6, 296).

9. Dipentene; Inactive Limoueue;
Cajeputene ; Terpilene ; Oiuene ; Di-
isoprene ; Isoterebeuthene ; Caout-
chene.

CH3

HC CH„

H,C

CH,

CH
H3C • C : CHj

Natural Sources.

Occurs in Russian and Swedish tur-
pentine oil (Bertram and Walbaum, Arch.
Pharm. 231, 290 ; Wallach, Ann. 230,
244 ; 346) ; in camphor oil from Cinna-
momum camphor a (Lallemand, Ann. 114,

196; Wallach, Ann. 227, 296); prob-
ably in oil of cascarilla from the bark
of Crotoneluteria, Bahamas (Briihl, Ber.
21, 152; compare Thoms,Ch.Centr. 1900,
2, 574) ; in kuromoji oil from the
leaves of Lindera fericia, Japan (Kwas-
nick, Ber. 24, 81) ; in oil of elemi resin
from Cnnarium sp. ? (Wallach, Ann.
246, 233; 252, 102), and in oil of
Canadian golden-rod from Solidago
caraar/(?wM5(SchimmeFsBer. April, 1897).

Dipentene is contained also in the oil
of lemon-grass from the Indian Andro-
pogoti citratus (Stiehl, Journ. pr. Ch.
58, 51 ; Tiemann, Ber. 32, 834, on
authority of Bertram) ; in oil of berga-
mot (Charabot, Comp. Rend. 129, 728) ;
in oil of pine-needle (Bertram and
Walbaum, Arch. Pharm. 231, 296 ;
Wallach, Ann. 227, 287); in Ceylon
citronella oil from Andropogon, nardus
and vars. (Bertram and Walbaum, Journ.
pr. Ch. [2] 49, 16; SchimmePs Ber.
Oct. 1899); in small quantity in East
Indian geranium or palmarosa oil from
Andropogon schcetianthus (Gildemeister
and Hoffmann, p. 364) ; possibly in oil
of bay from Pimenta acris (Mittmann,
Arch. Pharm. 227, 529 ; compare Power
and Kleber, Pharm. Ruud. 13, 60) ; as
^terpinol' (a mixture) in oil from the
Californian bay, Vmbellularia calif ornica
(Stillmann, Ber. 13, 630 ; Wallach,
Ann. 230, 251); in oil of cubebs from
Piper cubeba (Wallach, Ann. 238, 78) ;
possibly in oil of black pepper from Piper
nigrum (Wallach, Ann. 287, 372) ;
possibly in oil of Ceylon cardamom from
Eleltaria cardamomum^vax. (Weber, Ann.
238, 98) ; and in oil of mace or nutmeg
from Myristica fragrans (Semmler, Ber.
23, 1803; 24, 3818).

Dipentene is contained in oil of
Massoia bark (Schimmel's Ber. Oct.
1888; Wallach, Ann. 268,340; Arch.
Pharm. 229, 116); possibly in oil of
lime leaves from Citrus limetta (Watts,
Trans. Ch. Soc. 49, 316); in oil of
fennel from Fceniculuni vnlgare (Schim-
meFs Ber. April, 1890) ; in oil of
myrtle from MyrUis communis {Ibid.
April, 1889) ; in kesso oil from the root
of Japanese valerian, Valeriana officinalis
var. angustifolia ; possibly derived from
pinene or terpineol by the action of acid

8.]

DIPENTENE

87

(Gildemeister and Hoffmann, p. 869) ;
in oils from the Spanish Satureia thymbra
(SchimmeFs Ber. Oct. 1889) and Thymus
capitatus {Ibid.) ; in oil of frankincense
from Boswellia carteri, &c. (Wallach,
Ann. 252, 1 00) ; in wartara oil, probably
from the seeds of Xanthoxyhim alatum
and X. acanthopodium (SchimmePs Ber.
April, 1900).

Dipentene and d-liraonene are con-
tained in the ethereal oil from the
bucco-leaf, Barosma betulina and B.
serratifolia (Kondakoff and Bachtschieff,
Journ. pr. Ch. [2] 63, 49). Dipentene
is contained (with d-limonene) in man-
darin oil (SchimmeFs Ber. Oct. 1901 j
Ch.Centr. 1901,2, 1007), and (probably)
in oil of pennyroyal from Mentha
puleginm (Tetry, Bull. Soc. [3] 27, 186).
White camphor oil, n^roli oil (Cannes),
and oil of petit-grain contain dipentene
(Schimmel's Ber. Oct. 1902 ; Ch. Centr.
190a, 2, 1207).

Note : — The question of the existence of di-
pentene as such in plant oils is complicated by
the fact that many compounds of the terpene
group give this hydrocarbon when acted upon
by heat or chemical reagents.

Dipentene is racemic limonene or
(possibly) a pseudo-form of limonene
(Semmler, Ber. 83, 1455). d-Limonene
= hesperidene, carvene or citrene. The
synthetical product is inactive (= di-
pentene), but the occurrence of the active
limonenes is here included in anticipation
of some method of resolution of the
racemic form being discovered. The
dipentene found in some ethereal oils
may arise from limonene by the action
of the heat applied for distillation.

d-Limonene occurs in oil of sweet
orange, Portugal (Wright, Ch. News,
27, 260; Wallach, Ann. 227, 287 : see
also Wright and Piesse, Ch. News, 24,
147 ; Flatau and Labbe, Bull. Soc. [3]
19, 361 ; Fabris, Journ. Soc. Ch.
Ind. 19, 771), and in the n^roli oil from
the flowers (Theulier, Ch. Zeit. 26, 1 26) ;
in oil of mandarin orange from Citrus
madurensis (Gildemeister and Stephan,
Arch. Pharm. 235, 583 ; Flatau and
Labbe, loc. cit. 364 ; Fabris, loc. cit. : for
references to botanical source of man-
darin oil see Gildemeister and Hoffmann,
p. 626, note) ; in Italian limetto oil

from Citrus limetta (Gildemeister, Arch.
Pharm. 233, 1 74) ; in oil from the peel
of Citrus medica (possibly with dipen-
tene : Burgess, 'Analyst,"* 26, 260) ; in
Chinese neroli oil from Citrus triptera
(Umney and Bennett, Pharm. Journ.
[4] 15, 146) ; in oil of lemon (Wallach,
Ann. 227, 290) ; in oil of bergamot
{Ibid.; also Charabot, Comp. Rend. 129,
728; Fabris, loc. cit. 772); in oil of
caraway from Cartim carui (Schweizer,
Ann. 40, 333 ; Journ. pr. Ch. 24, 257 ;
Sauer and Griinling, Ann. 208, T^;
Wallach, loc. cit. 291) ; and in oil of
dill from Beucedanum graveolens (Nietzki,
Arch. Pharm. 204, 317; Wallach, loc.
cit. 292).

d-Limonene occurs also in oil of fleabane
from Erigeron canadensis (Beilstein and
Wiegand, Ber. 15, 2854); in kuromoji oil
(see above under dipentene) ; in neroli oil
from orange flowers, CzVrw* bigaradia (Tie-
mann and Semmler, Ber. 26, 371 1 ; E.
and H. Erdmann, Ber. 32, 1214) ; in oil
of petit-grain from the young fruit of the
same plant (Paraguay oil : Semmler and
Tiemann, Ber. 25, 1186 ; Charabot and
Pillet, Bull. Soc. [3] 21, 74) ; in oil of
Massoia bark (see above under dipen-
tene) ; possibly in small quantity in oil
of spoonwort from Cochlearia officinalis
(Gadamer, Arch, Pharm. 237, 92).

d-Limonene occurs also in oils of
American horse-mint from Monarda
punctata and wild bergamot from M.
Jistulosa (Kremers and Hendricks,Pharm.
Arch. 2, 73 ; 76 ; Brandel and Kremers,
Pharm. Rev. 19, 200 : the hydrocarbon
from the latter plant is entered simply
as limonene) ; in oil of Malabar carda-
mom from Elettaria cardamomum (Parry,
Pharm. Journ. [4] 9, 105); in oil of
Macedonian fennel (Schimmel & Co. ;
Gildemeister and Hoffmann, p. 741);
in oil of celery from herb and seeds of
Apium graveolens (SchimmeFs Ber. April,
3892); in Ceylon citronella oil (Lana
Batu) from Andropogon nardus and vars.
(SchimmeFs Ber. Oct. 1 899). Limonene
probably exists in the oleo-resin of
I) aery odes hexandra, Montserrat, W.
Indies (More, Trans. Ch. Soc. 75, 718).

1- Limonene occurs in oil from the
needles and cones of Pinus picea =■ Abies
alba (Wallach, Ann. 227, 287; 246,

38

HYDROCARBONS

[9-G.

221 ; Bertram and Walbaum, Arch.
Pharni. 231, 290 ; Schimmers Ber. Oct.
] 892 ; April, 1893) ; in American oil of
spearmint from Mentha viridis (Power,
quoted by Gildemeister and Hoffmann,
p. 852 ; in Russian oil, SchimmeFs
Ber. April, 1898; Ch. Centr. 1898, 1,
991); in Russian peppermint oil (Andres
and Andreef, Ber. 25,609); in American
peppermint oil (Power and Kleber,
Pharm. Rund. 12, 157 ; Arch. Pharm.
232, 639) ; in oil of cascarilla (see
above under dipentene ; also Fendler,
Arch. Pharm. 238, 671); in oil of rue,
probably Algerian (Power and Lees,
Trans. Ch. Soe. 81, 1590); in the oil
of Bystropogon onganifolins, Teneriffe
(SchimmeFs Ber, Oct. 1902; Ch. Centr.
1902, 2, 1208).

The oil from the leaves of Verbena
tripTiyUa (Grasse) probably contains
1-limonene (Theulier, Rev. gen. de Chim.
5, 324). A limonene is present in the
American oil of cedar leaves from Juni-
perus virginiana (Schimmel's Ber. April,
1898; Ch. Centr. 1898, 1, 990).

Synthetical Processes.

[A.] From terpineol [39] by heating-
the latter with acid potassium sulphate
to 190° (Wallach, Ann. 230, 258; 275,
104; 291, 362).

[B.] Cineole [40] gives a hydro-
chloride which yields dipentene on dry
distillation (Hell and Stiircke, Ber. 17,
197 1; Hell and Ritter, Ibid. 1979;
"Wallach and Brass, Ann. 225, 298).
Also from cineole by heating with
benzoyl chloride or by combining with
hydrogen iodide and then eliminating
hydrogen iodide from the dipentene
dihydriodide thus formed (Wallach and
Brass, loc. cit. ; Wallach, Ann. 230,

^55)-

[C] Geraniol [36] by the action of

dilute mineral acids gives terpin hydrate
(Tiemann and Schmidt, Ber. 28, 2137).
The latter on heating with acid potassium
sulphate at 200° gives dipentene (Wal-
lach, as under A above).

[D.] Linalool [37] also gives terpin
hydrate by the action of mineral acids
(Tiemann and Schmidt, /oc. cit.). Formic
acid acts on 1-linalool with the forma-

tion of dipentene and terpinene (Ber-
tram and Walbaum, Journ. pr. Ch. [2]
45, 601; Stephan, Ibvl. [2] 58, 109:
see also Charabot, Bull, Soc, [3] 23,
189),

[E.] From carvone [127] through its
oxime and dihydrocarvylamine by re-
duction. The hydrochloride of the
latter gives dipentene among other pro-
ducts on treatment with sodium nitrite
(Wallach, Kruse, and Kerkhoff, Ann,
275, 110), Dihydrocarvylamine can
also be obtained from carvone by heating
with ammonium formate (Leuckart and
Bach, Ber. 20, 105; Wallach, /oc. cit.
120; Ber. 24, 3984).

d-Carvone can be reduced by sodium
to dihydrocarveol and the latter con-
verted into the xanthic acid dihydro-
carvyl methyl ester by means of carbon
disulphide and subsequent methylation
of the sodium salt. The methyl dihydro-
carvyl xanthate on dry distillation gives
1-limonene (Tschugaeff, Ber, 32, 3332 ;

33, 735)-

[F.] From normal or isopropyl alcohol
[15 ; 16] and potassium cyanide [172]
through the nitrile of pyrotartaric acid
by the interaction of propylene bromide
and the cyanide (Simpson, Ann, 121, 160)
and p - methyltetramethylenediamine
by reduction (Oldach, Ber, 20, 1654),
The diamine is converted into 3-/:?-
methylpyrrolidine by the dry distillation
of the hydrochloride {Ibid. 1657), the
latter base into /3-methyl-N-dimethyl-
pyrrolidylammonium iodide; the latter
distilled with solid potash gives a base
which combines with methyl iodide to
form/3-methyl-N-trimethylpyrrolidylam-
monium iodide, and the latter on distilla-
tion with solid potash gives trimethyl-
amineand isoprene [CHg : C(CH3) , CH :
CHg] (Euler, Ber, 30, 1989). Isoprene
polymerises on heating to 250° or by
the action of dilute or alcoholic sulphuric
acid with the formation of dipentene
(Wallach, Ann, 227, 295 ; Bouchardat,
Comp. Rend. 89, 1217).

Note :— All generators of propylene thus be-
come, with potassium cyanide, generators of
dipentene.

[G.] From glycerol [48] through
allyl chloride (see under benzyl alcohol

G-12.]

DIPENTENE

39

[54 ; F]) and potassium cyayiide [172]
through pyrotartaric nitrile (Pinner,
Ber. 12^ 3053) and then as above.

10. Terpinene ; A^-^-Menthadiene.

CH3

/\

HC CH,

[p.] From carvone [127] through
dihydrocarveol by reduction. The latter
gives terpinene on boiling with dilute
sulphuric acid (Wallach, Kruse, and
Kerkhoff, Ann. 275, 113). Dihydro-
earvylamine also gives terpinene when
acted upon by acid (Wallach, Ber. 24,
3991) or by distilling the dry hydro-
chloride (Wallach, &c. Ann. 275, 120).

H,C

CH

./•

11. LsBVO-Isoterpene (?),

CHj . CH . CH3

For constitutional formula see Harries,
Ber. 35, 11 69.

Natural Sources.

In oil of Ceylon cardamom from
Elettaria cardamomum, var. major
(Weber, Ann. 238, 107), and in oil of
sweet marjoram from Origanum tnajo-
rana (Biltz, Ber. 32, 995).

Note : — It is possible that the terpinene does
not pre-exist in the oils from these plants, but
is formed from some compound in the oils by
the heat of distillation (Gildemeister and Hoff-
mann, p. 178 : see also Semmler, Ber. 34, 718).

Synthetical Processes.

[A.] Bipentene [9] gives terpinene
on treatment with hydrochloric or sul-
phuric acid in alcoholic solution (Wal-
lach, Ann. 239, 15; 35). Limonene
gives terpinene when distilled with
solid arsenic acid (Genvresse, Comp.
Rend. 134, 360).

[B.] Cineole [40] gives terpinene by
the same treatment (Wallach, Ann.
239, 2a).

[C] Terpineol [39] gives terpinene
among other products on heating with
dilute sulphuric acid (Wallach and
Kerkhoff, Ann. 275, 106) : also on boil-
ing for some time with oxalic acid
solution or with anhydrous formic acid
{Ibid. 291, 342).

[D.] From geraniol [36] through
terpin hydrate (see under dipentene [9 ;
C]) and the action of boiling dilute
sulphuric acid on the latter.

[E.] From linalool [37] through ter-
pin hydrate, &c. (see under dipentene
[9 ; D] ; also Bertram, Journ, pr. Ch.
45, 601).

^10^16

Natural Sources.

A hydrocarbon corresponding with
the above possibly exists in elemi resin
from species of Canarium and in the
resins from Pifius and Abies (Kuriloff,
Journ. Russ. Soc. 21, 362).

Synthetical Process.

[A.] IWpineol [39] gives isoterpene
on heating with acetic anhydride to
135-150° (Flawitzky, Ber. 12, 2356).

Note : — The synthetical product was obtained
from 1-terpineol acetate prepared by the action
of zinc chloride and acetic acid on pinene
(Ertschikowsky, Journ. Russ. Soc. 28, 132).
The synthesis is thus complete only in so far
as the synthesis of 1-terpineol is complete.
d-Isoterpene is also said to have been syn-
thesised from d-terpineol (Flawitzky, Ber. 20,
1961)

12, Naphthalene.

H

H

HC C CH

I II I

HC C CH

\/ \/

H H

Natural Sources.

According to v. Soden and Rojahn
(Pharm. Zeit. 47, 779) this hydrocarbon
is contained in certain ethereal oils from
clove stems and storax bark.

Syntheses of naphthalene are given
under hydrojuglone (90).

40

[13.

ALCOHOLS

MONOHYDRIC OF FATTY SERIES

13. Methyl Alcohol; Carbinol;
Methanol ; Wood Spirit,

CH3.OH

Natural Sources.

Methyl alcohol is contained in the
steam distillate from meadow grass
(Lieben, Monats. 19, 333) ; in the dis-
tillation water from oil of cloves (Schim-
meFs Ber. Oct. 1H96), from oil of
caraway {Ibid. Oct. 1899), from vetiver
oil from the roots of Andropogon muri-
catus {Ibid. April, 1900), from the oil
of the fruit of Heradeiim giganieum
(Zincke and Franchimont, Ber. 4, 832 ;
Moslinger, Ber. 9, 999 ; Gutzeit, Ann.
177, 344) and H. sphondyliu7n (Moslin-
ger, Ber. 9, 998; Ann. 185, 26), and
fi-om oil of tea from leaves of Thea
chinensis (Van Romburgh, SchimmeFs
Ber. April, 1897, and April, 1898 ; Ger-
ber, Mon. Sci. [4] 11, 880; Ch. Centr.
1898, 1, 122).

Methyl alcohol occurs also in the
aqueous distillate from the unripe fruit
of Anthriscus cerefoUum (Gutzeit, Ann.
177, 382), from the oil obtained by dis-
tilling the leaves of Indigofera galego'ides
(Van Romburgh, Schimmel's Ber. Oct.
1894; April, 1896), from oil of bay
(SchimmePs Ber. April, 1901), and in
the steam distillate from the root of
Acorus calamus (Schnedermann, Ann.
41, 374; Kurbatoff, Ber. 6, 1210;
Gladstone, Journ. Ch. Soe. 17, i ;
Geuther, Ann. 240, 109).

It is doubtful in these cases whether
the alcohol exists in the free state
in the plant or whether it is produced
by the hydrolysis of esters. (For refer-
ences to the occurrence of free methyl
alcohol in juices of plants see Gutzeit,
Jahresber. 1879, 905 ; Maquenne, Comp.
Rend. 101, 1067 ; also Lieben as above.)

Methyl alcohol is found in the fer-
mented juice of fruit, such as currants,
plums, apples, cherries, grapes, &c.
(Wolff, Comp. Rend. 131, 1323).

Esters of methyl alcohol occur very
frequently in volatile plant oils. Me-
thyl esters of fatty acids occur in the
fruit of Heradeiim giganieum and H.
sphondylium ; methyl butyrate probably
occurs in the oils from the fruit of
Anthriscus cerefoUum and Pastinaca
sativa (Gutzeit, Ann. 177, 344) ; methyl
esters of myristic and (possibly) oleic
acids occur in the oil of orris-root from
(?) Iris germanica (Tiemann and Kriiger,
Ber. 26, 2675 : Iris pallida and /.
jiorentina also furnish orris-root oil :
the botanical source of the oil examined
by Tiemann and Kriiger is not stated).

Methyl salicylate occurs in many
plants, notably in oil of wintergreen
(as the glucoside gaultherin) from
Gaultheria procumbe?is (Cahours, Ann.
Chim. [3] 10, 327; Ann. 48, 60; 52,
327 ; Procter, Am. Journ. Pharm. 14,
211; Ann. 48, 66; Kremers, Pharm.
Rev. 20, 350), from the leaves of G.
punctata (De Vrij, Pharm. Journ. [3]
2, 503 ; Kohler, Ber. 12, 246 ; Brough-
ton, Pharm. Journ. [3] 2, 281 : the
latter refers to the oil from Andromeda
leschenaultii, probably = G. punctata),
and from the leaves of G. leucocarpa,
Java (De Vrij, loc. cit. ; Kohler, loc.
cit.).

Methyl salicylate occurs (also as the
glucoside gaultherin) in the bai*k of the
sweet birch, Betula lenta (Procter, Am.
Journ. Pharm. 15, 241 ; Schneegans
and Gerock, Arch. Pharm. 232, 437 ;
Power and Kleber, Pharm. Rund. 13,
228 ; Kremers, Pharm. Rev. 20, 350).
The oil from the flowers of the meadow-
sweet. Spiraea ulmaria, contains me-
thyl salicylate (Schneegans and Gerock,
Jahresber. Pharm. 1892, 164) and also
the oil from the roots (Nietzki, Arch.
Pharm. 204, 429). According to Bey-
erinck (Centr. Bakter. 5, 425) the
roots, rhizomes, and lower parts of
SpircBa ulmaria, S. jilipendula, and 8.
palmata contain the glucoside gaultherin.
Methyl salicylate is present in oil of

13.]

METHYL ALCOHOL

41

rue, probably from Algeria (Power and
Lees, Trans. Ch. See. 81, 1587). The
oils from the following plants also
contain methyl salicylate : —

Spicewood or spicebush oil from the
N. American Laurus benzoin (Schim-
meFs Ber. Oct. 1885 and Oct. 1890);
oil from the leaves of Erythroxylon coca
(Van Romburgh, Rec. Tr. Ch. 13,
435; SchimmeFs Ber. Oct. 1895 ; April,
1896) ; oils from roots of Puli/gala
senega, var. latifolia (Renter, Arch.
Pharm. 227, 313); -?• variabilis = ^-
albiflora, P. oleifera, and P. javana (Van
Romburgh, Rec. Tr. Ch. 13, 421),
P. vulgaris, P. calcarea, and P. serpyl-
lacea = depressa (Bourquelot, Comp.
Rend. 119, 80a; Journ. Pharm. [5]
30, 96; 188; 433; [6] 3, SIT' ac-
cording to Bourquelot the roots contain
gaultherin) ; roots of Monotropa hypo-
joitys as gaultherin (Bourquelot, Journ.
Pharm. [5] 30, 435 ; [6] 3, 577 ; Comp.
Rend. 119, 8oii ; 122, 1002) ; oils from
Viola tricolor^ Acacia intsia, A. phiri-
cajoitata, A. sarmentosa, A. tenerrima,
and A. farnesiana (SchimmeFs Ber.
Oct. 1899; Journ. Soc. Ch. Ind. 18,
1 153); oil of tea (SchimmeFs Ber.
April, 1898; see also above) ; ylang-
ylang oil (SchimmeFs Ber. Oct. 1901 ;
Ch. Centr. 1901, 2, 1007). Methyl
benzoate may also be present in this
last oil {Ibid.).

The following list of plants contain-
ing methyl salicylate is given by
Schimmel & Co. (Ber. April, 1900)
as having been investigated in the
Government Laboratory of the Botani-
cal Gardens at Buitenzorg : —
Anacardiaceae. Mangifera sp. ; Seme-
carpus sp.
Anonaceae. Cananga odorata.
Apocynacese. Allamanda hendersoni ;
Ch'ilocarpus densijiorns ; C. denu-
datus ; Melodinus leevigatus ; M.
orientalis ; Landolphia watsonii.
Artocarpacese. Cecropia schiedeana ;
Ficus elastica ; F. benjamina and
var. crassinervis ; F. annulata ; F.
geniculata ; F. pilosa and var.
chrysocoma ; F. retusa, var. nitida ;
F.xylophylla ; Streblus mauriiianus ;
Sloetia sideroxylon.
Boraginaceae. Cordia asperrima.

Burseraceae. Canariunt sp.
Cupuliferae. Castanopsis javanica ; and
var. tungurrut ; Quercus sp. ; Q.
bancana; Q. glandulifera ; Q.jung-
hulinii ; Q. teysmannii.
Euphorbiaceae. Antklesma diandrum ;
Adenocrepis javanica ; Agyneia multi-
jiora ; Baccaurea sp. ; Cyclostemon
sp. ; Flateriosjjermum tokbrai; Cluy-
tia oblongifolia ; Euphorbia sp. ;
Leiocarpus sp. ; L. arboreus ; Pie-
rardia dulcis and other sp. ; Phyl-
lanthus zeylanicus ; Rottlera dis-
par ; Spihenodesme pentandra ; Tre-
wia sp.
Gnetaceae. Gnetum gnemon = j3-ovali-

folium,
Myrtaceae. Memecylon sp.
Podocarpaceae. Podocarpus chinensis;

P. nageia.
Rhizophoraceae. Carallia integerrima.
Rosaceae. Rubus sundaicus.
Rubiaceae. Cantkium sp. ; Gardenia
schoemannii ; Nauclea sp. ; Pavetta
angustifolia ; P. arborea ; P. bar-
bata ; P. grandijiora, vars. lutea
and aurantiaca ; P. littorea ; P.
longijiora ; P. rosea ; P. paludosa ;
P. longipes and other sp. ; Pe-
tunga roxburghii ; Psychotria cela-
stroides ; Wendlandia sp.
Styraceae. Symplocos sp.
Ternstrcemiaceae. Camellia lanceolafa ;

Thea cockincAi?ie7isis.
Tiliaceae. ElcBocarpus resinosiis.
Urticaceae. Gironniera subaqualis and
another sp.
(For localities of species the original
must be consulted ; see also Journ. Soc.
Ch. Ind. 19, SS^.)

The methyl ester of anthranilic acid
occurs in neroli oil from the flowers of
the bitter orange. Citrus bigaradia
(SchimmeFs Ber. April, 1899 ; Wal-
baum, Journ. pr. Ch. [2] 59, ^S^'i
Ber. 32, 1512; E. and H. Erdmann,
Ber. 32, 1213; 33, 2061; also Germ.
Pat. 5958 of 1898 ; Hesse and Zeit-
schel, Ber. 34, 299 ; Journ. pr. Ch. 64,
245 ; Theulier, Bull. Soc. [3] 25, 762) ;
also in oil from the peel of the sweet or
Portugal orange (Parry, Ch. Drug.
56, 462; 722; SchimmeFs Ber. April,
3 900 and Oct. 1900; compare Theulier,
Bull. Soc. [3] 25, 762), in oil of limette

42

ALCOHOLS

[13.

(Parry, loc. cit. 993), in oil of Gar-
denia (Parone, Boll. Ch. Farm. 41, 489 ;
Ch. Centr. 190a, 2, 703), in Chinese
neroli oil from Ciinis triptera (Umney
and Bennett, Pharm. Jom-n. 69, 146),
and in oil of berg-amot leaves (Schim-
meFs Ber. Oct. 1902; Ch. Centr.
1902, 2, 1207 ; Gulli, Ch. Drug. 60,

995)-

The methyl ester of methylanthra-
nilic acid occurs in mandarin oil from
the rind of Citrus wadurensis ( Walbaum,
Journ. pr. Ch. [2] 62, 135) and from
the leaves (Charabot, Comp, Rend. 135,
580), and possibly in oil of rue from
Ruta graveolens (Schimmel's Ber. Oct.
1901 ; Ch. Centr. 1901, 2, 1007; see
also Houben, Ber. 35, 3587).

Oil of jasmine from the flowers of
Jasminum grandijiorum contains methyl
anthranilate (Hesse, Ber. 32, 2616 ;
33, 1585; 34, 291; 2916; Zeit. an-
gew. Ch. 1900, p. 270; see also E. Erd-
mann, Ihid., and Ber. 34, 2281, and
Germ. Pat. 122290 of 1898 : accord-
ing to Hesse the methyl anthranilate
does not pre-exist in the flowers in the
free state, Ch. Ind. 25, i : compare
Erdmann, Ber. 35, 27).

Methyl cinnamate occurs in the oil
from the root, stems, and leaves of
Aljmiia malaccensis (SchimmeFs Ber.
April, 1899) and in wartara oil, pro-
bably from the seeds of Xanthoxylum
alatum zn^X.acanthopodiiim (Schimmers
Ber. April, 1900, and May, 1901).
Methyl benzoate occurs in oil of cloves
(SchimmeFs Ber. April, 1902) and in
ylang-ylang oil [Ibid. Oct. 1901 ; see
also Darzens, Bull. Soc. [3] 27, 83).

The vegetable alkaloids cocaine, y, 8,
and €-isatropylcocaine from the leaves
of Err/throoBi/lon coca; colchicine from
the seeds of meadow saffron, Colchicum
autumnale ; ricinine from the seeds of
Ricinus communis, and arecoline from
the nuts of Areca catechu are the methyl
esters of complex acid radicles. Me-
thysticin or kawain from kawa-root
[Piper methysticmri) is the methyl ester
of methysticinie = 3 : 4-phenediol-i^-
heptylonic acid. Gummigutt resin,
the dried sap of Garcinia morella,
yields a gum which may contain a
methyl ester (Tassinari, Gazz. 26, 249).

Many products obtained from lichens
appear to be methyl esters : —

Atranorin or atranoric acid = par-
melin from Lecanora atra, L. subfusca,
L. sordida and vars. glaucoma and
swartzii, L. campestris, L. thiodes, Cla-
donia rangiferina, C. rangiformis, Evernia
prunastri, E.farfuracea, E. vxdpina, Par-
melia perlata, P. ceratophylla or physodes,
P. tiliacea, P. ciliaris (probably), P.
fuliginosa, P. aleurites, P. oliveforum, P.
saxatilis, var. phaotropa, var. sulcata,
and var. panniformis, P. stellaris, var.,
P. speciosa, P. acetabulum, P. oynpha-
lodes, P. perforata, P. nilgherrensis,
P. encausta, P. pertusa, Parmeliopsis
hyperopia, Ramalina pollinaria, Placo-
dium saxicolum, var. compactmm, P. me-
lanaspis, Terecaulon sp., Physcia parie-
tina, P. ceesia, P. pulverulenta var. ^-
pityrea, P. endococcina, P. tenella, P.
aipolia, Anaptychia ciliaris, Sphyridium
placophylliim, Cetraria fahlunensis, C.
chlorophylla, C. complicata, Platysma
glaticiim, Mycoblastus sanguinarius, Ever-
niopsis trulla, Stereocaulon vesuvianum^
S. alpinum, S, corallo'ides, S. salazinum,
S. incrustatum, S. denudatum, var. gemii-
num, S. tomenfosum, S. pileatum, S. con-
densatum, S. paschale, S. virgatum^ forma
primaria, S. ramulosum, HiBmatomma
coccineum, and vars. leiphcBmum and
abortivum, Urceolaria scrvposa, var. vul-
garis {^), U. cretacea (?), Pnlveraria [Jjc-
praria) latebrarum, Blasfenia arenaria^
var. teicholytum = Callopisma teicholy-
tum, Pachnolepia decussata. (For dis-
tribution, synonymy, and nomenclature
of these and other lichens see Paternb
and Oglialoro, Jahresber. 187V, 811 ;
Paternb, Gazz. 10, 157 ; 12, 256 ; Zopf,
Ann. 284, 174; 288, 38; 295, 222;
292; 297, 271 ; 300, 322; 306, 282;
313, 317; 317, 120; 139; 321, 37;
324, 39 ; Hesse, Ann. 284, 157; Ber.
30, 357 ; 1983 ; 31, 663 ; Journ. pr.
Ch. [a] 57, 232 ; 409 ; 58, 465 ; ^^^ ;
62, 321 ; 430; 63, 522 ; 65, 537 : the
view that atranorin is a methyl ester is
due to Hesse, Journ. pr. Ch. [2] 57,

232-) . . . .^

Physcianin = atraric acid = cerato-

phyllin, a product of decomposition of

atranorin, is ^-orcinolcarboxylic methyl

ester (Hesse, Ber. 30, 359 ; 1988 ;

13-B.]

METHYL ALCOHOL

43

Journ. pr. Ch. [2] 57, 287 ; 422 ; Ch.
Centr. 1898, 1, 1303: see also under
^-oreinol [77]).

Bangiformic acid from Cladonia ran-
giformis (Paterno, Gazz. 12, 259 ; Zopf,
Ann. 288, 6'^ ; Hesse, Journ. pr. Ch.
[2] 57, 275), and chrysocetraric =
pinastric acid from Cetraria juniperina,
G.pinastri, Calycium jlavum^zxA Lepraria
fiava are methyl esters, the latter of
oxypulvic acid (Zopf, Ann. 284, 107 ;
Hesse, Ibid. 176; Journ. pr. Ch. [2]
57, 307 ; 62, 34a ; 65, 537 ; 552, &c.).

Lecidic acid from Lecidea cinereo-afra
is a methyl ester (Hesse, Journ. pr. Ch.
[2] 58, 508). Caperatic acid from
Farmelia caperata, Mycohlastus sangui-
nariiis, var. endorhodea, and Tlatysma
glaucum may be a methyl ester (Hesse,
Ber. 30, 365 ; Journ. pr. Ch. [2] 57,
427 ; Zopf, Ann. 306, 306 ; 312).

Parellic acid = psoromic = squamaric
and (?) zeoric acid is a methyl ester
found in the following lichens: — Le-
canora parella {OchroJechia pallescens,
y-parella), L. varia, L. sordida, var.
glaucoma, Placodium crassum, var. ccespi-
tosmn^ P. lagaftccB, P. gypsaceiim, P. cir-
cinatum, Rhizocarpon geographicum, var.
lecanorina, and vars. contiguum and
geronticum, Stereocaulon corallo'ides (?),
S. incrustatum^ S. vesuvianum, S. demi-
datum, var. genuinum or pulvinatum,
Catocarpus alpicoltts, Roccella intricata,
R. tinctoria, Darhishirella gracillima,
Cladonia pyxidata^ Vsnea ceratina, U.
harbata and jiorida (Schunck, Ann. 54,
274 ; Spica, Gazz. 12, 431 ; Zopf, Ann.
284, 129; 288, 59; 295, 2-33; 236;
248; 251; 273; 295; 297,285; 317,
no; 321, 37; Hesse, Journ. pr. Ch.
[2] 57, 272; 274; 58, 518; 62,430;
462 ; 465 ; 65, 537 ; Ber. 30, 363 ;
31, 663. Hesse was unable to find this
acid in Lecanora parella, from which it
was first said to be obtained by Schunck,
and concludes that this last author had
some other species in hand ; see Ch.
Centr. 1902, 2, 38a).

Thamnolic acid from Thamnolia ver-
micularis, Cladonia jioerkeana, and Cla-
dina nncialis may be a methyl ester
(Zopf, Ch. Centr. 1 893, 2, 54 ; Journ.
pr. Ch. [2] 58, 465 ; 62, 441 ; 446 ;
Ann. 324, 39).

Vulpic acid is the methyl ester of
pulvic acid = diphenylketipic anhy-
dride, and is found in the following
lichens: — Cetraria (= Evernia) vtdpina,
C. pinastri, C. tubulosa, C. juniperina,
Cyphelium ckrysocephalum, Calycium
chlorinum, C. chlorellum, C. stenhamari,
Parmelia perlata, American, (Moller
and Strecker, Ann. 113, ^6 ; Bolley,
Jahresber. 1864, 554 ; Zopf, Ann. 284,
120; 324, 39 ; Hesse, Ann. 284, 173;
Journ. pr. Ch. [2] 57, 316; 62, 340;
65, 537 : the later papers of Zopf and
Hesse referred to above under atranorin
may also be consulted for references to
vulpic acid : for references to con-
stitution see also Spiegel, Ann. 219,
I, &c.).

The. methoxy group, CH3.O, is con-
tained in large numbers of natural pro-
ducts belonging to nearly every family
of organic compounds. Such com-
pounds are in a sense ethers of methyl
alcohol.

Methyl alcohol is among the products
of fermentation of glycerol by Bacillus
boocopricus (Emmerling, Ber. 29, 2727),
of the bacterial fermentation of calcium
glycerate (Fitz, Ber. 13, 131 2), and of
the fermentation of the juice of the
sugar-cane by a special (wild) yeast
(Marcano, Comp. Rend. 108, 955).

Synthetical Pkocesses.

[A.] From carbon, oxygen, and hy-
drogen, a mixture of carbon monoxide,
and the latter giving methyl alcohol
among other products under the influence
of the electric discharge in an ' ozoniser'
(Slosse and Solvay, Bull. Acad. Roy.
Belg. 35, 547; Ch. Centr. 1898, 2,
421).

[B.] From methane [l] by chlorination
and the action of aqueous potash on
the methyl chloride (Berthelot, Ann.
105, 241 ; Ann. Chim. [3] 52, loi).
Methane and air (the mixture contain-
ing insufiicient oxygen for complete
combustion) give methyl alcohol among
other products when passed over finely
divided copper, asbestos, or coppered
pumice (Glock, Germ. Pat. 1090 14 of
1898; Ch. Centr. 1900, 2, 304; see
also Coquillon in Journ. Soc. Ch. Ind.

44

ALCOHOLS

[13 B-14.

19, 684, abst. from Zeit. Spiritusind.
23, 18a).

[C] From glycerol [48], methyl
alcohol being among the products formed
by the dry distillation of the calcium
compound (Destrem, Ann. Chim, [5]
27, 20; Comp. Rend. 90, 1213) or by
heating the sodium compound above
245" (Fernbach, Bull. Soc. [2] 34, 146).

[D.] From formic aldehyde [9l] by
heating with strong sodium hydroxide
solution (Low, Ber. 20, 144) or lime
water {Ihid. 21, 271), or by the pro-
longed action of potassium hydroxide
solution at ordinary temperatures (Del^-
pine. Bull. Soc. [3] 17, 938 : see also
Comp. Rend. 123, J 20 ; Bull. Soc. [3]
15, 997, and Lieben, Monats. 22, 289).

[E.] From formic acid [Vol. II],
methyl alcohol being among the pro-
ducts formed by the dry distillation of
the calcium salt (Friedel and Silva,
Bull. Soc. [2] 19, 481; Comp. Rend.
76, 1545; Lieben and Paternb, Ann.
167, 293 ; Gazz. 3, 290).

[P.] From acetic acid [Vol. II] by
acting with iodine on the silver salt
and hydrolysing the methyl acetate
formed (Simonini, Monats. 13, 320 ;
see also Birnbaum, Ann. 152, iii).
Methyl acetate is among the products
of electrolysis of potassium acetate in
aqueous solution (Kolbe, Ann. 69, 279),
especially in presence of acid (Petersen,
Ch. Centr. 1897, 2, 518). The alcohol
is produced by electrolysis from sodium
or potassium acetate in presence of
sodium perchlorate (Hofer and Moest,
Ann. 323, 284).

[G.] From methylamine [Vol. II] by
the action of nitrous acid (Linnemann,
Zeit. [2] 4, 284).

[H.] From trimethylamine [Vol. II]
through methyl chloride by heating the
dry hydrochloride (Vincent, Journ.
Pharm. [4] 30, 132). From methyl
chloride as above under B.

[I.] From ethyl alcohol [14] through
chloral by chlorination. Methyl chloride
is among the products of reduction of
chloral by zinc or iron dust in aqueous
solution(Cotton, Bull. Soc. [2] 42,622).

[J.] From aldehyde [92] through
chloral (see under methane [l ; l]), and
then as above under I.

[K.] From malonic acid [Vol. II] by
electrolysis of a solution of the potas-
sium salt (Petersen, Zeit. physik. Ch. 33,
714).

14. Ethyl Alcohol;
Methyl Carbinol ; Ethauol.

CH3 . CH2 . OH

Natdeal Soueces.

Ethyl alcohol is contained in the
steam distillate from grass and leaves
previously macerated in very dilute
sulphuric acid (Lieben, Monats. 19,
$'^'^). According to Berthelot (Comp.
Rend. 128, 1366 ; see also Devaux,
Ibid. 1346) alcohol is formed in the
tissues of growing plants (wheat and
hazel).

Alcohol is formed by the cells of
plants from carbohydrates by ^intra-
cellular respiration' when they are
insufficiently supplied with oxygen
(J. R. Green's 'Soluble Ferments and
Fermentation,' p. 327 et seq. ; Lafar's
'Technical Mycology,' Vol. II, p. 78;
Pasteur, Comp. Rend. 76, 1054 ; Le-
chartier and Bellamy, Comp. Rend. 79,
949; 1006; 81, 1 1 29; Brefeld, Land-
wirth. Jahrbuch, 5 ; De Luea, Ann.
Sei. Nat. [6], 6 ; Miintz, Comp. Rend.
86, 49; Ann. Chim. [5] 13, 543;
Gerber, Ann. Sci. Nat. [8] 4 : for
production of alcohol by intracellular
respiration in beet see Strohmer, Zeit.
Zucker. 24, 685; v. Lippmann, Ber.
31, 677 ; by peas, Godlewski and Pol-
zeniusz, Bied. Centr. 27, 135 ; Journ.
Ch. Soc. 74, II, Abst. 400; 80, II,
Abst. 618; Ch. Centr. 1901,2,595;
Maze, Comp. Rend. 128, 1608; Ann.
Inst. Past. 16, 195 ; Takahashi, Bull.
Coll. Agric. Tokio, 5, 243 ; by deep
tissues of woody stems, Devaux, Comp.
Rend. 128, 1346 : for general sum-
mary see also J. R. Green's address to
the Brit. Assoc. Belfast, 1902 : for
isolation of the enzyme causing anaero-
bic cellular respiration in higher animals
and plants see Stoklasa and Czerny,
Ber. 36, 622).

Ethyl alcohol is formed by yeast as
a product of auto-fermentation (Har-

14.]

ETHYL ALCOHOL

45

den and Rowland^ Trans. Ch. Soc. 79^
1237).

Ethyl alcohol is contained in the dis-
tillate from rose leaves, but this may
arise from carbohydrates by fermenta-
tion (Eckart;, Arch. Pharm. 229, ^!^^;
Ber. 24, 4305 ; SchimmeFs Ber. Oct.
1892).

Ethyl alcohol is found in the distilla-
tion water from the unripe fruit of
Heradeum giganteum (Gutzeit, Ann.
177, 344)^ from the fruit of H. sphon-
dylium (Moslinger, Ber. 9, 998 ; Ann.
185, 26) and of Pastinaca sativa and
Anthriscus cerefolium (Gutzeit, loc. cit.
372 ; 382), from the oil of the leaves of
Indigqfera galego'ides (SchimmeFs Ber.
April, 1896), and from the oil of storax
from Liquidamhar orientalis (v. Miller,
Ann. 188, 1 84). The forerunnings from
iheoi\oiEiicali/ptus globulus C0TitQ,met}iy\
alcohol (Bouchardat and Oliviero, Bull.
Soc. [3] 9, 429). The alcohol in these
cases probably arises partly or wholly
from esters by hydrolysis (Gutzeit con-
sidered the alcohol to exist in the free
state in the fruit of Heradeum, Ann.
240, 243).

The ethyl ester of butyric acid is
contained in the oil from the unripe
fruit of Heradeum giganteum (Gutzeit,
Ann. 177, 344). Ethyl butyrate is
contained also in the oil from the fruit
of Heradeum sphondylium (Moslinger,
loc, cit.). Ethyl acetate is contained in
the flowers of Magnolia fuscata (Goppert,
Ann. Ill, 127) ; ethyl valerate probably
occurs in Algerian oil of rue (Power and
Lees, Trans. Ch. Soc. 81, 1589) ; ethyl
cinnamate in liquid storax from
Liquidamhar orientalis (v. Miller, loc.
cit. ; Tschirch and Van Itallie, Arch.
Pharm. 239, 506) and in the oil from
Kaempferia galanga (Van Romburg-h,
Proc. K. Akad. Wetensch. Amsterdam,
4, 618; Journ. Ch. Soc. 82, I, Abst.

Ethyl esters of hexoic, octoic, decoic,
lauric, palmitic, and oleic acids are
present in the juice from the fruit of
the saw palmetto, Sahal serrulata (Sher-
man and Brig-gs, Pharm. Arch. 2, loi).
The oil from the root of Kaempferia
galanga contains the ethyl ester of
p-methoxycinnamic acid (Van Rom-

burgh, SchimmeFs Ber. Oct. 1900;
Journ. Ch. Soc. 78, I, Abst. 677).

Rhizocarpic acid, a product from
certain lichens, is an ethyl ester of
a complex acid (Hesse, Journ. pr. Ch.
[2] 58, 510). This acid has been
obtained from the following species : —
Rhizocarpon geographicum and vars. con-
tiguum, lecanorinum, and geronticuMy
R. viridi-atrum, Pleopsidium chloro-
johanum, Acarospora chlorophana, Haphio-
spora jiavovirescens, Biatora lucida,
Catocarpus alpicolus = Catocarpon chino-
philum, Acolium tigillarey Gasparinia
elegans, G. medians (Zopf, Ann. 284,
114; 295, 275; 313, 334; 321, 37;
Hesse, Ber. 30, 362; 31, 66^; Journ.
pr. Ch. [2] 57, 446; 58, 511 ; 62,
343 ; see also Salkowski, Ann. 319,

391)-

An ethyl ester of vulpic acid (see
under methyl alcohol [l3]) = callopismic
acid occurs in the lichens Physcia
medians, Callopisma vitellinum^ Cande-
laria concolor, and Gyalolechia aurella
(Zopf, Ann. 284, 123; 295,239; 297,
290).

Hsematommic acid obtained from the
lichens Hcematomma coccineum, Physcia
ccBsia, Stereocaulon ramulosum, and Par-
melia perlata, is an ethyl ester of atra-
norin (Zopf, Ann. 288, 39; 44; 295,
280 ; 297 ; Hesse, Journ. pr. Ch. [3]
57, 292).

Ethyl alcohol is a product of fer-
mentation of various sugars by species
of yeasts, Saccharomyces. The follow-
ing species or forms are now recognized
as alcoholic ferments : —

Saccharomyces cerevisiee I, Hansen ;
S. pastorianus I, II, and III, Hansen;
S. logos, Van Laer; S. ellipsoideus I
and II, Hansen ; S. ilicis, Gronlund ;
S. aquifolii, Gronlund ; S. pyriformis,
Marshall Ward; S. vordermanni, Went
and Geerligs; S. marxianns, Hansen;
S. exiguus, Reess and Hansen ; S. jor-
gense?m, Lasch^ ; S. ludwigii, Hansen ;
S. octosporus, Beyerinck; S. pombe,
Saare and Zeidler ; -5^. mellacei, Holn
and Jorgensen ; S. acidi lactici, Groten-
f elt ; S. fragilis, Jorgensen ; S. ano-
malus, Hansen ; S. conglomeratus, Reess
(doubtful ferment) ; 8. apiculatus,

46

ALCOHOLS

[14.

Reess. (See for further particulars
Jorgensen^s ' Mikroorg-anismen der
Garungsindustrie/ chap, vj Klocker's
' Garungsorganismen^ &c.' ; and Lafar^s
'Technical Mycology/ Vol. 11.) Sac-
charomyces saturnus, Klocker, from soil
in the Himalayas, can ferment wort
(Klocker, Abst. in Journ. Fed. Inst.
8, 523). S. awamori, Inui, a yeast
which is concerned in the production
of the Japanese drink ' awamori,' is an
alcoholic ferment (Inui, Journ. Imp.
Coll. Sci. Tokio, 1901, 15; Abst. in
Journ. Fed. Inst. 8, 529).

Certain ethyl esters, such as ethyl
acetate, propionate, butyrate, valerate,
hexoate, heptoate, octoate, ennoate,
palmitate, and oleate, are found in fusel
oils and in whisky, and may be secon-
dary products of alcoholic fermenta-
tions by yeasts and therefore of bio-
chemical origin (Perrot, Comp. Rend.
45, 309 ; Ann. 105, 64 ; Rabuteau,
Comp. Rend. 87, 501 ; Ordonneau,
Ibid. 102, 217 ; Bell as quoted by
Allen, Journ. Fed. Inst. 3, 36 ; Barker,
Ann. Bot. 1900, 215).

Synthetical carbohydrates, such as
'glycerose,' obtained by the oxidation
of glycerol and now known to be
a mixture of glyceraldehyde and di-
hydroxyacetone [l5l] (Van Deen,
Jahresber. 1863, 501 ; Stone, Am. Ch.
Journ. 15, 6^6 ; Fischer, Ber. 20,
1088; Fischer and Tafel, Hid. 3384;
21, 3634; Grimaux, Comp. Rend. 104,
1276; Bull. Soc. [2] 46, 481; 49,
251), dextrose [l54], Isevulose [l55],
d-mannose [l56], and mannononose
(Fischer and Passmore, Ber. 23, 2237)
give alcohol on fermentation by yeasts.
According to Piloty (Ber. 30, 3166)
and Bertrand (Comp. Rend. 126, 842 ;
984 ; Bull. Soc. [3] 19, 502) dihydroxy-
acetone is not fermentable. According
to Emmerling (Ber. 32, 542) neither
dihydroxyacetone nor glyceraldehyde
are fermentable when pure.

The f ermentability of sugars, natural
and synthetical, by yeasts is associated
with the number of the carbon atoms
in the sugar, the configuration of the
atoms in the molecule, and the nature
of the yeast. According to Fischer
(Ber. 23, 2114) the fermentable sugars

contain multiples of three carbon atoms.
As regards configuration, while the
three hexoses and the nonnose men-
tioned above are with d-galactose fer-
mentable, the following sugars are
unfermentable :— d-gulose and 1-gulose
(Fischer, Ber. 24, 521 ; Fischer and
Stahel, I6id. 528; 2144); d-talose
(Fischer, ioc. cit. 3622) ; sorbose (Pe-
louze, Comp. Rend. 34, 377 ; Ann.
Chim. [3] 35, 222); tagatose =l-sor-
bose (Lobry de Bruyn and Van Eken-
stein, Rec. Tr. Ch. 16, 257 ; 262 ;
19, i) ; glutose {Ibid. 16, 257 and 274);
the hexoses of the 1-series, such as
1-fructose (Fischer, Ber. 23, 370),
1-mannose (Fischer and Thierf elder, Ber.
27, 2031), 1-xylose (Koch, Ber. 20, ref.
145 ; Thomsen, Journ. pr. Ch. 19, 146 ;
Stone, Ber. 23, 3791), the pentoses,
rhamnose, the synthetical heptoses and
octoses (Fischer, Ber. 23, 930 ; Fischer
and Piloty, 7^/fi?. 3102; 3827; Fischer
and Morrell, Ber. 27, 382 ; Fischer
and Passmore, Ber. 23, 2226 ; Fischer,
Ann. 270, 64; 288, 139 ; Smith, Ann.
272, 182); glucononose (Fischer, Ann.
270, 104).

[For general summary see Fischer
and Thierf elder, Ber. 27, 2031 ; Fischer,
Zeit. physiol. Ch. 26, 60 : for resolu-
tion of i-glucose, i-mannose, i-fructose,
and i-galactose by partial fermentation
with brewer''s yeast see Fischer, Ber.
23, 382; 2620; 25, 1259.

The fermentability of twenty-one
sugars and carbohydrates by various
yeasts and yeast-like fungi, without
reference to products, has been investi-
gated on a microscopic scale by Lindner,
Woch. Brau. 17, 713 ; 733; 746; 762;
Ch. Centr. 1901, 1,57; 4^4 ^ Journ.
Fed. Inst. 7, 224 : for experiments on
the relative fermentability of dextrose
and laevulose by Niirnberg, &c., sedi-
mentary and other yeasts see Knecht,
Centr. Bakter, II, 7, 161 ; 215.]

Manneotetrose, Cg^H^gOg,, a sugar
contained in ' manna, ■* is fermentable
by yeast (Tanret. Comp. Rend, 134,
1586 ; Bull. Soc. [3] 27, 947). Three
synthetical disaccharides, glucosido-
galactose, galaetosidoglucose (? meli-
biose), and galactosidogalactose, are
unattacked by surface yeast, and only

14.]

ETHYL ALCOHOL

47

the two first are fermented by sedi-
mentary yeast (Fischer and E. F. Arm-
strong, Ber. 35j 3144).

The various species of Saccharomyces
behave differently towards different
sugars, their behaviour having relation-
ship to the enzymes contained in the
yeast cell : —

S. cerevisice, S. pastoriannSy and S. el-
lipsoicleus ferment saccharose, maltose,
and the products of their inversion,
i. e. dextrose and Isevulose, but not lac-
tose; S. ilicis and S. aquifolii ferment
saccharose, maltose, and dextrose ; S.
pyriformis and S. vordennanni ferment
saccharose; S. exiguus, S. marxianus,
and S. jorgensenii ferment saccharose
and dextrose, but not maltose; S. lud-
wigii ferments dextrose and saccharose,
but neither maltose nor lactose ; S.pombe
ferments dextrose and saccharose ;
S. acidi laclici and S. fragilis ferment
lactose (summarised from Jorgensen's
' Mikroorganismen, &c/ chap. v).
S. membranafaciens is inactive towards
most sugars (Fischer and Thierf elder,
Ber. 27, 203 1 ). So also is S. kansenii.
S. kyalosporus , S.farinosus, and S. ano~
malus, var. belgicus (all Lindner''s), can-
not ferment maltose, dextrose, or sac-
charose (^DieGarungsorganismen, &c.,'
Klocker, p. 203). S. bidwigii is inca-
pable of fermenting galactose, and may
therefore be used for separating this
sugar from dextrose (Thomas, Comp.
Rend. 134, 610). S. apiculatus fer-
ments dextrose and mannose (Cremer,
Zeit. Biol. 29, 525), but not saccharose,
lactose, maltose, or galactose (Voit, Zeit.
Biol. 29, 149 ; Hansen and Amthor,
Zeit. physiol. Ch. 12, ^6^).

S. (= Schizomccharomyces) octosporus
ferments dextrose and maltose, but not
saccharose (Beyerinck, Centr. Bakter.
12, 49 ; Fischer and Lindner, Ber. 28,
984 ; 3034). S. productivus, S. mem-
branafaciens, and S. pombe are incapable
of fermenting d-galactose under ordinary
conditions, but this sugar is ferment-
able under suitable conditions by S.
cerevisieB, by S. pastorianus I, II, III, by
S. ellipsoideus I, II, by S. marxianus,
and (slowly) by the mould Monilia Can-
dida (Bau, Bied. Centr. 26, 213). The
yeasts appear to be capable of gradual

adaptation or ' acclimatisation * towards
this sugar (Dubourg, Comp. Rend. 128,
440 ; Dienert, Ibid. 569 ; 617; Ann.
Inst. Past. 14, 139 : S. ludwigii does
not seem to be amenable to this treat-
ment : for adaptation of yeasts to
saccharose see also Dubourg, loc. cit. :
for variation in chemical activity of
yeasts produced by cultivation see Han-
sen, Zeit. ges. Brau. 25, 41 ; 57 ; 70 ;
82 ; Journ. Fed. Inst. 7, 299).

S. anomalus, vars. I, II, III, and IV, has
been investigated by Steuber (Zeit. ges.
Brau. 23, 3; 17; 33; Journ. Fed.
Inst. 6, 123). I ferments saccharose,
glucose, and fructose, but not maltose,
lactose, or galactose ; II ferments sac-
charose slowly, but not fructose, glucose,
maltose, lactose, or galactose ; III and
IV produce a trace of alcohol from
fructose, but do not ferment any of the
other sugars.

According to Barker (Ann. Bot.
1900, 215) S. anomalus of Hansen
can ferment glucose, fructose, and
saccharose, but not maltose. This
yeast also produces ethyl and amyl
acetates. S. bailii of Lindner can fer-
ment dextrose and ' invert ' sugar ; S.
mali duclauxi of Kayser (found in cider)
can ferment invert sugar, but neither
maltose nor saccharose (' Die Garungs-
organismen, &c.,^ Klocker, p. 215). Sac-
char omyces opunticB, which ferments the
must of Indian figs, can ferment dex-
trose and Isevulose, but not lactose,
rafl[inose, galactose, mannitol, or dulcitol
(Ulpiani and Sarcoli, Gazz. 31, 395).
From a mixture of S, pastorianus II
and S. opuyitice sodium fluoride elimi-
nates the latter [Ibid. Atti Real. Accad.
[5] 11, 173).

Milk sugar is fermentable by three
yeasts from Armenian ^mazun,' by
Weigmann^s yeast, Sachsia suaveolens,
and, possibly, by Monilia variabilis
(Lindner, Ch. Centr. 1901, 1, 56 ;
Woch. Brau. 17, 713). The top fermen-
tation yeast, S. pastorianus arborescens,
can ferment dextrose and laevulose,
but not galactose nor di- and trisac-
charides (Van Laer, Bull. Assoc. Belg.
16, 177 ; Journ. Fed. Inst. 8, 763).

S. [Schizosaccharomyces) pombe and
octosporus and S. logos are said to be

48

ALCOHOLS

[14.

dextrin-ferments (Jorgensen, loc. cit.
p. 216, note ; see also Marshall Ward,
Journ. Fed. Inst. 4, ^SS). S. pomhe,
S. octosporus, and S. mellacei are included
by Lindner {loc. cit.) among dextrin
ferments.

The pentoses from the straw of
cereals which give furfural on distil-
lation with dilute acid are said to yield
alcohol on fermentation by yeast (Cross,
Bevan, and Smith, Trans. Ch. Soc. 71,
1003 ; Bailey and Ford, Germ. Pat.
97238 of 1896; Ch. Centr. 1898, 2,
590). Pentoses generally, such as xylose
and arabinose, are not fermentable by
yeast (Stone, Ber. 23, 3796 ; Stone
and Tollens, Ann. 249, 267 ; Tollens,
Journ. Fed. Inst. 4, 447 ; Schone and
Tollens, Journ. Ch. Soc. 80, I, 367).
The pentosans from jute and brewer's
grains give alcohol on fermentation by
pure-culture yeast from lager beer yeast
{Ibid : also Journ. Fed. Inst. 7, 472).

The transformation of sugar into
alcohol by yeast has been found by
Buchner to be brought about by the
action of an enzyme-like nitrogenous
compound (zymase) formed by the
living cell, but capable of acting on
BUgar when removed from the cell.
The literature relating to this discovery
is given below : Buchner, Ber. 30,
117; 1110; Buchner and Rapp, Ibid.
266S ; Stavenhagen, Ibid. 2422 ; 2963 ;
Neumeister, Ibid. ; v. Manassein, 3id.
3061 ; Green, Ann. Bot. 11, ^55; 12,
491; Will, Ch. Centr. 1898, 1, 69;
Delbriick, Ibid. 70 ; Hahn, Ber. 31,
300 ; Geret and Hahn, Ibid. 202 ;
Buchner and Rapp, Ibid. 209 ; Schunck,
Ibid. 309 ; Buchner and Rapp, Ibid.
1531 ; Will, Ch. Centr. 1898, 2, 439 ;
Lange, Ibid. 548 ; Abeles, Ber. 31,
2261; Geret and Hahn, Ibid. 2335;
Wroblewski, Ibid. 3218 ; Centr. Physiol.
12, 697 ; Martin and Chapman, Proc.
Physiol. Soc. June, 1898; Buchner
and Rapp, Ber. 32, 127; 2086;
Wroblewski, Centr. Physiol. 13, 284 ;
Cremer, Ber. 32, 2062; Albert, Ibid.
2372; Albert and Buchner, Ber. 33,
266; 971; Ahrens, Zeit. angew. Ch.
1900, 483; Macfayden, Morris, and
Rowland, Ber. 33, 2764; Hahn and
Geret, Ch. Centr. 1900, 2, 641 ; Buch-

ner, Ber. 33, 3307; 331 1 ; Albert,
Ibid. 3775 ; Prior and Schulze, Zeit.
angew. Ch. 14, 208 ; Buchner and
Rapp, Ber. 34, 1523 ; Wroblewski,
Bull. Acad. Sci. Cracow, 1901, 94;
Journ. pr. Ch. [2] 64, i ; R. and W.
Albert, Centr. Bakter. II, 7, 737 ;
Buchner and Spitta, Ber. 35, 1703;
Buchner and Rapp, Ibid. 2376 : for gene-
ral summary see ' Die Zymasegarung,'
by E. and H. Buchner and Martin
Hahn, Munich and Berlin, 1903.

Not only the true yeasts but other
related micro-fungi, and certain moulds
and bacteria, are capable of producing
alcohol from sugars as well as from more
complex carbohydrates : —

Hansen has investigated certain
species of Torula. Sp. Ill can ferment
hexose, but not saccharose ; Sp, IV and
VI can transform saccharose, but not
maltose; Sp. VII ferments dextrose,
but not saccharose or maltose. Sp. I,
II, and V appear to be incapable of
producing alcoholic fermentation. T.
nova carlsbergifB of Gronlund can in-
vert and ferment saccharose, maltose,
and dextrose. The red pigment-form-
ing Torula of Kramer inverts and fer-
ments saccharose and ferments maltose
and dextrose, but not lactose (summar-
ised from Jorgensen's ' Mikroorganis-
men,'' &c. ch. v).

A Torula-\\kQ species discovered in
milk by Duclaux (Ann. Inst. Past.
1, 573) ferments lactose, which is not
attacked by ordinary yeasts. * Sac-
charomycea ' lactia of Adametz (Centr.
Bakter. 5, l^?)C)),\\ie non-Saccharomyces
of Kayser (Ann. Inst. Past. 8, 737),
and Beyerinck's ' Saccharomyces ' kephir
and tyrocola (Centr. Bakter. II, 6, 44)
are said to produce alcohol from lactose.
Lactomyces i?ijlans caseigrana from cheese
(Bochiccio, Centr. Bakter. &c. 16, 546)
can ferment lactose in bouillon.

Certain species of Mycoderma formerly
confused with M. cerevisice of Hansen
produce alcohol in wort (Lasche, as
quoted by Jorgensen, loc. cit. 4th ed.
p. 263). Species of Mycoderma can
produce small quantities of alcohol from
dextrose under appropriate conditions
(Beyerinck : see paper by Van Laer,
Journ. Fed. Inst. 7, 352).

14.]

ETHYL ALCOHOL

49

The moulds Mncor racemosns, M. sto-
lonifer, M. circineUo'ides, M. spi?iosj(s)
31. erechis, Mxoasciis alnitorquus (Sade-
beck), Penicillium glaucum, and Rhizopus
nigricans are generally included among'
alcohol-producing fungi (Reess^ ' Botan.
Untersuch. iiber die Alkoholgarungs-
pilze/ 1870; also J. R. Green's ^Fer-
mentation/ p. 325 et seq.). Mucor
spinosus and M. circinelloules ferment
glucose (Gayon, Ann. Chim. [5] 14,
258 ; Comp. Rend. 86, 52 ; Bull. Soc.
[2] 31, 139; for earlier work on alco-
holic fermentation by Mucor racemosus
see Fitz, Ber. 6, 48 ; 8, 1540; 9, 1352 ;
1354; Brefeld, Ber. 7, 282). Mncor
mucedo, M. erectus, M. sj)i?io,ms, M.
alternans, M. circinelldides, and Rhizopus
nigricans cannot invert and ferment
saccharose; with the exception of the
latter they can all produce alcohol from
maltose and they all ferment dextrose
and laevulose, Mucor alternans fer-
ments trehalose, but not raffinose. These
moulds cannotfermentgalactose directly,
but only after inversion (Lafar's ' Tech-
nical Mycology,' II, 81). M. racemosus
is the only one of these species of Mucor
that can invert and ferment saccharose
(for quantitative results see Emmerling,
IBer. 30, 454) ; the others ferment not
only glucose, but ' invert ' sugar and
maltose. M. erectus can produce alcohol
from dextrin (Hansen as quoted by
Jcirgensen, ' Mikroorganismen,' &c.
126). Chinese yeast contains Mucor
{Am)jlomyces\rouxii (Calmette, Ann. Inst.
Past. 6,604), and this produces alcohol in
culture solutions of dextrose, d-f ructose,
galactose, trehalose, d-mannose, maltose,
dextrin, and a-methylglucoside, but not
from saccharose, lactose, xylose, arabinose,
rhamnose, tagatose, raffinose, melibiose,
^-methylglucoside, or inulin (Sitnikoff
and Rommel,quoted by Lafar, 'Technical
Mycology,' II, 89 : see also ref. given
below and Wehmer, Centr. Bakter. II,
6, 353 ; for industrial use see Boidin
and Rolants, Abst. in Journ. Fed. Inst.
3, 445 ; Collette and Boidin, Ibid. 4,
4325 ^lS'-> 5, 128: for behaviour of
two other species of Amylomyces towards
various carbohydrates see Sitnikoff and
Rommel, Journ. Fed. Inst. 7, 1 12, from
Woch. Brau. 17, 621 : for technical pro-

duction of alcohol by joint action of
Mucedina and yeast see Lafar's ' Tech-
nical Mycology,' II, 94 ; also Barbet,
Germ. Pat. 128173 of 1899 ; Ch. Centr.
1902,1,444).

Chinese yeast from Cambodia eon-
tains Mucor Cambodia, which produces
alcohol in saccharine solutions (Chrzascz,
Centr. Bakter. II, 7, 326).

The ' koji ' ferment used for prepar-
ing rice wine {' sake ') in China and
Japan (see also under dextrose [154])
can produce alcohols from sugars (not
lactose). The ferment is said to con.-
i^axx Eurotium {Aspergillus) oryzcs (Lieb-
scher, Bied. Centr. 1881, 707) yeasts,
a red yeast, Penicillium glaucum, Mucor
stolonifer, a Torula, and a white mould-
fungus : the latter ferments saccharose,
raffinose, dextrose, maltose, and d-f ruc-
tose (all slightly), but not trehalose,
rhamnose, lactose, or melezitose. The
yeast (sake -yeast) ferments saccharose,
maltose, d-mannose, dextrose, d-f ructose,
and methylglucoside (all readily) ; tre-
halose and d-galactose (less readily) ; and
not lactose or rhamnose (Kozai, Centr.
Bakter. II, 6, 385 et seq. : see also
Kellner, Mori, and Nagaoka, Zeit.
physiol. Ch. 14, 297).

The ferment used in Java for pro-
ducing ' raggi ' saccharifies starch by
the mycelium of Chlamydomucor oryzee,
and alcohol is produced by the fermen-
tation of the sugars by Moniliajavaniea
and Saccharomyces vordermanni, the other
constituents of the ferment (Went and
Prinsen Geerligs, Bot. Zeit. 1895, 143 ;
Sorel, Rev. Ch. Ind. 8, 13; Journ.
Fed. Inst. 3, 443). The Monilia can
ferment dextrose, Isevulose, maltose,
saccharose, and raffinose, but not lactose.
The Javan product contains also Mucor
javanicus, which produces alcohol from
cane sugar, glucose, and lactose (Weh-
mer, Centr. Bakter. II, 6, 610; Journ.
Fed. Inst. 7, 113)- The Chlamydomucor
is accompanied by a mould, Mucor
dubius (? n. sp. ; Ibid. Centr. Bakter. II,
7, 313 ; Journ. Fed. Inst. 7, 493)-

A Monilia resembling M. variabilis,
Lindner, contained among the organ-
isms concerned in the production of the
Japanese ' awamori ' can produce slight
fermentation in wort (Inui, Journ. Imp,

50

ALCOHOLS

[14

Coll. Sci. TokiOj 1901, 15 ; Abst. in
Journ. Fed. Inst. 8, 529).

3Io7nUa Candida ferments dextrose,
saccharose, and maltose (Hansen, Ber.
Deut-seh, hot. Gesell. 1884; Fischer and
Lindner, Ber. 28, 3037 ; Fischer, Zeit.
physiol. Ch. 26, 60 et seq.). The milk-
sugar ferment O'idium lactis of Freseuius
can produce alcohol from lactose, glu-
cose, and (less readily) from saccharose
and maltose (Lang and Freudenreich,
quoted by Jorgensen, loc. cit. 131 ; see
also Jensen, Centr. Bakter. II, 8, 248
et seq.). O'idium (Afonilia) albicans pro-
duces alcoholic fermentation in Isevulose,
glucose, and maltose, but not in lactose
(Linossier and Roux, Comp. Rend. 11,0,
868).

The mould Ettrofiopsis gai/oni can
produce alcohol from hexoses when the
mycelium is completely immersed in
the solution (Laborde, Ann, Inst. Past.
11, I ; Duclaux, Abst. in Journ. Fed.
Inst. 6, 412). According to Maze
(Comp. Rend. 128, 1608; 134, J 91)
alcohol is the first product of the assimi-
lation of the sugar by the mould. This
mould also appears to be capable of pro-
ducing alcohol from lactic acid and
glycerol {Ibid. 134, 240 ; see also Ann.
Inst. Past. 16, 433). The mould J/o-
nilia sitophila, used in W. Java for de-
composing aracliis seed-cake, and found
on putrefying bread, flour, &c., hydro-
lyses and finally ferments many carbo-
hydrates with the production of alcohol
and ethyl esters (Went, Journ. Ch,
Soc. 80, II, Abst. 412 ; Centr. Bakter.

11,7,544; 591).

Starch, dextrin, and saccharose give
rise to the formation of more or less
alcohol by the action of Aspergillus
oryzfP, Mucor alternatis of Gayon, and
Mucor {Amylomyces) rouxii in appropriate
nutrient solutions (Sanguinetti, Ann.
Inst. Past. 11, 264).

Raffinose or melitriose and melibiose
can yield alcohol under the influence of
appropriate ferments. The first of
these sugars is only completely ferment-
able by energetic sedimentary beer
yeasts, and is only incompletely fer-
mented by surface yeasts (Berthelot,
Comp, Rend, 109, 548 ; Ann. Chim.
[3] 46, 66; [6] 19, 500; Bull. Soc.

[3] 2, 6^^ ; Scheibler and Mittelmeier,
Ber. 22, 3 r i 8 ; Loiseau, Comp. Rend.
109, 614; Ban, Ch, Zeit. 18, 1794;
Woch. Brau. 15, 389 ; Andrlik, Ch.
Centr. 1898, 2, 1273: for references to
species which can resolve raffinose see
under Isevulose [l55]). All the races
of wine yeast examined by Schukoffi
(Woch. Brau. 16, 195) can only par-
tially ferment raffinose.

Pure melibiose is neither hydrolysed
nor fermented by surface yeast, but is
resolved by sedimentary yeast into
d-glucose and d-galactose and finally
completely fermented (Bau, Woch.
Brau. 16, 397; Ch. Zeit. 21, 186;
26, 69 ; see also Gillot, Bull. Assoc.
Belg. 16, 240; Ch, Centr. 1902, 2,
811).

Yeasts that have been 'acclimatised'
by cultivation in a nitrogenous medium
containing glucose and saccharose can,
according to Dubourg (Comp. Rend.
128, 440), ferment all sugars excepting
lactose. The sugars experimented with
comprised galactose, raffinose, and tre-
halose. Mucor alternans submitted to
this treatment can ferment trehalose,
d-glucose, d-maltose, d-fructose, and
d-galactose, but not lactose, saccharose,
or raffinose (Dubourg). These results
are contested by Kloeker (Centr. Bakter.
II, 6, 241), who was unable to ' adapt ^
S, warxiamis or S. apiculatus by the
method of Dubourg. S. apiculatus
could not be brought to invert sac-
charose nor 8. marxianus to ferment
maltose (see also Hansen, in Zeit. ges.
Brau. 25, as quoted above).

Trehalose is slowly fermented by sur-
face and sedimentary yeasts of the
Frohberg and Saaz types, by 8. ellipsoi-
deus II, 8. pastor ianus I, II, and III,
by 8. logos, and by Monilia Candida ; a
milk-sugar yeast had a slight effect, and
8. pombe and 8. apiculatus were without
action (Bau, Woch, Brau. 16, 305 ; see
also Kalanthar, Zeit. physiol. Ch. 26,
88). The alcohol produced from arti-
choke tuber with yeast (Levy, Comp.
Rend. 116, 1381) is probably due to
the fermentation of laevulose resulting
from the resolution of inulin (see under
laevulose [155]).

Fermentation with the production of

14.]

ETHYL ALCOHOL

51

alcohol from sugars is brought about in
some cases by symbiotic associations of
yeasts and bacteria. The ' kephir '
ferment used for preparing- an effer-
vescent beverage from milk is some-
times considered to be of this nature.
The bacterium of kephir grains is
l)isj)ora [Bacillus) caucasica of Kern.
There are also present two species of
Streptococcus and a yeast. The latter
can produce feeble fermentation in wort,
but cannot attack lactose (Kern, Bot.
Zeit. i8«2; Biol. Centr. 1882; Freu-
denreich, Centr. Bakter. II, 3, 47 ; 87 ;
135). According to Jorgensen (' Mi-
kroorganismen,^ p. 92) a ti'ue Saccharn-
wyce^ is present in Russian kephir grains
which is capable of fermenting lactose
independently of other organisms.
Among the yeasts recently identified in
kephir grains are S. cartUaginosus of
Lindner and S.fragilis of Jorgensen.

Among the organisms which ferment
milk and convert it into the alcoholic
beverage * koumiss ' is a Bacillus which
produces alcohol from milk-sugar
(Schipin, Centr. Bakter. II, 6, 775).
Ethyl alcohol is among the products
of fermentation of milk-sugar by lactic
acid bacteria (Barthel, Centr. Bakter.
II, Q, 417). The species experimented
with was possibly Bacteritmi lactis
acidi of Leichmann [Ibid. II, 5, 344).

The ' ginger-beer plant ' consists of
a symbiotic association of Saccharomyces
pyriformis and Bacterium vermiforme
(Marshall Ward, Phil. Trans. 1892,
183. B, 125). A similar ferment found
as a parasitic growth on the sugar-cane
(Madagascar) consists of a yeast and
Bacterium, and can ferment saccharose,
maltose, d-glucose, and d-fructose (Mar-
shall Ward and Green, Proc. Roy. Soc.
65, 6^). The industrial production of
alcohol from starch by Amylomyces
rouxii of Calmette (see above for refer-
ences to process of Boidin and Collette)
is regarded as a case of symbiotic
association between the Amylomyces and
the yeast (' gentil ') which is subse-
quently added (Marbach, Abst. in Journ.
Fed. Inst. 5, 479).

Glycerol gives alcohol among the
products of its fermentation by various
bacteria in appropriate nutrient solu-

E

tions in presence of chalk (Fitz, Ber.
9,1348; 10,266: 11,42; 1892; 12,
481 ; 13, 1311 ; 15, 873; Morin, Bull.
Soc. [9] 48, 803). The glycerol fer-
menting organism obtained from hay
infusion by Fitz is Bacilhis jitzianus of
Zopf, and the butyl alcohol producing
organism obtained from cow-dung by
this author is B. butylicns (see Emraer-
ling, Ber. 30, 451). These organisms,
or bacteria associated with them, are
said to give small quantities or traces
of alcohol among the products of their
fermentation of erythritol, mannitol,
starch, dextrin, inulin, lactose, dulcitol,
calcium citrate and malate (during
propionic fermentation), calcium lactate
(propionic fermentation), calcium gly-
cerate, calcium tartrate, gelatine, and
albumin (Fitz ; erythritol, Ber. 11, 45 ;
1890 ; 12, 475 ; mannitol, 10, 280 ; 11,
1895; 15, 875; 16, 845; starch, 10,
282 ; 11, 44; dextrin, 10, 382 ; inulin,

11, 45 ; lactose. Ibid. ; dulcitol, Ibid. ;
Ca-citrate, 11, 1895; Ca-malate, 11,
1896; 12, 481 ; Ca-lactate, 11, 1898 ;

12, 47,5; 13, 1309; Ca-glycerate, 12,
474; 13, 1 31 2; 16, 844; Ca- tartrate,
12, 475 ; gelatine and albumin, 12,
480). Bacteria from blue pus produce
alcohol among other products from
glycerol (Fitz, Ber. 11, 1 893). Glycerol
gives alcohol among the products of its
fermentation by Fiieumococcus (Grim-
bert) and by Bacillus acidi Icevolactici
(Schardinger : see Emmerling's ' Die
Zersetzung, &c.' p. 61).

The Granulobacter saccJiarobutyricutn
obtained by Beyerinck from graiti
(Centr. Bakter. 15, 171) produces alco-
hol from glycerol (Emmerling, loc. cit.
453). Glycerol gives alcohol when fer-
mented by the Bacillus ethaceticus of
Frankland and Fox (Proc. Roy. Soc.
46, 345). The latter produces alcohol
also from mannitol, arabinose, glucose,
lactose, saccharose, and calcium gly-
cerate (Frankland and Fox, loc. cit. ;
Frankland and Lumsden, Trans. Ch.
Soc. 61, 432; F. and MacGregor,
Ibid. 737 ; F. and Frew, Ibid. 59, 81).

The Bacilhis butylicus of Fitz pro-
duces alcohol (trace) also from saccha-
rose (Ber. 15, 876) and from glucose
(Emmerling, Ber. 30, 451). Bacillus

52

ALCOHOLS

[14.

ethacetosuccinicus produces alcohol from
manni'tol and dulcitol (Frankland and
Frew, Trans. Ch. Soc. 61, 254).

The Pneumocoectis of Friedlander pro-
duces small quantities of alcohol from
arabinose, glucose, galactose, lactose,
saccharose, maltose, and raffinose (traces),
mannitol, dextrin, and creatinine (Brie-
ger, Zeit. physiol. Ch. 8, 306 ; 9, i ;
Grimbert, Comp. Rend. 121, 698 ; Bull.
Soc. [3] 15, 52 ; 87 ; Ann. Inst. Past.
9, 840 ; Frankland, Stanley, and
Frew, Trans. Ch. Soc. 59, 253), and
from xylose (Grimbert; Bull. Soc. [3]
15, 340).

The Bacillus of malignant oedema
produces alcohol from lactose, saccha-
rose, and calcium lactate in an atmo-
sphere of hydrogen (Kerry and Friinkel,
Monats. 12, 350). Pasteur's ' butyric
ferment' produces a trace of alcohol
from calcium lactate (Fitz, Ber. 13,
1 3 10). Bacillus boocopricns from cow-
dung produces alcohol from glucose
and lactose (Emmerling, Ber. 29,
2726).

Alcohol is among the final products
of (lactic) fermentation of lactose by
Bacillus acidi lactici (Haacke, Arch.
Hyg. 42, 16; Ch. Centr. 1902, 1,
1 1 22 ; by Bac. ac. l-lactici, Schardinger,
as quoted by Emmerling in the work
referred to below) and by Slaphylococcus
pyogenes aureus (Liibbert : Emmerling,
^ Die Zersetzung stickstofffreier or-
ganischer Substanzen durch Bakterien/
p. no). TyrothrioD claviformis and
Actinobakter polymorphtis can produce
alcohol from lactose (Duclaux, Ann.
Inst. Agron. 4"^" Annee, 1879-80,
p. 103 ; also Gayon and Dubourg,
Ann. Inst. Past. 15, 567). The 'man-
nitol ferment ' of Gayon and Dubourg
{loc. cit. 527) can produce alcohol from
most sugars excepting laevulose (which
it converts into mannitol [5l]). Alco-
hol is among the products of fermenta-
tion of glucose by Dunbar's and other
Vibrios (Gosio ; quoted by Emmerling,
loc. cit. pp. 47 and 56), and of maltose
hj Bacillus fervitosus (Adametz; quoted
by Emmerling, loc. cit. p. 59).

The Bacillus amylozymicus of Per-
drix (Ann. Inst. Past. 5, 287) hydro-
lyses and finally ferments starch with

the formation of alcohol among other
products. Saccharomyces associate them-
selves symbiotically with the Bacillus
and increase the production of alcohol
to 90 per cent. Alcohol is among the
products of fermentation of starch by
Bacillus suaveolens (Sclavo and Gosio,
Bied. Centr. 20, 419 ; Journ. Ch. Soc.
60, Abst. 1284). Some of the organ-
isms of putrefying cheese produce traces
of alcohol from glycerol, mannitol, and
sorbose in presence of chalk (Berthelot,
Jahresber. 1857, 509 ; Ann. Chim. [3]
50, 350).

A 1-lactic organism obtained from
ripe pears can produce alcohol from
mannitol and dextrose (Tate, Trans.
Ch. Soc. 63, 1263). Alcohol is formed
in traces during the fermentation of
dextrose and lactose, and in considerable
quantity during the fermentation of
mannitol by Bacillus lactls aerogenes
(Emmerling, Ber. 33, 2477). Accord-
ing to Grimbert and Legros (Comp,
Rend. 130, 1425) this Bacillus is
identical with the Pneumobacillus of
Friedlander, and can ferment glucose,
saccharose, glycerol, mannitol, and dex-
trin, but not dulcitol.

Alcohol is among the products of
fermentation of mucic acid (Bechamp,
Bull. Soc. [3] 3, 770). Staphylococcus
pyogenes aureus and Bacillus coli com-
munis produce alcohol (traces) from
dextrose in nutrient solution in presence
of calcium carbonate (Hugounenq and
Doyon, Ann. Chim. [7] 15, 145; also
Liibbert as quoted by Emmerling, ' Die
Zersetzung,' &c. p. 49).

Bacillus coli communis, B. typhosus,
and allied species produce alcohol among
the products of fermentation in nutrient
solutions of d-glucose, laevulose, gly-
cerol, mannitol, d-galactose, and 1-ara-
binose in an atmosphere of nitrogen
(Harden, Trans. Ch. Soc. 79, 610).
Bacterium, icferoides ferments dextrose
in a similar manner {Ibid. Trans. Path.
Soc. 52, 115). An organism from sour
milk produces alcohol from pure arabi-
nose (Schone and Tollens, Journ. Ch.
Soc. 80, I, 368).

Saccharobacilluspastorianus (Van Laer)
produces alcohol among other products
from dextrose, maltose, and saccharose

14-A.]

ETHYL ALCOHOL

53

(Klocker, 'Die Garungsorganismen^ &c/
p. 277). Alcohol is among the products
of the butyric fermentation of dextrose,
saccharose, and starch by the anaerobic
Amylohacter hutylicum and A. cBthylicum
(Duclaux, Ann. Inst. Past. 9, 811), and
of the fermentation of sugar in nutrient
solution by a slime-forming Bacillus
isolated from impure water (Schar-
dinger, Centr. Bakter. II, 8, 144;
175). Soil bacteria produce alcohol
among the products of fermentation of
saccharose (Deherain and Maquenne,
Comp. Rend. 97, 803).

The sugar gelatinising Clostridium
gelatinosum produces alcohol in nutrient
solutions containing saccharose (Laxa,
Zeit. Zuckerind. 26, 123; Journ. Fed.
Inst. 8, 639).

Alcohol is formed in small quantity
as a product of putrefaction of fish
(Morner, Zeit. physiol. Ch. 22, 514).
The bacteria which cause putrefaction
of proteids are capable of producing
alcoholic fermentation (Vital i, Ch.
Centr. 1900, 1, 141). Arabinose gives
alcohol on putrefaction (Salkowski,
Zeit. physiol. Ch. 30, 478). Alcohol
and ethyl acetate are formed when blood
saturated with saccharose is kept for
fifteen months {Ibid. 27, 297). Fibrin
kept for several years under chloroform
water gives a cupric reducing substance
which is fermentable by yeast with the
production of alcohol {Ibid.). Rancid
butter contains alcohol and ethyl esters,
especially butyrate, which are probably
bacterial products (Amthor, Zeit. anal.
Ch. 38, 10). Alcohol is among the
products of anaerobic putrefaction of
milk by Bacillus putrificus and by the
Bacilli of malignant oedema and of
symptomatic anthrax (Bienstock, Ch.
Centr. 1901, 1, 1209).

Alcohol is said to occur in animal
tissues such as muscle, brain, and liver,
and in diabetic urine (Rajewski, Pflii-
ger's Arch. 11, 122; Bechamp, Comp.
Rend. 89, 573 ; Zeit. anal. Ch. 20,
603 ; Markownikoff, Ber. 9, 1441 ;
1603). Ethylsulphuric acid (a salt)
occurs under certain conditions in horse
urine (Pfeiffer and Eber, Landw. Ver-
suchs-Sta. 49, 97), and in human fistula
bile (Brand, Pfliiger^s Arch. 90, 491)-

Synthetical Peocesses.

[A.] From acetijlene (see under me-
thane [1 ; a]) through ethylene by
reduction (Berthelot, Comp. Rend. 50,
806 j 54, 515; 132, 281 J Wilde, Ber.
7, "^S"^) ethylsulphuric acid by com-
bination of latter with sulphuric acid
(Faraday, Phil. Trans. 1825, 448;
Hennell, Ibid. 1826, 240 ; 1828, 365 ;
Berthelot, Ann. Chim. [3] 43, 385),
and decomposition of ethylsulphuric
acid by hydrolysis (Hennell; Berthe-
lot ; see also Butleroff and Gorjainoff,
Ann. 169, 147). There is said to be
some practical difiiculty in reducing
acetylene to ethylene (Kriiger, Elektro.
Zeit. 1895, 32; Wood, Ch. News, 78,
308).

Acetylene can be partially reduced to
ethylene bypassing it mixed with hydro-
gen over finely divided nickel heated to
300° (Sabatier and Senderens, Comp.
Rend. 128, 1 1 73), or over finely divided
copper at 130-180° {Ibid. 130, 1559)
or iron at 180° {Ibid. 1628) or platinum
black at ordinary temperature {Ibid.

131, 40), or by the action of heated
finely divided nickel on acetylene jper se
{Ibid. 187). Ammoniacal chroraous
sulphate solution is said to reduce
acetylene to ethylene (Coudert, Eng.
Pat. 17159 of 1898; Journ. Soc. Ch.
Ind. 17, 1 178; also Villon process.
Elect. Rev. 35, 375; Journ. Soc. Ch.
Ind. 19, ^^^ ; Berthelot, Comp. Rend.

132, 281).

Acetylene is reduced to ethylene by
the action of sodammonium (Moissan,
Comp. Rend. 127, 914). Acetylene
can be reduced to ethylene and ethane
electrolytically, and in sulphuric acid
solution (with mercury cathode) gives
rise to small quantities of alcohol (Bil-
litzer, Sitzungsber. Wien. Akad. 110 ;
' Nature,' 67, 425).

Acetylene combines with mercuric
chloride to form a compound which is
decomposed on heating with aqueous
hydrochloric acid with the formation of
aldehyde [92]. The latter can be re-
duced to alcohol as below under H
(Kriiger and Piickert, Ch. Ind. 1895,
454 ; see also Caro, Ibid. 226 and 454 ;
Kutscheroff, Ber. 17, 13). Acetylene

54

ALCOHOLS

[14 A-B.

gives a trace of alcohol when oxidised
by hydrogen peroxide in presence of
ferrous sulphate (Cross^ Bevan, and
Heiberg, Ber. 33, 2015).

Certain metallic carbides (especially
uranium) give ethylene among the gases
produced by interaction with water
(Moissan, Bull. Soc. [3] 17, 15 ; for
production of ethylene, acetylene, &c., by
the action of water on carbides of cerium,
lanthanum, yttrium, and uranium see
also Berthelot, Comp. Rend. 132, 281;
for production of ethylene by the action
of water on mixed barium carbide and
silicide see paper by Tucker and Moody,
Journ. Soc. Ch. Ind. 20, 97 1)-

Note : — For generators of ethylene see also
under methane [1 ; D, note].

[B.] From methane [l] through
chloroform by chlorination (Regnault,
Ann. Chim. [2] 71, 380). Chloroform
gives acetylene by passing over heated
copper (Berthelot, Comp. Bend. 50,
805) or by the action of potassium
amalgam (Kletzinsky, Zeit. [2] 2, 127;
see also Fittig, loc. cif.).

Or from methane through methyl
chloride by chlorination (Berthelot, Ann.
Chim. [3] 52, 97). Ethylene is among
the products formed by passing methyl
chloride through a hot tube (Perrot,
Ann. 101, 375).

Or from methyl chloride and hydrogen
cyanide [l72] through methyl cyanide
(acetonitrile) and ethylamine [Vol. II],
and then as under FP below.

[C] From heptane [2], ethylene being
among the products formed on heating
the vapour to 900° (Worstall and Bur-
well, Am. Ch. Journ. 19, 815).

[D.] From methyl alcohol [13] through
ethane by the action of zinc or sodium
on methyl iodide (Frankland, Journ. Ch.
Soc. 2, 173; Ann. 71, 213; Wanklyn
and Buckeisen, Ann. 116, 329 : methyl
cyanide as a 'catalytic'reagentfacilitates
this condensation, Michael, Am. Ch.
Journ. 25, 419). Ethane gives ethyl
chloride by chlorination (Schorlemmer,
Comp. Rend. 58, 703; Ann. 132, 234;
Darling, Ann. 150, 216). The chloride
gives alcohol on heating with aqueous
alkali (Balard, Ann. Chim. [3] 12, 302).

According to Glock alcohol is formed

by passing a mixture of ethane and air
over heated copper, asbestos, &c. (Germ.
Pat. 109015 of 1899; Ch. Centr. 1900,
2, 304; also Coquillon as quoted in
Journ. Soc. Ch. Ind. 19, 684).

Or from methyl alcohol and potassium
cyanide [172] thi-ough methyl iodide
and cyanide and ethylamine [Vol. II]
and then as under FP below.

Note : — Many synthetical products give
ethane on heating with strong aqueous hydr-
iodic acid in sealed tubes : acetaldehyde [92] ;
acetone [106] ; acetic acid ["Vol. II] ; ethylamine
[Vol. II] ; styrene [7] ; tartronie acid from tar-
taric or malonic acid [Vol. II] ; ethylbensene [7 ; A] ;
naphthalene [12 ; 90] ; anthracene [144] ; alizarin
[145] (Berthelot ; for I'eferences see under
methane [1 ; I]).

Ethylene also is reduced to ethane by passing
in admixture with hydrogen over heated finely
divided nickel (Sabatier and Senderens, Comp.
Rend. 124, 1358), and acttt/lene also gives ethane
among other products when passed mixed with
hydrogen over heated finely divided nickel,
copper, iron, cobalt, or platinum (Ibid. Comp.
Rend. 128, 1173; 130, 1559; 1628; 131, 40;
187. Further particulars as to temperature,
&c., are given above under A).

Primary alcohols, such as methyl [13], isobutyl
[18], and amyl cdcohol [22], when their vapours
are passed over calcium carbide heated to 500°
give acetylene, ethylene, and ethane among
other products (Lefebvre, Comp. Rend. 132,
1221).

Acetylene and ethane are produced directly
by the combination of carbon and hydrogen
when an electric arc passes between carbon
poles in an atmosphere of hydrogen (Bone and
Jordan, Trans. Ch. Soc. 79, 1042).

Ethane and ethylene are among the products
of pyrogenic contact decomposition of isopropyl
[16] and isoamyl alcohol [22] (Ipatieff, Ber. 35,
1053 ; 1056). Propyl alcohol gives ethane
among the products of pyrogenic contact de-
composition by plumbago crucible material
(Ipatieff, Ber. 35, 1059).

[E.] From carbon disulphide [I60],
ethylene being among the products
formed by passing a mixture of the
vapour with hydrogen sulphide and
phosphine over heated copper or a mix-
ture of the vapour with hydrogen sul-
phide and carbon monoxide over heated
iron (Berthelot, Comp. Rend. 43, 236).

Or from cai-bon disulphide through
the tetrabromide (Bolas and Groves,
Journ. Ch. Soc. 23, 161 ; 24, 773 ;
Ann. 156, 60 ; 160, 160 ; Holand, Ann.
240, 238; Mouneyrat, Bu ^ .. '"'^'^
19, 262). The latter on treat 8-iij-)oo
excess of alcoholic potash yields etuyiene
(Nef, Ann. 308, 329). Or through
the tetrachloride (see under methane

14 E-J.]

ETHYL ALCOHOL

55

[l; L]), iodoform, and acetylene, &c.,
as under II below.

Note : — Many compounds which can be syn-
thesised give carbon tetrabromide on treatment
with bromine in the presence of alkali (from
acetone [106], Wallach, Ann. 275, 149 ; from
loBVulic acid [50 ; D], acetoacetic acid [Vol. II],
dehydracetic acid [75 ; D], &c. Farb. vorm.
Meister, Lucius and Briining, Germ. Pat. 76362
of 1893 ; Ber. 27, Ref. 930) or with a strong
solution of sodium hypobromite (acetone, glycol,
glycerol, mannitol, sugars, malic and citric acids, all
unsaturated acids, phenol, orcinol, the naphthols,
anthracene derivatives, &c. Collie, Trans. Ch. Soc.
65, 262).

[F.] Geraniol [36] on heating- with
strong alcoholic potash to 150° gives
(with methylheptenone) ethyl alcohol
(Tiemann, Ber. 31, 2989).

[G.] From glycerol [48], alcohol
being among the products of the dry
distillation of the calcium and sodium
derivatives (Destrem, Ann. Chim. [5]
27, 20 ; Fernbach, Bull. Soc. [2] 34,
146).

Or glycerol can be converted into
allyl alcohol by distillation with oxalic
acid (ToUens, Ann. 156, 129; Tollens
and Henninger, Bull. Soc. [2] 0, 394;
Briihl, Ann. 200, 174; Linnemann,
Ber. 7, 854 ; see also Bigot, Ann. Chim.
[6] 22, 464). Allyl alcohol gives ethyl
alcohol among the products of decom-
position by heating with solid potash
(Tollens, Ann. 159, 92) or with phos-
phorus pentoxide (Behal, Ann. Chim.
[6] 16, 360).

[H.] From aldehyde [92] by reduction
with sodium amalgam (Wurtz, Ann.
123, 140). Or indirectly through iodo-
form (see under methane [l ; l]) and
acetylene as below under I.

Or from aldehyde through ethylidene
chloride by the action of phosphorus
pentachloride (Wurtz and Frapolli,
Comp. Rend. 47, 418; Ann. 108, 223;
Beilstein, Ann. 113, no; Geuther, Ann.
105, 321). Acetylene, ethylene, and
ethane are produced by the action of
sodium at 200° on ethylidene chloride
(Tollens, Ann. 137, 311).

Or from aldehyde through the oxime

whioh ^^ i nitroethane among the pro-

,i)xidation by permonosulphuric

,. ^^aro's reagent; Bamberger and

Scheutz, Ber. 34, 2029). From nitro-
ethane through eihijlamine [Vol. II]

and then as under FF below. Or the
phenylhydrazone of aldehyde gives
ethylamine (with aniline) by electrolytic
reduction in sulphuric acid (Tafel and
Pfeffermann, Ber. 35, 1510).

Note : — Ethane is among the products of de-
composition of acetaldehyde and yroj)ionic alde-
hyde [86 ; 2-methylpentanaI, A] at a high
temperature (Tischtschenko, Ch. C( ntr. 1900, 1,
586, from Journ. Russ. Soc. 31, 784).

[I.] From n-propyl alcohol [15]
through iodoform (see under methane
[l; E]). The latter gives acetylene
by the action of certain finely divided
metals, such as silver, &c. (see under
cymene [6 ; HI]).

Or iodoform can be converted into
methylene iodide by heating with
iodine (Hofmann, Ann. 115, 267), with
sodium ethoxide in alcohol (Butleroff,
Ann. 107, 1 10 ; 111, 242), by boiling-
with strong aqueous hydriodic acid and
phosphorus (Lieben, Zeit. 1868, 712;
Baeyer, Ber. 5, 1095), or by heating
with water and reduced iron (Caze-
neuve, Comp. Rend. 98, 369). Methyl-
ene iodide on heating with water and
copper gives ethylene among other pro-
ducts (Butleroff, Ann. 120, 356) ; also
on heating with silver powder (Sud-
borough, Journ. Soc. Ch. Ind. 16, 408).

Or from n-propyl alcohol through
n-hexane (see under n-hexyl alcohol
[23]). Ethylene is among the products
formed by passing a mixture of hexane
and air over heated platinum (v. Stepski,
Monats. 23, ']']'^. Subsequent steps
as under A above.

[J.] From n-lAiti/l alcohol [17]
through iodoform (l ; F) and then
as above. Or from isohufyl or tertiary
hdyl alcohol [18; 19] through isobutyl-
ene (see under isobutyl alcohol [18 ; A]
and under tertiary butyl alcohol [l9 ;
B]). Ethylene is among the products
of pyrogenic decomposition of isobutyl-
ene (Noyes ; Beilstein, 1, 115). Ethyl-
ene is among the products formed by
passing the vapour of isobutyl alcohol
mixed with air over heated platinum
(v. Stepski, Monats. 23, 773).

Note :— Other generators of isobutylene given
under isobutyl and tertiary butyl alcohols are :
isoamyl alcohol [22] ; isovaleric acid [Vol. II] ;
acetic acid [Vol. II] ; acetone and glycerol [106 ;
48].

56

ALCOHOLS

[14 K-T.

[K.] From octijl alcohol [28] through
iodoform (l ; Gr) and then as above.

[L.] From butyric aldehyde [04]
through iodoform (l ; K) and then as
above.

[M.] From acdone [106] through
chloroform or iodoform (l ; J). Iodo-
form gives acetylene or ethylene as
above. Chloroform gives acetylene by
passing the vapour over heated copper
(see under cymene [6 ; III])- Or
chloroform can be converted into methyl-
ene iodide by heating with aqueous
hydriodic acid at 130° (Bljuducho, Zeit.
[2] 1, 91). From methylene iodide to
ethylene as above under I.

Or from acetone through bromof orm
(Lowig, Ann. 3, 295 ; Dumas^ Ann.
Chim. [2] 56, I20; Giinther, Arch.
Pharm. [3] 25, 373)- The latter gives
ethylene by the action of alcoholic
potash (Hermann, Ann. 95, 211 ; Long,
Ann. 194, 23).

Or from acetone through acrolein
[101] and allyl alcohol (see under
glycerol [48 ; E]) and then as above
under G.

[N.] From phenol [6O], ethylene
being among the products of pyrogenic
decomposition (Miiller, Journ. pr. Ch.
58, i). Or from phenol through chlor-
aa-glyceric acid and chloroform (see
under methane [l; M]),and then through
acetylene, &c., as above under M.

[O.] Yxom cresol\Q\; 62; 63], ethyl-
ene being among the products of pyro-
genic decomposition (Miiller, loc. cit.).

[P.] From dextrose [154], ethyl
alcohol being produced in small quan-
tity by the action of an alternating
electric current on an aqueous solution
(Berthelot, Ann. Chim. [5] 16, 450).
Ethyl alcohol is among the products
of reduction of dextrose by sodium
amalgam (Bouchardat, Comp. Rend.
73, 1008; Ann. Chim. [4] 27, 68).

* Sugar ' in alkaline solution is said
to yield alcohol under the influence
of light in the absence of all life
(Duclaux, Ann. Inst. Past. 10, 168).

[Q.] From hydrogen cyanide [l72] or
metallic cyanides, these by interaction
with red-hot magnesium giving mag-
nesium carbide. The latter is decom-
posed by water with the formation of

acetylene (Eidmann, Journ. pr. Ch. [2]
59, n).

[R.] Yrom formic acid [Vol. II] and
methyl alcohol [l3] through methyl for-
mate, perchlormethyl formate, and car-
bon tetrachloride (see under methane
[1; O]), The latter on heating with
strong aqueous hydriodic acid at 130°
gives iodoform (Walfisz, Bull. Soc. [3]
7, 256), from which acetylene, &c., can
be obtained as above under I. Barium
formate gives ethylene among the pro-
ducts of dry distillation (Watts' Diet.
II, 484 ; comp. Merz and Weith, Ber.
15, 151 1).

[S.] From acetic acid [Vol. II]
through acetyl chloride or acetic anhy-
dride and reduction with sodium amal-
gam (Linnemann, Ann. 148, 249 ;
Saytzeff, Journ. pr. Ch. [2] 3, 76).
Or indirectly through ethane by electro-
lysis (Kolbe, Ann. 69, zyg; Kuenen,
Proc. Physical Soc. 15, 237) and then
through ethyl chloride, &c., as above
under D.

Ethylene is among the products
formed by dropping acetic acid on to
heated zinc chloride (LeBel and Greene,
Am. Ch, Journ. 2, 26), and among the
products of electrolysis of an acid solu-
tion of potassium acetate (Petersen, Ch.
Centr. 1897, 2, 518).

A solution of the potassium salts of
acetic and gly collie acid [Vol. II], the
acetate being at the anode, give alcohol
on electrolysis (v. Miller and Hofer,
Ber. 28, 2437).

Or from acetic acid through ethyl-
amine [Vol. II] and then as under PF
below.

[T.] From propionic acid [Vol. II],
which gives ethane by photochemical
decomposition in presence of uranium
salts (Fay, Am. Ch. Journ. 18, 269).
Ethyl propionate is formed by the elec-
trolysis of an acid solution of potassium
propionate (Petersen, Ch. Centr. 1897,
2, .518).

Ethyl iodide is formed by the elec-
trolysis of sodium propionate with
potassium iodide for the negative elec-
trolyte (v. Miller and Hofer, Ber. 28,
2430). Ethylene is among the pro-
ducts of electrolysis of a neutral solution
of potassium propionate (Bunge, Journ.

14 T-KK]

ETHYL ALCOHOL

57

Russ. Soc. 21, 551 ; Petersen^ loc. cU.).
Ethyl alcohol is among the products of
electrolysis of sodium propionate in
presence of sodium perchlorate (Hofer
and Moest, Ann. 323, 284).

Or from propionic acid through nitro-
ethane or propionamide and ethylamine
[Vol. II] and then as under PF below.

[U.] From butyric acid [Vol. II],
which gives a small quantity of ethyl
butyrate on oxidation with sulphuric
acid and manganese dioxide (Veiel, Ann.
148, 164.

[v.] From lactic acid [Vol. II],
alcohol being among the products
formed by heating the calcium salt
with lime (Hanriot, Bull. Soc. [2] 43,
417; 45, 80), or by photochemical
decomposition in aqueous solution
(Duclaux, Ibid. 47, 385). Ethylene
also is among the products of distil-
lation of calcium lactate (Gossin, Ibid.

43,49)-

Or from lactic acid through iodoform

by the action of iodine in presence of

alkali (Lieben, Ann. Suppl. 7, 2i8;

377) and then as above under A.

Or from lactic acid through alanine
[Vol. II] and ethylamine [Vol. II] as
under GG below.

[W.j From malonic acid [Vol, II],
ethylene (small quantity) being among
the products of electrolysis of the acid
potassium salt (Petersen, Ch. Centr.
1897, 2, 519).

[X.] From succinic acid [Vol. II],
the acid potassium salt givmg some
alcohol (by reduction of aldehyde) at
the kathode (Petersen, Zeit. physik. Ch.
33, 698 ; Ch. Centr. 1900, 2, 172).

Ethylene is formed also by the elec-
trolysis of a strong solution of the
sodium salt (Kekule, Ann. 131, 79 : see
also Clark and Smith, Journ. Am. Ch.
Soc. 21, 967) and of the acid potassium
salt (Petersen, Ch. Centr. 1897, 2, 519
and 1900, 2, 171).

Also from succinic acid through the
dibromo-acid, acetylenedicarboxy lie acid,
and acetylene (see under methane [l ;
T]).

[Y,] From azelaJic acid [Vol. II]
through ethylene (see under methane
[1; V]).

[Z.] From fumaric or male'ic acid

[Vol. II] through acetylene by electro-
lysis (see under methane [l ; U]), or
through dibromsuccinic acid and acety-
lene [I/Ad.).

[AA.] From malic acid [Vol. II]
through bromoform (see under methane
[1 ; BB]) and then as above under M.

[BB.] From citric acid [Vol. II]
through bromoform (see under methane
[1 ; CC]) and then as above under M.

[CO.] From salicylic acid [Vol. II]
through trichlor-aa-glyceric acid and
chloroform (see under methane [l; W])
and then through acetylene, &c., as
above under M.

[DD.] From gallic acid [Vol. II]
through trichlor-aa-glyceric acid and
chloroform (see under methane [1; X])
and then as above.

[EE.] From trimethylamine [Vol. II]
through methyl chloride by heating the
hydrochloride of the base to 326° (Vin-
cent, Journ. Pharm. [4] 30, 132;
.Tahresber. 1878, 1135). Subsequent
steps as under B above.

[FP.] From ethylamine [Vol. II] by
the action of nitrous acid (Linnemann,
Ann. 144, 129; Hofmann, Journ. Ch.
Soc. 3, 231).

[GG.] From alanine [Vol. II] through
ethylamine [Vol. II] by dry distillation
(Limpricht and Schwanert, Ann. 101,
297) and then as above.

[HH.] Mannitol [5l] gives methyl-
ene iodide among the products of the
action of phosphorous iodide (Butleroff,
Ann. Ill, 242). From methylene iodide
through ethylene as above under I.
Or from mannitol through n-hexane
(see under n-hexyl alcohol [23 ; B])
and then as above under I.

Note : — All generators of n-hexane referred
to under n-hexyl alcohol [23] thus become,
through ethylene, generators of ethyl alcohol.

[II.] From isovaleric acid [Vol. II],
ethylene and ethane being among the
products of the dry distillation of the
calcium salt (Dilthey, Ber. 34, 2115).

[JJ.] From n-hexyl alcohol [23]
through n-hexyl iodide and hexane by
reduction and then as under I above.

[KK.] From tartaric acid [Vol. II
through pyroracemic acid (benzyl alcoho
[54 ; N]), which gives ethyl acetate on

58

ALCOHOLS

[14 KK-15 A.

electrolysis in alcoholic solution in
presence of acid or alkali (Rockwell,
Journ. Am. Ch. Soc. 24, 719)-

[LL.] From acrolein [lOl] through
propinal and acetylene (see under cy-
mene [6 ; XVIII]) and then as above
under A.

15. Normal Propyl Alcohol; Ethyl
Carbiuol ; 1-Fropanol.

CH3.CH2.CH2.OH

Natural Sotjeces.

A secondary product of alcoholic fer-
mentation by Saccharomyces, being- found
in most fusel oils (Chancel, Comp. Rend.
37, 410 j 68, 659; 726; Jahresber.
1853, 503; Ann. 151, 298; Kramer
and Pinner, Ber. 3, 75 ; Fittig, Zeit.
[3] 4, 44 j Pierre and Puehot, Ann.
163, 265 ; Comp. Rend. 66, 302 ; 70,
406; Linnemann, Ann. 160, 195;
Ekman, Ch. Zeit. 12, 564 ; in old
cognac fusel oil, Ordonneau, Comp.
Rend. 102, 217; Claudon and Morin,
Ibid. 104, 1187; 105, 1019; in fusel
oil from potato spirit, Rabuteau, Comp.
Rend. 87, 501 ; see also Bell as quoted
by Allen in Journ. Fed. Inst. 3, 36).

n-Propyl alcohol is among the pro-
ducts of fermentation of glycerol in
presence of calcium carbonate and nu-
trient salts by Bacillus hutylicus (Fitz,
Ber. 13, ofi; 1311 ; Morin, Bull. Soc.
[2] 48, 803) and among the products
of the lactic and butyric fermentation
of sugar (Bouchardat, Comp. Rend. 78,
1 145 j Meyer and Forster, Ber. 9, ^'^^'

The Bacillus of malignant oedema
produces n-propyl alcohol among other
products from lactic acid in an atmo-
sphere of hydrogen (Kerry and Frank el,
Monats. 12, 350).

Granulohacter butylictim of Beyerinck
(Ree. Tr. Ch. 12, 141) produces n-propyl
and not, as formerly supposed, butyl
alcohol during butyric fermentation
(Emmerling, 'Die Zersetzung,' &c.
p. J 15, note).

n-Propyl alcohol is among the pro-
ducts of fermentation of starch by the
anaerobic Amylohacter hutylicuw and
A. aihylicum of Duclaux (Ann. Inst.
Past. 9, Bit).

Synthetical Peocesses.

[A.] From ethyl alcohol [14] through
ethyl iodide, cyanide [172] (Williamson,
Phil. Mag. [4] 6, 205; Buckton and
Hofmann, Journ. Ch. Soc. 9, 250;
Rossi, Ann. 159, 79), propylamine by
reduction, and action of nitrous acid on
the amine (Mendius, Ann. 121, 133 ;
Siersch, Ann. 144, 137; Silva, Zeit.
[2] 5, 638 ; Linnemann, Ann. 161, 44 ;
Meyer and Forster, Ber. 9, 535 : iso-
propyl alcohol is simultaneously formed
in this process ; see under the latter
[16; C]).

Or ethyl iodide and methyl iodide
(from viethyl alcohol [13]) can be con-
densed to propane by the method of
Wurtz (sodium in ethereal solution ; see
under n-heptane [2; A]). Propane
on chlorination gives n-propyl chloride
(Schorlemmer, Ann. 150, 209 ; 152,
159), which can be converted into the
alcohol by the usual methods.

Or from ethyl alcohol through ethylene
(see under methane [l; D]), ethylene
chloride, vinyl chloride, chloracetalde-
hyde, and (with hydrogen cyanide [l72])
iS-chlorlactic acid, glyceric acid, and
pyrotartaric acid (see under benzyl
alcohol [54 ; A]) ; n-propyl alcohol is
among the products of electrolysis of
potassium pyro tartrate (Petersen, Zeit.
physik. Ch. 33, 698; Ch. Centr. 1900,
2; 173).

Note : — Ethyl alcohol is also a generator of
chloracetaldehyde through ethyl ether or chlor-
acetal, or through chloral (see under beuzyl
alcohol [54 ; I]).

Or from ethyl alcohol through iodo-
form, which by the action of sodium
ethoxide gives acrylic acid (Butleroff,
Ann. 114, 204). The latter can be
converted into a-chlorlactic acid (benzyl
alcohol [54 ; l]), glyceric acid {WuK),
and pyrotartaric acid {Ibid. F).

Or ethylene can be combined with
phosgene (carbon oxychloride) to form
^-chlorpropionyl chloride, from which
the acid can be obtained by the action
of water (Lippmann, Ann. 129, 81 ;
Henry, Comp. Rend. 100, 114). The
chloro-acid on treatment with alcoholic
potash or lead oxide or sodium hydroxide

15 A-E.]

NORMAL PROPYL ALCOHOL

59

^ives acrylic acid (Moureu^ Ann. Chim.
[7] 2, 158 ; see also Schneider and
Erlenmeyer, Ber. 3, 339; Wislicenus^
Ann. 166, 2).

Or ethylene combines with hypo-
chlorous acid to form glycolchlorhydrin
(Carius, Ann. 126, 197 ; Butleroff, Ann.
144, 40 : practically fflj/col from ethyl-
ene may be treated with hydrogen
chloride). The chlorhydrin with, potas-
ffium cyanide [172] and by hydrolysis of
the nitrile gives hydracrylic acid (Wisli-
cenus, Ann. 128, 4 ; 167, 346 ; Erlen-
meyer, Ann. 191, 268}. The salts of
the latter give acrylic acid on dry
distillation (Beilstein, Ann. 122, 372).
From acrylic acid via glyceric acid and
pyrotartaric acid as above.

Note : — By these processes all generators of
ethylene become generators of n-propyl alcohol.

Or from ethyl alcohol and trioxy-
methylene \_ formic aldehyde : 9l] by the
interaction of magnesium ethobromide
and trioxymethylene in ethereal solution
(Grignard and Tissier, Comp. Rend.
134. 107).

[B.] From isopropyl alcohol [16]
through isopropyl iodide, which gives
propane by reduction with zinc and acid
(Schorlemmer, Ann. 150, 209). Or from
isopropyl alcohol through propylene
and conversion of latter into pyrotartaric
nitrile (by means of potassinni cyanide
[172]) and pyrotartaric acid (see under
aipentene [9 ; F]) and then as under A.

[C] From normal butyl alcohol [17]
through n-butyl iodide, n-butylene by
the action of alcoholic potash on the
latter (Saytzeff, Journ. pr. Ch. [2] 3,
88; Lieben and Rossi, Ann. 158, 164;
Grabowsky and Saytzeff, Ann. 179, 330),
and secondary butyl iodide = 2-iodo-
butane by combining the n-butylene
with hydrogen iodide (Wurtz, Ann.
152, 23). 2-Iodobutane gives propane
among other products on heating with
aluminium chloride above 160° (Lothar
Meyer, Ber. 27, 2766 ; Kluge, Ann.
282, 227).

[D.] From tertiary butyl alcohol [19]
through tertiary butyl iodide, which
also gives propane when heated with
aluminium chloride as above (Lothar
Meyer, lac. cit. ; Kluge, loc. cit.).

[E.] From glycerol [48], which gives
propane on heating in a closed vessel
with strong aqueous hydriodic acid
(Berthelot, Bull. Soc. [2] 7, 60; 9, 13;
184).

Or through allyl alcohol by distilling
glycerol with oxalic acid (see under
ethyl alcohol [14; G]). Allyl alcohol
gives n-propyl alcohol on reduction with
zinc and dilute sulphuric acid (Linne-
mann, Ber. 7, 852), on heating with
solid potash (Tollens, Ann. 159, 92 ;
Zeit. [2] 7, 242), or by reduction with
aluminium in alkaline solution (Spe-
ranski, Journ. Russ. Soc. 31, 423).

Glycerol gives n-propyl alcohol among
the products of decomposition of the
sodium compound above 245° (Fernbach,
Bull. Soc. [2] 34, 146).

Or from glycerol through allyl brom-
ide (Henry, Zeit. [2] 6, 575; Tollens,
Ann. 156, 152 ; Grosheintz, Bull. Soc.
[2] 30, 98 ; Jacobi and Merling, Ann.
278, 11), trimethylene bromide by com-
bination with hydrogen bromide (Gero-
mont, Ann. 158, 370 ; Reboul, Ann.
Chim. [5] 14, 472 ; Erlenmeyer, Ber,
12, 1354; Roth, Ber. 14, 1351 ; Bogo-
molitz, Bull. Soc. [2] 30, 23), tri-
methylene = cyclopropane by the action
of sodium or of zinc dust on trimethylene
bromide in alcohol (Freund, Monats. 3,
626; Journ. pr. Ch. [2] 26, 367; see
also Reboul, Ann. Chim. [5] 14, 488;
Gustavson, Journ. pr. Ch. [2] 36, 300 ;
50, 381; 59, 302; Journ. Russ. Soc.
19, 495 ; Comp. Rend. 128, 437 ;
Wagner, Ber. 21, 1 236 ; Tornoe, Ibid.
1282; Wolkoff and Menschutkin, Ber.
31, 3072; Journ. Russ. Soc. 32, 118;
Tanatar, Ber. 32, 702 ; 1965). Tri-
methylene combines with strong sul-
phuric acid to form dipropyl sulphate
(Freund), which gives n-propyl alcohol
on decomposition by hot water (Gustav-
son; Berthelot, Ann. Chim. [7] 4, 102).
Or trimethylene combines with hydro-
gen iodide to form n-propyl iodide, from
which the alcohol can be obtained by
the usual methods (Freund).

Or from glycerol through acrolein
[101] (see also undercymene [6 ; X VIII])
and oxidation of latter to acrylic acid
(Claus, Ann. Suppl. 2, 123; also Red-
tenbacher, Ann. 47, 125). From acrylic

60

ALCOHOLS

[15 E-L.

acid through a-chlorlaetic, glyceric, and
pyro tartaric acids as above under A.

Or from glycerol a.nd /)otassi?im cyanide
[172] through allyl chloride and pyro-
tartaric nitrile and acid (dipentene [9;
G]) and then as under A above.

[P.] Eryihritol [50] gives a-iodo-
butane on heating with aqueous hydr-
iodic acid (De Luynes, Bull. Soc. [a]
2, 3; Ann. 125, 252). Subsequent
steps through propane as above under C.

[G.] From mannitol [5l] through
secondary hexyl iodide = 2-iodohexane
by heating with aqueous hydriodic acid
(Wanklyn and Erlenmeyer, Jahresber.

1861, 731 ; 1862, 480 ; Zeit. 1861, 606 ;

1862, 641 ; Ann. 135, 130 ; Domac,
Monats. 2, 310 ; Hecht, Ann. 165, 146 ;
209, 311 j Uppenkamp, Ber. 8, ^^-j
Schorlemmer, Ann. 199, 139 : accord-
ing to Combes and LeBel, Bull. Soc.
[3] 7, 551, the iodohexane thus formed
is 3-iodohexane). Propane is among
the products formed by heating a-iodo-
hexane with aluminium chloride to 225°
(Lothar Meyer, Ber. 27, 2766; Kluge,
Ann. 282, 227).

Or from mannitol through acrolt'in
and acrylic acid (see under benzyl alcohol
[54; AA and E]). From the latter
through a-chlorlactic acid, glyceric acid,
and pyro tartaric acid as above under A.

[H.] From formic aldehyde [9l]
through ' oxy methylene,^ which results
from its polymerisation (see under
formic aldehyde). Oxy methylene gives
n-propyl alcohol by dissolving in strong
sulphuric acid and distilling the product
with water (Gustavson, Journ. pr. Ch.
[2] 36, 301).

Or oxymethylene forms a compound
with zinc ethyl which is decomposed by
water with the formation of n-propyl
alcohol (Tischtschenko, Journ. Russ.
Soc. 19, 483).

[I.] From crotonic aldehyde [102]
through crotonic acid (see under benzyl
alcohol [54 ; H]). The acid combines
with hydrogen bromide to form a-brom-
butyric acid (Naumann, Ann. 119, 115;
Wislicenus and Urech, Ann. 165, 93 ;
Ley, Journ. Russ. Soc. 9, 129; Tupoleff,
Ann. 171, 249 ; Hemihan, Ann. 174,
325). The latter, on distillation of the
potassium salt with a solution of sodium

nitrite, gives nitropropane (Auger, Bull.
^^^- [3] 2^^ 333)> which can be reduced
to propylamine and treated as above
under A.

Or from crotonic acid, the ester of
which condenses under the influence of
sodium ethoxide to form dicrotonic ester,
from which the acid can be obtained by
hydrolysis. Dicrotonic acid gives pyro-
tartaric acid on oxidation by alkaline
permanganate (v. Pechmann, Ber. 33,
3323). From pyrotartaric acid as above
under A.

[J.] From acetic aldehyde [92] through
butyrochloral and allylene dichloride
(see under benzyl alcohol [54; H]).
The dichloride on heating with water at
1 80° gives acrylic acid (Pinner, Ber. 7,
66). Subsequent steps through a-chlor-
lactic acid, glyceric, and pyrotartaric
acids as above under A.

Or from acetic aldehyde through
crotonic aldehyde [l02] and crotonic
acid and then as above under I.

Aldehyde and hydrogen cyanide [172]
give a cyanhydrin which, by the ac-
tion of phosphorus pentachloride, gives
a-chlorpropionitrile, from which a-chlor-
propionic acid can be obtained by
hydrolysis. The acid on heating with
barium hydroxide solution gives acrylic
acid (Michael and Garner, Ber. 34,
4049).

[K.] Acetone [IO6] gives propane on
heating in a sealed tube with strong
aqueous hydriodic acid (Berthelot, Bull.
Soc. [2] 7, 69). From propane as
above under A. Or acetone on chlorina-
tion gives i : i -dichloracetone (Fittig,
Ann. 110, 40; Borsche and Fittig,
Ann. 133, 1 1 2), which gives acrylic acid
on boiling with potassium carbonate
solution (Faworsky, Journ. pr. Ch. [2]
51, ^S^- From acrylic acid through
pyrotartaric acid as above under A.

Or from acetone, acetic acid, and
ethyl alcohol through acetylaeetone and
methylpropyl ketone (as under n-pri-
mary amyl alcohol [20 ; B ; C] and n-
secondary amyl alcohol [21 ; D]). From
the ketone through the oxime to propyl-
amine as below under AA.

[L.] Ptclegone [128] gives pyrotar-
taric acid among the products of its oxi-
dation by potassium permanganate (Mar-

15 L-P]

NORMAL PROPYL ALCOHOL

61

kownikoff, Ber. 33, 1909). Subsequent
steps as above under A.

[M.] Menthone [129] gives pyrotar-
taric acid as above [Ibid.).

[N.] From propionic acid [Vol. II]
through propionic anhydride, which
gives n-propyl alcohol on reduction
with sodium amalgam (Linnemann,
Ann. 148, 251; 160, 231 ; 161, 18;
see also Saytzeff, Zeit. [2] 6, 105). Or
ammonium propionate on dry distilla-
tion gives propionamide, which on heat-
ing with phosphorus pentoxide gives
propionitrile = ethyl cyanide (Dumas,
Malaguti, and Leblanc, Ann. 64, 334;
see also Aschan, Ber. 31, 2344). The
latter can be reduced to propylamine
and treated as above under A.

Or from propionic acid through pro-
pionyl chloride, /3-chlorpropionyl chlo-
ride by chlorination and /3-chlorpropionic
acid by hydrolysis (Michael and Garner,
Ber. 34. 4046). From the ,i3-chloro-
acid through acrylic acid to pyrotar-
taric acid as above under A.

Or from propionic acid through the
aa-dibromo-acid and the a^-dibromo-
acid by transformation of the latter (see
under benzyl alcohol [54 ; O]). From
the a/3-dibromo-acid through glyceric
to pyro tartaric acid {Ibid.) and then as
above under A.

Or from propionic and formic acid
[Vol. II] through propionic aldehyde
by distilling a mixture of the calcium
salts (Williamson, Journ. Ch. Soc. 4,
138 ; Lieben and Rossi, Ann. 158,
137; 159, 58; 79; 165, 109; 167,
293 ; Lieben and Janecek, Ann. 187,
126). The aldehyde gives the alcohol
on reduction (Rossi, Comp. Rend. 70,
129; Ann. 159, 80). Propaldoxime
also gives nitropropane among the pro-
ducts of oxidation by permonosulphuric
acid (Carols reagent; Bamberger and
Scheutz, Ber. 34, 2032). From nitro-
propane through propylamine as above
under I and A.

Note : — Generators of propionic aldehyde are
given under hexanal (2-methylpentanal [96 ;
C, &c.]).

[O.] From acetic acid [Vol. II] and
hydrogen cyanide [172] through acetyl
cyanide, pyroracemic (pyruvic), and

pyrotartaric acid (see under benzyl
alcohol [54 ; l]). Then as above under
A.

Or from acetic acid and potassium
cyanide through cyanacetic acid by the
interaction of chloracetic acid and the
cyanide (Miiller, Ann. 131, 348; 350 ;
Meves, Ann. 143, 201 ; Fiquet, Ann.
Chim. [6] 29, 439). The sodium deri-
vative of cyanacetic ester interacts with
ethyl iodide to form a-cyanobutyric
ester (Henry, Bull. Soc. [2] 48, 656 ;
Comp. Rend. 104, 161 8), which gives
ethylmalonic acid as below under P and
n-propyl alcohol as under T.

[P.] Normal butyric acid [Vol. II]
gives n-propyl butyrate when the silver
salt is acted upon by iodine (Simonini,
Monats. 14, 81), when the acid is oxi-
dised by manganese dioxide and dilute
sulphuric acid (Veiel, Ann. 148, 164),
or by the electrolysis of the solution of
the acid potassium salt (with some iso-
propyl butyrate in latter process ; Ha-
monet, Comp. Rend. 123, 252 ; Peter-
sen, Ch. Centr. 1897, 2, 519; 1900, 2,
172). The ester gives the alcohol by
hydrolysis. The alcohol is among the
products of electrolysis of sodium butyr-
ate in presence of sodium perchlorate
(Hofer and Moest, Ann. 323, 284).

Or from butyric acid through butyr-
amide by distilling the ammonium
salt (Hofmann, Bei". 15, 982). The
amide gives n-propylamine by the action
of bromine in presence of caustic potash
{Ibid. 769). From the amine to the
alcohol as above under A.

Butyric acid also gives propane by
photochemical decomposition in the
presence of uranium nitrate (Wisbar,
Ann. 262, 235).

Or butyric acid by bromination gives
a-brombutyric acid (Gorup-Besanez and
Klincksieck, Ann. 118, 248 ; Nauraann,
Ann. 119, 115; Borodin, Ibid. 123;
Friedel and Machuca, Ann. 120, 279;
Suppl. 2, 70 ; Ley, Journ. Russ. Soc.
9, 129 j Wislicenus and Urech, Ann.
165, 93 ; TupolefP, Ann. 171, 249 ;
Genvresse, Bull. Soc. [3] 7, '^66 ;
Michael and Graves, Ber. 34, 4041).
From a-brombutyric acid through nitro-
propane and propylamine, &c., as above
under I.

62

ALCOHOLS

[15 P-U.

Or from a-brombutyric acid (ester)
through crotonic acid (see under benzyl
alcohol [54 j K]), and then as above
under I through dicrotonic and pyro-
tartaric acid, &c.

Or a-brombutyric acid (ester) by
interaction with potassium-mercuric
cyanide [172] gives a-cyanobutyric ester
(Markownikoff, Ann. 182, 330), and
this on hydrolysis gives ethylmalonic
acid (Wislicenus and Urech, Ann. 165,
93 j Tupoleff, Ann. 171, 243 ; Markow-
nikoff, he. cit. 329). The latter gives
n-propyl alcohol as below under T.

Or from butyric acid through butyr-
one (see under n-nonyl alcohol [29 ;
D]), which gives dinitropropane by the
action of nitric acid (Chancel, Comp.
Hend. 96, 1466; Bull Soc. [2] 31,
503; Ann. 52, 296; 64, 331 ; Kurtz,
Ann. 161, 208 ; Fileti and Ponzio,
Journ. pr. Ch. [2] 55, 193). From
dinitropropane through propylamine
and propaldehyde as below under AA.

Note : — Mothylpropyl ketone from acetic and
butyric acids (see under n-secondary amyl
alcohol [21 ; A]) and ethylpropyl ketone from
propionic and butyric acids or from zinc ethyl
and butyryl chloride (VOlker, Ber. 8, 10 19;
Popoff, Ann. 161, 289) also give dinitropropane
on nitration (Chancel, Jahresber. 1884, 1048;
Fileti and Ponzio, loc. cit), Methylpropyl
ketone is also convertible into propylamine
through the oxime as below under AA.

[Q.] Isohufyric acid [Vol. II] gives
propane among the products of photo-
chemical decomposition in presence of
uranium salts (Fay, Am. Ch. Journ.
18, 286). From propane as above
under A.

[R.] From lactic acid [Vol. II], which
gives acrylic acid among the products
of the distillation of the calcium salt
(Claus, Ann. 136, 288). From acrylic
acid to pyro tartaric acid, &c., as above
under A.

Or lactic acid by the action of phos-
phorus pentachloride gives a-chlorpro-
pionic acid (Wurtz, Ann. Chim. [3]
49, 58 ; Briihl, Ber. 9, 35). From
the latter through acrylic acid by heat-
ing with barium hydroxide solution
(Michael and Garner, Ber. 34, 4050).

Or lactic acid gives pyroracemic
(pyruvic) acid on oxidising the calcium
salt with potassium permanganate (Beil-

stein and Wiegand, Ber. 17, 840).
Pyroracemic acid gives pyrotartaric
acid on heating with hydrochloric acid
to 100° or per se to 170° (Clermont,
Ber. 6, 72; Bottinger, Ber. 9, 837;
1823 ; Ann. 188, 308 ; De Jong, Eec.
Tr. Ch. 20, 81; 21, 191 ; see also
Wolff, Ann. 317, 22).

Or lactic acid gives citraconic acid
on distillation (Engelhardt, Ann. 70,
243 ; 246). The latter can be con-
verted into pyrotartaric acid (see under
benzyl alcohol [54 ; M]).

[S.] Hydracrylic acid [Vol. II] gives
aciylic acid on distillation of its salts
(Beilstein, Ann. 122, 372). Subse-
quent steps as above.

[T.] From malo7iic acid [Vol. II]
and ethyl alcohol [14] through ethyl-
malonic acid (see under hexanal [2-
methylpentanal ; 96 ; G]). The latter
gives n- (with iso-) propyl alcohol on
electrolysis of a solution of the potas-
sium salt (Petersen, Zeit. physik. Ch.
33, 698; Ch. Centr. 1900, 2, 172).

Or from malonic acid, aldehyde (par-
aldehyde) [92], and acetic acid through
crotonic acid (see under benzyl alcohol
[54 ; G]). From crotonic acid through
a-brombutyric acid and nitro-propane,
&c., as above under I.

Note : — Malonic acid (ester) on treatment
with chloroform and sodium ethylate gives
dicarboxyglutaconic ester (Conrad and Guth-
zeit, Ann. 222. 250), and tliis on boiling with
baryta water gives (with glutaeonic acid) /3-oxy-
glutaric acid (Guthzeit and Bolam, Journ. pr.
Ch. [2] 54, 365), from which crotonic acid can
be obtained as below under "W.

Or from malonic ester, methyl iodide
[13], and chloracetic acid through pro-
pan etricarboxy lie acid = a-methyleth-
enyltricarboxylic acid (see under benzyl
alcohol [54 ; G]) and pyrotartaric acid
{It)id.).

Malonic diethyl ester and aldehyde
[92] condense when heated with acetic
anhydride to form ethylidenemalonic
diethyl ester (Komnenos, Ann. 218, 157),
and the latter on heating with potas-
sitim, cyanide [172] in alcoholic solution
gives /3-cyano butyric ester, which gives
pyrotartaric acid on treatment with
alkali (Bredt and Kallen, Ann. 293,

350).

[IT.] From ^-hydroxyljutyric acid

15 U-AA.]

NORMAL PROPYL ALCOHOl

[Vol. II], which gives crotonic acid on
distillation (benzyl alcohol [54 ; L]).

[v.] From tartaric acid [Vol. II]
through pyrotartaric acid by heating-
per se or with hydrochloric or acetic
acid (Fourcroy and Vauquelin, Ann.
Chim. [i] 35; i6i ; 64, 42; Rose,
Gehlen's Journ. 3, 598 ; Pelouze, Ann.
Chim. [2] 56, 297 ; Weniselos, Ann.
15, 148 ; Arppe, Ann. 66, 73 ; 90,
138; Geuther and Riemann, Zeit. [2]
5, 318; Bechamp, Ibid. [2] 6, 371 ;
Sace, Ibid. 432 ; Bourgoin, Ann. Chim.
[5] 12, 419). From pyrotartaric acid
as above under A.

[W.] From citric acid [Vol. II]
through citraconic,mesaconic,or itaconic
acid (see under benzyl alcohol [54 ; M]).
From these acids through pyrotartaric
acid {Ibid.).

Note : — The following generators of citra-
conic acid given under benzyl alcohol [54 ; M]
thus become genei-ators of n-propyl alcohol
through pyrotartaric acid : — Lactic acid (see
above under R) ; acetoacetic ester and hydrogen
cyanide through hydroxypyrotartaric acid ; iso-
valeric acid through hydroxypyrotartaric acid ;
propionic and malonic acids through propanetri-
carboxylic = )3 - methylethenyltricarboxylic
ester ; acetic and propionic acids, ethyl alcohol and
potassium cyanide through a mothyl-;8-cyano-
succinic ester ; oxalic and propionic acids and
ethyl alcohol through methyloxalacetic ester
and /S-methylmalic acid.

Tlie propanetricarboxylic acid above referred
to gives pyrotartaric acid directly '^see under
benzyl alcohol [54 ; G]).

Or from citric acid through acetone-
dicarboxylic acid (see under orcinol [75 ;
C]), which gives /3-oxyglutaric acid on
reduction (v. Pechmann and Jenisch,
Ber. 24, 3250). The latter on distilla-
tion 7?i vacuo gives vinylacetic acid
(Fichter and Krafft, Ber. 32, 2799; F.
and Sonneborn, Ber. 35, 938), which is
readily transformed into crotonic acid
by the action of mineral acids. From
crotonic acid as above under I.

[X.] From aconitic acid [Vol. II]
through itaconic acid (see under benzyl
alcohol [54; X]) and then through
pyrotartaric acid, &c., as above under W.

[Y.] From succinic acid [Vol. II] and
alcohot [14] through succinylsuccinic
ester (see under quinol [71; N]). The
latter forms a dinitroso-derivative (Ebert,
Ann . 229, 55) , which on longcontact with
water yields ethyl isonitrososuccinate =

NiVERSfr

03

a (anti-) oximinosuccmate [^una. 65), the
acid from which decomposes on heating
with water with the formation of cyan-
acetic acid (Cramer, Ber. 24, 1208).
The latter gives a-cyanobutyric acid,
ethylmalonic acid, &c., as above under O.

Or from succinic acid through the di-
bromo-acid by bromination (see under
methane [l ; T]). The dibromo-acid
gives ethoxyfumaric ester on treatment
with sodium ethoxide (Michael and
Bucher, Ber. 29, 1792). The ester
gives oxalacetic acid by the action of
hydrochloric acid {Ibid.) or alcoholic
potash (Nef, Ann. 276, 230). The ester
of oxalacetic acid gives pyrotartaric or
ethylmalonic acid as below under Z.

[Z.] From oxalic and acetic acids
[Vol. II] and alcohol [l4]. Diethyl
oxalate and ethyl acetate condense
by the action of sodium or sodium
ethoxide with the formation of diethyl
oxalacetate (Wislicenus, Ann. 246, 315 ;
Piutti, Gazz. 17, 520 ; Drude, Ber. 30,
952). The latter on heating with 10
per cent, sulphuric acid gives pyrora-
cemic and through this pyrotartaric
acid (Wislicenus, loc. cit,).

Or ethyl oxalacetate combines with
hydro xyliimine to form /3-{syn)-oximino-
succinic ester (Cramer, Ber. 24, 1206),
the acid from which decomposes on
heating with the formation of cyanacetic
acid {Ibid.). Subsequent steps through
ethylmalonic acid as above.

[AA.] From acetoacetic ester [Vol.
II] through acetyl cyanide and pyrora-
cemic acid (see under benzyl alcohol
[54; I]). From the latter through
pyrotartaric acid, &c., as above under
O, &e.

Or from acetoacetic ester and a-hrom~
propionic ester through /3-methylaceto-
succinic ester and pyrotartaric acid
(benzyl alcohol [54; l]). Or from
acetoacetic ester and chloracetic ester
through acetosuccinic ester, a-methyl-
acetosuccinic ester, and pyrotartaric acid
(54; I).

Or from acetoacetic ester and metht/l
iodide through methylacetoacetic ester
and mesaconic acid (54 ; I). From the
latter through pyrotartaric acid, &c.,
as above under W.

Or from acetoacetic ester and ethyl

64

ALCOHOLS

[15 AA-16.

iodide tli rough ethylacetoacetic ester
and methyl-n-propyl ketone (see under
n-secondary amyl alcohol [21 ; C]). The
oxime of the ketone on heating- to i oo°
with a solution of hydrogen chloride in
acetic acid (with a little acetic anhydride)
gives propylamine. Other acids, acetyl
chloride, or phosphorus pentachloride
bring about a similar decomposition
(Beckmann, Ber. 20, 2580; Hantzsch,
Ber. 24, 4018). From propylamine as
above under A.

Or from acetoacetic ester through
crotonic acid (64 ; I). From the latter
through a-brombutyric acid and nitro-
propane, or through pyro tartaric acid as
above under I.

Or acetoacetic ester on bromination
under appropriate conditions gives y-
bromacetoacetic ester (Duisberg, Ber.
15, 1379; Ann. 213, 138; Conrad and
Schmidt, Ber. 29, 1045 : see also Haller
and Held, Comp. Bend. 114, 452), and
this by the action of sodium ethoxide,
of alcoholic ammonia, or of sodium in
ethereal solution gives suceinylsuccinic
ester (Wedel, Ann, 219, 94 ; Duisberg,
Ann. 213, 149 ; Conrad and Schmidt,
loc. cit. ; Mewes, Ann. 245, 74). From
suceinylsuccinic ester through ethyl-
malonic acid as above under Y and O.

Or dibromacetoacetic ester (see under
quinol [71; O]) gives dihydroxytere-
phthalic diethyl ester [Ibid.). The latter
on reduction with zinc and hydrochloric
acid or with sodium amalgam gives
suceinylsuccinic ester (Baeyer, Ber. 19,
432 ; Baeyer and Noyes, Ber. 22, 2 168).
Ethylacetoacetic ester on treatment
with nitric acid gives I : i -dinitropropane
(Chancel, Jahresber. 1883, 1079), and
this when reduced in ethereal solution
with aluminium amalgam gives propyl-
amine and propionic aldehyde (Ponzio,
Journ. pr. Ch. [2] 65, 197).

[BB.] From thymol [67] through
thymoquinone, thymoqidnol [82], and
dihydroxyterephthalic acid (see under
quinol [71; P]), and then through suc-
dinylsuccinic acid, &c., as above.

[CO.] From carvacrol [66] through
thymoquinone, &c. (quinol [71 ; Q]).

[DD.] From malic acid [Vol. II]
through oxalacetic acid by oxidising
with hydrogen peroxide and a ferrous

salt at a low temperature (Fenton and
Jones, Trans. Ch. Soc. 77, 77). From
oxalacetic acid through pyrotartarie or
through ethyl malonic acid as above
under Z.

[EE.] From fumaric or male'ic acid
[Vol. II] through dibromsuccinic acid
(methane [l ; U]) and then through
oxalacetic acid, &c., via ethoxyfumaric
ester as above under Y. From oxal-
acetic acid through pyrotartarie or
ethylmalonic acid as under Z.

[FP.] From allyl imUiiocyanate [I66]
through allyl cyanide and crotonic acid
(benzyl alcohol [54 ; J]). From crotonic
acid as above under I.

[GG.] From glycocoll [Vol. II] and
ethyl alcohol [14] through n-propyl-
amine by distilling the hydrochloride of
the ethyl ester with sodium carbonate
(Schilling, Ann. 127, 97 ; Kraut, Ann.
177, 267 ; Hantzsch and Silberrad, Ber.
33, 70 ; Auger, Bull. Soc. [3] 21, 5 ;
see also Curtius and Jay, Ber. 27, 60;
Hantzsch and Metcalf, Ber. 29, 1684 j
for production of propylamine see Curtius
and Goebel, Journ, pr. Ch. [2] 37, 163).
From propylamine as above under A.

[HH.] From alanine [Vol. II] and
methyl alcohol [13] through acrylic acid
(benzyl alcohol [54; BB]). From
acrylic acid through a-chlorlactic acid,
glyceric acid, and pyrotartarie acid as
above under A (see also under benzyl
alcohol [54 ; I and F]).

[II.] From lysine [Vol. II], pyro-
tartarie acid being a product of the
oxidation of the base by barium per-
manganate (Zickgraf, Ber. 35, 3401).

16. Isopropyl Alcohol ;

Dimethyl Carbinol ;

2-Fropanol.

CH3.CH(OH).CH3

Natural Source.

Said to have been found as a secon-
dary product of fermentation in potato
fusel oil (Rabuteau, Comp. Bend. 87,
50 1 ). According to Victor Meyer and
Jaeobson (Lehrb. d. org. Ch. I, 161 ;
see also Bouchardat, Ber. 7, Ref. 657)
this statement is erroneous.

16 A-B.]

ISOPROPYL ALCOHOL

65

Synthetical Pkocesses.

[A.] From acetone [106] by reduction
with sodium amalgam (the acetone
should contain water) (Friedel, Ann.
124j 327 ; Linnemann, Ann. 136, 38).
Acetone also gives isopropyl alcohol
(with pinacone) by electrolytic reduc-
tion (Merck, Germ. Pat. 11 37 19 of
1899 ; Ch. Centr. 1900, 2, 794; Elbs
and Brand, Zeit. Elektroch. 8, 783).

Or from acetone through 2 : 2-di-
chlorpropane (Friedel, Ann. 112, 'Z'^6),
a-chlorpropylene (CH, : CCl. CH3) by
the action of alcoholic potash or am-
monia, a-chlorallyl chloride by chlori-
nating the chlorpropylene in the dark
(Friedel and Silva, Comp. Rend. 73,
957; 74, 806; 75, 81; Fittig, Ann.
135, 359), a-chlorallyl alcohol by boil-
ing with aqueous potassium carbonate
(Henry, Comp. Rend. 95, 849), and
acetyl carbinol [43] by the action of
sulphuric acid (Henry, Bull. Soc. [2]
39, 526). Acetyl carbinol reduces to
propylene glycol (W. H. Perkin, junr..
Trans. Ch. Soc. 59, 786), the latter by
the action of hydrogen chloride giving
propylene chlorhydrin (Oser, Ann.
Suppl. 1, 254; Morley, Ber. 13, 1805;
also Morley and Green, Trans. Ch. Soc.
47, 133); which by the action of alcoholic
potash gives propylene oxide (Oser, loc.
cit.; Linnemann, Ann. 140, 178;
Monats. 6, 369 ; Henry, Ann. Chim.
[4] 27, 261). The latter yields iso-
propyl alcohol on reduction by sodium
amalgam (Linnemann, loc. cit.).

Or from acetone through acrylic and
pyrotartaric acids (see under n-propyl
alcohol [15; KandA]). The latter gives
isopropyl alcohol among the products
of electrolysis of the potassium salt
(Petersen, Zeit. physik. Ch. 33, 698 ;
Ch. Centr. 1900, 2, 172).

Or from acetoneoxime, which gives iso-
propylamine by reduction with sodium
amalgam in acetic acid solution (Meyer
and Warrington, Ber. 20, 505 ; Gold-
schmidt. Ibid. 728) or by electrolytic
reduction (Tafel and Pfeffermann, Ber.
35, 1510).

Or from acetonephenylhydrazone,
which gives isopropylamine on reduc-
tion with sodium amalgam and acetic

acid (Tafel, Ber. 19, 1926) or by
electrolytic reduction (Tafel and Pf effer-
mann, Ber. 35, 1207). Isopropylamine
is converted into isopropyl alcohol by
the action of nitrous acid (Siersch, Ann.
148, 263 ; Meyer and Forster, Ber. 9,

535)-

[B.] From normal propyl alcohol [15
through propylene by the action o
dehydrating agents (LeBel and Greene,
Am. Ch. Journ. 2, 23; Beilstein and
Wiegand, Ber. 15, 1498 ; Berthelot,
Comp. Rend. 129, 483 ; Newth, Proc.
Ch. Soc. 17, 147). Propylene combines
with strong sulphuric acid, and the
product gives isopropyl alcohol on
hydrolysis (Berthelot, Ann. Chim. [3]
43, 399 ; Ann. 94, 78 ; Comp. Rend.
57, 797; Ann. 129, 126).

Note: — Propylene is produced from propyl
alcohol to the extent of 933 per cent, by pass-
ing the vapour over heated plumbago crucible
material (Ipatieft", Ber. 35, 1059).

Or n-propyl alcohol can be con-
verted into n-propyl iodide and the
latter into propylene by the action of
alcoholic potash (Freund, Monats. 3,
633). Propylene combines with hydro-
gen iodide to form isopropyl iodide
(Berthelot, Ann. 104, 184; Erlen-
meyer, Ann. 139, 228 ; Butleroff, Ann.
145, 275 ; Michael and Leighton,
Journ. pr. Ch. [2] 60, 447). The
latter is converted into the alcohol by
heating with water and lead hydroxide
or with water only (Flavitzky, Ann.
175, 380; Niederist, Ann. 186, 391).
Or propylene combines with bromine
and the bromide can be converted into
propylene glycol (Wurtz, Ann. Chim.
[3] 55, 438; 63, 124; Henry, Rec.
Tr. Ch. 18, 221). From propylene
glycol through propylene oxide as above
under A.

Or propylene glycol by the action of
hydrogen iodide gives isopropyl iodide
(Wurtz, Ann. Suppl. 1, 381), which
can be converted into the alcohol as
above.

Or propylene combines with chlorine
to form propylene chloride, which by
the action of alcoholic potash gives
a- (with some /3-) chlorpropylene (Ca-
hours, Jahresber. 1850, 496; Reboul,

I \

-w>

C«v \

CU

c \-^^^

66

ALCOHOLS

[16 B-P.

Ann. Chim. [5] 14, 462). From a-
chlorpropylene through propylene oxide
as above under A.

n-Propyl alcohol can also be con-
verted into n-propyl chloride (Pierre
and Puchot, Ann. 163, 266; Ann.
Chim. [4] 20, 234; Malbot, Bull.
Soc. [3] 2, 136). The latter when
chlorinated in the presence of aluminium
chloride gives propylene chloride (Mou-
neyrat, Bull. Soc. [3] 21, 616). Sub-
sequent steps as above.

[C] From methyl and ethyl alcohols
[13 ; 14] through propane and propyl
chloride (see under n-propyl alcohol
[15; a]). From propyl chloride through
propylene chloride as above under B.

Or fr-om ethyl alcohol through
ethylene (see under methane [l; D]),
ethylene bromide, and glycol [45]
(Wurtz,Ann.Chim.[3] 55,400; Atkin-
son, Phil. Mag. [4] 16, 433 ; Ann. 109,
232; Debus, Ann. 110, 316; Demole,
Ann. 173, 117 ; 177, 4,5 ; Henry, Ann.
Chim. [4] 27, 250; Jeltekoff, Ber. 6,
558; Bornstein, Ber. 9, 480 ; 917;
Zeller and Hiifner, Journ. pr. Ch. [2]
11, 229 ; Stempnewsky, Ann. 192, 240 ;
Erlenmeyer, Ann. 192, 244 ; Gros-
heintz, Bull. Soc. 31, 293 ; Pribram
and Handl, Monats. 2, 673; Niederist,
Ann. 196, 354 ; Beilstein and Wie-
gand, Ber. 15, 1368 ; Bouchardat,
Comp. Rend. 100, 452 ; Wagner, Ber.
21, 1234; Haworth and W. H. Perkin,
junr.. Trans. Ch. Soc. 69, 175; Henry,
Bull. Acad. Roy. Belg. [3] 36, 9 ; Rec.
Tr. Ch. 18, 221). Glycol is converted
into the chlorhydrin by the action of
hydrochloric acid (Wurtz, Ann. 110,
125; Ladenburg, Ber. 16, 1408) and
into the iodhydrin by the action of
potassium iodide on the chlorhydrin
(Butleroff and Ossokin, Ann. 144, 42 ;
Demuth and Meyer, Ann. 256, 28;
Henry, Bull. Acad. Roy. Belg. [3] 18,
182). The iodhydrin by the action of
zinc methyl and decomposition of the
product with water gives isopropyl
alcohol (Butleroff and Ossokin, Ann.
145, 257 ; Charon and Paix-Seailles,
Comp. Rend. 130, 1407).

Glycol chlorhydrin = chlorethyl alco-
hol can also be obtained directly from
ethylene and hypochlorous acid (Carius,

Ann. 126, 197; Butleroff, Ann. 144,
40).

Note : — By the above process all generators
of ethyleae become with methyl alcohol (for
zinc methyl) generators of isopropyl alcohol.

Or from ethyl alcohol through pyro-
tartaric acid (see under n-propyl alcohol
[15 ; a]). From the latter by electro-
lysis as above under A.

Or from ethyl alcohol through ethyl
cyanide and propylamine and the action
of nitrous acid as under n-propyl alco-
hol [15 ; a] (Linnemann and Siersch,
Ann. 144, 140 ; Linnemann, Ann. 150,
370; 161,44; Ber. 10, iiii; Meyer
and Forster, Ber. 9, ^"^^ ; Erlenmeyer,
Ber. 30, 2961).

Also from ethyl alcohol and bromo-

form (see under methane [l; D]) or

carbon tetrachloride (see under methane

[l; L]) through propylene (see under

glycerol [48 ; D]).

From propylene as above under B.

[D.] Yvomn-butyl alcohol [17] through
2-iodobutane and propane (see under
n-propyl alcohol [15 ; C]). From pro-
pane through propyl chloride and pro-
pylene chloride, &c., as above under B.

Or isobvlyl alcohol [18] gives isobutyl
chloride or bromide, which yields pro-
pylene among other products when
passed over soda-lime heated above
600° (Nef, Ann. 318, 22). Isobutylene
from isobutyl alcohol also gives pro-
pylene among the products of pyro-
genic decomposition (Noyes; Beilstein,
' Handbuch,' I, 115). The vapour of
isobutyl alcohol yields propylene among
other products when mixed with air and
passed over heated platinum (v. Stepski,
Monats. 23, 773).

[E.] From tertiary butyl alcohol [19]
through the iodide and propane (15 ; D).
Subsequent steps as above. Or through
isobutylene (see under isobutyl alcohol
[I8; a]) and from the latter through
propylene as above under D.

[F.] From amyl alcohols of fusel oil
[22], propylene being among the pro-
ducts formed by passing the vapour
through a hot tube (Reynolds, Journ.
Ch. Soc. 3, III; Ann. 77, 118; Wurtz,
Ann. 104, 242). From propylene as
above under B.

16 G-0.]

ISOPROPYL ALCOHOL

67

[G.] From (jli/cerol [48] tliroug-h
propane (15 ; E) and then as above
throug-h propyl and propylene chlorides,
&e. Or from glycerol through allyl
iodide (see under isobutyl alcohol [l8 ;
D]) and propylene; or through allyl
alcohol and propylene (see under ace-
tone [106 ; F]). Or from glycerol
through allyl bromide (15 ; E). The
latter gives propylene on heating the
alcoholic solution vrith zinc dust (Wol-
koff and Menschutkin, Ber. 31, 307 a ;
Journ. Russ. Soc. 30, 559). Or allyl
bromide can be converted into tri-
methylene (15 ; E), and this yields pro-
pylene when heated to 600° (Tanatar,
Zeit. physik. Ch. 41, 735 : see also Ber.
32, 702 ; 1965).

Glycerol gives propylene among the
products obtained by distilling it with
iodine and phosphorus (Berthelot and
De Luca, Ann. 92, 306 ; Ann. Chim.
[3] 44, 350 ; Oppenheim, Ann. Suppl.
6, 354), or with zinc dust (Westphal,
Ber. 18, 2931).

From glycerol through isopropyl
iodide by distilling with iodine and
phosphorus in presence of water (Erlen-
meyer, Ann. 126, 305 ; 139, 21 1 ;
Markownikoff, Ann. 138, 364; Meyer,
Journ. pr. Ch. [2] 34, 98), and then as
above under B.

Or from glycerol through dichlor-
hydrin by the action of hydrochloric
acid (Berthelot, Ann. Chim. [3] 41,
297 ; Reboul, Ann. Suppl. 1, 222 ;
Carius, Ann. 122, 73 ; Hiibner and
Miiller, Zeit. [2] 6, 344; Watt, Ber.
5, 257 ; Claus, Kolver, and Nahm-
macher, Ann. 168, 43 ; Markownikoff,
Ann. 208, 358 ; Fauconnier and San-
son, Bull. Soc. [2] 48, 236 ; Fauconnier,
Ibid. 50, 212; Bigot, Ann. Chim. [6]
22, 437). Dichlorhydrin gives iso-
propyl alcohol among the products of
reduction by sodium amalgam (Buff,
Ann. Suppl. 5, 250).

Or (indirectly) dichlorhydrin can be
converted into i : 2 : 3-trichlorpropane
(Berthelot and De Luca, Ann. Chim.
[3] 48, 304; 52, 433; Fittig and
Pfeffer, Ann. 135, 359), a-chlorallyl
chloride (CHgiCCl.CH.Cl) by the
action of potash or triethylamine (Re-
boul, Ann. Suppl. 1, 229 ; Comp. Rend.

95, 993), a-chlorallyl alcohol by heating
with aqueous potassium carbonate, and
then through aceti/l carbitiol,%cc.,Qs above
under A.

[H.] From erj/thritol [50] through
2-iodobutane and propane (15 ; P).

[I.] From mannitol [5l] through
2-iodohexane and propane or through
acrolein [lOl], acrylic acid, &c., to pyro-
tartaric acid (15 ; G) and then as above
under A.

Or from mannitol through n-hexane
(see under n-hexyl alcohol [23 ; B] and
n-propyl alcohol [15 ; Gj). Propylene
is formed among other products by
passing u-hexane mixed with air over
heated platinum (v. Stepski, Monats.
23, 7TS)-

Note : — All generators of n-hexane given
under n-hexyl alcohol [23], viz. n-propyl alcohol
[15] ; glycerol [48] ; suberic acid [Vol. II] ; acetone
[106], &c. ,thus become generators, through pro-
pylene, of isopropyl alcohol.

[J.] Thymol [67] gives propylene on
heating with phosphorus pentoxide
(Engelhardt and Latschinoff, Zeit. [2]
5, 616). Or from thymol through
thymoquinone to succinylsuccinic acid
(ester) and ethylmalonic acid as under n-
propyl alcohol (15; O; Y; BB). Ethyl-
malonic acid gives isopropyl alcohol
among the products of electrolysis of
the solution of the potassium salt
(Petersen, Zeit. physik. Ch. 33, 698;
Ch. Centr. 1900, 2, 172).

[K.] From carvacrol [66] through
thymoquinone, &c. (15 ; CC), and then
as above.

[L.] From aldehyde [92] through
butyrochloral to acrylic and pyrotar-
taric acids (15 ; J). From the latter
as above under A. Or from aldehyde
and methyl alcohol by the interaction
of magnesium methiodide and the alde-
hyde (Grignard, Ch. Centr. 1901, 2,
622).

[M.] From acrolein [lOl] through
acrylic to pyrotartaric acid (15 ; E).

[N.] From crotonic aldehyde [l02]
through crotonic acid to pyrotartaric
acid, or through a-brombutyric acid,
nitropropane, and n-propylamine (15;
I). From the latter as above under C.

[O.] From acetyl carbinol [43] as above
under A.

f2

68

ALCOHOLS

[16 P-AA.

[P.] From dextrose [157], acetyl
carbinol being among the products of
fusion with alkali (Emmerling and
Loges, Ber. 16, ^S7)- According to
Bouchardat (Comp. Rend. 73, looSj
Ann. Chim. [4] 27, 68) isopropyl alco-
hol is among the products of reduction
of dextrose by sodium amalgam.

[<i.] From pulegone [l28] through
pyro tartaric acid (15 ; L).

[R.] From menthone [l29] through
pyro tartaric acid (15 ; M).

[S.] From acetic acid [Vol. 11], pro-
pylene being among the products formed
by passing the vapour over heated zinc
dust (Jahn, Ber. 13, 21 ii).

Or from acetic acid and potassimn
cyanide [172] and ethyl alcohol [l4]
through pyrotartaric or ethylmalonic
acid (15 ; O) and then as above under
A and J.

[T.] From propionic acid [Vol. II]
through the amide, nitrile, and n-pro-
pylamine (15 ; liT) and then as above
under C. Or from propionic acid
through pyrotartaric acid (15 ; N).

[U.] From butyric acid [Vol. II],
isopropyl butyrate being among the
products of electrolysis of the acid
potassium salt (15 ; P). Or from
butyric acid through n-propylamine
(15 ; P) and then as above under C.

Or from butyric acid through pro-
pane (15 ; P) and then as above under
■ B. Or from butyric acid through
crotonic to pyrotartaric acid (15 ; P)
and then as above under A. Or from
butyric acid and ethyl alcohol [14]
(and potassium-mercuric cyanide) through
ethylmalonic acid (15 ; P) and then as
above under J.

Butyric acid gives propylene when
passed over hot zinc dust (Jahn, Ber.
13, 2115)- Propylene is also among
the products of electrolysis of a solution
of potassium butyrate (Bunge, Journ.
Buss. Soc. 21, 552; Hamonet, Comp.
Rend. 123, 252 ; Petersen, Ch. Centr.
1897, 2, 519). From propylene as
above under B.

[v.] From isohutyric acid [Vol. II]
through isopropylamine by the action
of bromine in the presence of alkali
on isobutyramide (Hofmann, Ber. 15,
768). From the amine as above under

A and C. Isopropyl isobutyrate and
propylene are among the products of
electrolysis of a solution of potassium
isobutyrate (15 ; P ; also under U
above). Isopropyl alcohol is among
the products of electrolysis of sodium
isobutyrate in presence of sodium per-
chlorate (Hofer and Moest, Ann. 323,
284).

Or from isohutyric acid through
diisopropyl ketone by distillation of the
calcium salt (Popoff, Ber. 6, 1255;
Miinch, Ann. 180, 327). The osime
of the ketone is transformed by acetyl
chloride into isopropyl -isobutyramide,
which gives isopropylamine (with iso-
hutyric acid) on hydrolysis (Meyer and
Warrington, Ber. 20, 500).

Also from isobutyric acid through
propane (15 ; Q).

[W.] From isovaleric acid [Vol. II],
propylene being among the products
of pyrogenic decomposition (Hofmann,
Journ. Ch. Soc. 3, 121). Propylene
is among the products of the dry distil-
lation of calcium isovalerate (Dilthey,
Ber. 34, 2 115). Or from isovaleric
acid through hydroxypyrotartaric, citra-
conic, and pyrotartaric acids (benzyl
alcohol [54 j M]).

[X.] From lactic acid [Vol. II], which
gives propylene among the products
of distillation of the calcium salt (Gos-
sin. Bull. Soc. [2] 43, 49). Or from
lactic acid through acrylic or citraconic
acid to pyrotartaric acid (15 j R).

[Y.] From hydracrylic acid [Vol. II]
through acrylic acid to pyrotartaric
acid (15 ; S).

[Z.] From ^-hydroxyhutyric acid [Vol.
II] through crotonic acid to nitro-
propane and n-propylamine (15 ; U)
and then as above under C.

[AA.] From oxalic and acetic acids
[Vol. II], propylene being among the
products of dry distillation of a mixture
of calcium oxalate and potassium acetate
(Dusart, Ann. 97, 127). Or from oxalic
and acetic acids and ethyl alcohol [l4]
through pyrotartaric or through ethyl-
malonic acid (15 ; Z). Or from oxalic
and propionic acids and alcohol [l4]
through jQ-methylmalic to citraconic
and pyrotartaric acid (benzyl alcohol
[54 J M]).

16 BB-17.]

ISOPROPYL ALCOHOL

69

[BB.] From malonic acid [Vol. II]
and et/ii/l alcoliol [14] through ethyl-
malonic acid (15 ; T). Or from malonic
acid, aldehyde [92], and acetic acid
through crotonic acid to nitropropane
and n-propylamine {Ibid.). Or from
malonic acid and alcohol [14] and
methyl iodide []3] through propanetri-
earboxylic and pyrotartarie acids {Ibid.).
Or from malonic and propionic acids
through propanetricarboxylic ester,
citraconic and pyrotartarie acid (benzyl
alcohol [54; M]).

[CO.] From succinic acid [Vol. II]
and ethyl alcohol [14] through ethyl-
malonic or pyrotartarie acid (15 ; Y).

[DD.] From azela'ic acid [Vol. II],
propylene being among the products
of distillation with soda-lime (Miller
and Tschitschkin, Journ. Russ. Soc.
31,414; Ann. 307, 375).

[EE.] From acetoacetic acid (ester)
[Vol. II] through pyrotartarie acid or
n-propylamine or ethylmalonic acid (15 ;
AA; and benzyl alcohol, 54; I).

[FF.] From malic acid [Vol. II]
through pyrotartarie or ethylmalonic
acid (15 ; DD).

[GCx.] From fiimaric or male'ic acid
[Vol. II] through pyrotartarie or ethyl-
malonic acid (15 ; EE).

[HH.] From tartaric acid [Vol. II]
through pyrotartarie acid (15 ; V).

[II.] From citric acid [Vol. II]
through pyrotartarie acid (15 ; W).

[JJ.] From aconitic acid [Vol. II]
through itaconic to pyrotartarie acid
(15; X).

[KK.] From glycocoll [Vol. II] ethyl
ester [14] through n-propylamine (15 ;
GG) and then as above under C.

[LL.] From alanine [Vol. II] and
methyl alcohol [13] through acrylic to
pyrotartarie acid (15 ; HH).

[MM.] From allyl isothiocyanate
[I66] through allyl cyanide to crotonic
acid (15 ; FP). From crotonic acid
through nitropropane and n-propylamine
or through pyrotartarie acid (15 ; I).

[NN.] Choline [Vol. II] gives glycol
[45] on boiling the aqueous solution
(Wurtz, Ann. Suppl. 6,200). From glycol
and zinc methyl as above under C.

[00.] From acetyl carbinol [43] as
above under A.

[PP.] From isobutyric aldehyde [94],
which condenses under the influence
of alcoholic potash to form 2:2: 4-tri-
methylpentane-i : 3-diol (Fossek,'Mo-
nats. 4, 664 ; Brauchbar, HAd. 17, 641).
The latter on oxidation with potassium
permanganate gives diisopropyl ketone
(Lieben : Franke, Monats. 17, 92 ; 673).
From the ketone through the oxime to
isopropylamine as above under V.

17. ITormal Butyl Alcohol ; Normal
Propyl Carbinol; l-Bntanol.

CH3.CH2.CH2.CH2.OH

Natural Sources.

A product of fermentation of glycerol
in presence of calcium carbonate by
Bacillus butylicus and other Schizomy-
cetes (Fitz, Ber. 9, 1348; 10, 276;
2226; 11,42; 13, 1311; Vigna, Ber.
16, 1438 ; Emmerling, Ber. 29, 2726 ;
30, 451). Butyl alcohol is formed also
from mannitol (Fitz, Ber. 10, 280; 11,
42; 15, 875; Emmerling, Ber. 30,
452) and from saccharose by this Bacillus
(Fitz, Ber. 15, 876), which cannot pro-
duce butyl alcohol from dextrose
(Emmerling, loc. cit. 453).

The butyl alcohol producing Bacillus
has been found on hay and on rotten
wood and is not identical with Gra?iulo-
hacter saccharobutyricum of Beyerinck
(Centr. Bakter. 15, 171), which can pro-
duce butyl alcohol from dextrose and
starch, but not from glycerol (Emmer-
ling, Ber. 30, 453)-

Granulobacter polymyxa, Beyerinck
( = ? Clostridium, polymy oca, Prazmowski),
gives a trace of butyl alcohol when
grown anaerobically (Lafar^s ' Tech-
nical Mycology, 1,' 189, &c.).

llicrococcus acidi paralactici and the
Bacillus of symptomatic anthrax when
grown together in a nutrient solution
containing saccharose produce butyl
alcohol (Nencki ; Centr. Bakter. 11,
225; see also Lafar, ^Techn. My col.'
1,87).

Bacteria from blue pus can produce
butyl alcohol from glycerol during bu-
tyric fermentation (Fitz, Ber. 11, 1893).

The species of butyric ferments com-

70

ALCOHOLS

[17-E.

prised under Clostridium hufyricnw, of
Prazmowski ( = Bacillus amylohacter,
Van Tieghem) can produce butyl alcohol
from carbohydrates (Gruber ; quoted
by Jorgensen, ^ Mikroorganismen,^ &c.

p. 87)-

Butyl alcohol is formed during the
butyric fermentation of milk by Bacillus
hutyricus of Bodkin (Ch. Centr. 1891,
1, 183 j 1892, 1, 484). A butyl alcohol
(? normal) occurs in rancid butter, pro-
bably a bacterial product (Nagel, Am.
Ch. Journ. 23, 172).

Bacillus orthohutyliciis from ferment-
ing calcium tartrate solution ferments
saccharose, lactose, maltose, glucose,
galactose, mannitol, glyceiol, glycogen,
arabinose, inulin, and starch with the
production of butyl alcohol among
other products (Grimbert, Ann. Inst.
Past. 7, 353)- Amylohacter hitylicum
and A. cetkylicum of Duclaux produce
small quantities of butyl alcohol during
the fermentation of glycerol, glucosC;
saccharose, maltose, lactose, and starch
(Duclaux, Ann. Inst. Past. 9, 811).

n- Butyl alcohol has been said to be
a constituent of the fusel oils of brandy
(Ordonneau, Comp. Rend. 102, 217;
Claudon and Morin, Ibid. 104, 11 87)
and potato starch spirit (Rabuteau,
Ibid. 87, 501 : see also Allen, Journ.
Fed. Inst. 3, 33). According to Bannow
(Meyer and Jacobson^'s ' Lehrbuch
d. org. Ch.' I, 161, note) n- butyl
alcohol is not a normal constituent of
fusel oil. Emmerling has found n-
butyl alcohol (2-5 grams from 10 kilos.)
in fusel oil from grain spirit (Ber. 35,
694).

Synthetical Processes.

[A.] From ethyl alcohol [14], n-butyl
alcohol being among the products
formed by heating barium ethylate and
ethyl alcohol to 230-340° (Guerbet,
Comp. Rend. 133, 300; Bull. Soc. [3]
27, 578).

Or from ethyl alcohol through butane
from ethyl iodide (Frankland, Ann. 71,
'^H'} 77, 221; Schoyen, Ann. 130,
Q-^^', Lowig, Jahresber. 1860, 397).
From butane through n-butyl chloride
by chlorination (Schoyen, loc. cit. 235).

Butyl chloride can be converted into
the alcohol by the usual methods (see
under methyl alcohol [13 ; B] ; ethyl
alcohol [14; D]).

Or from ethyl and methyl alcohols
[14; 13] and potassitim cyanide [l72].
Methyl iodide is converted into methyl
cyanide (see under ethyl alcohol [l4;
D]), and this by the action of sodium
and ethyl iodide gives n-propyl cyanide
(Holtzwart, Journ. pr. Ch. [2] 39, 233).
The latter reduces to n-butylamine
(Linnemann and Zotta, Ann. 162, 3),
which yields the alcohol on treatment
with nitrous acid {Ibid,. ; also Victor
Meyer, Ber. 10, T30 : methylethyl
carbinol is the chief product by this
method).

[B.] From normal propyl alcohol [l5]
through n-propyl iodide and cyanide
(Schmidt, Zeit. [2] 6, 576). From the
latter through n-butylamine as above.

Or from n-propyl and methyl alcohol
[13] through n-butane by combining
the alky Is by the method of Wurtz
(see under n-heptane [2 ; A]). From
butane through butyl chloride as above.

From n-propyl alcohol and trioxy-
methylene {formic aldehyde [9l]) by the
interaction of magnesium propyl brom-
ide and trioxymethylene (Grignard and
Tissier, Comp. Rend. 134, 107).

[C] From isoamyl alcohol [22], iso-
amyl iodide giving butane when heated
with aluminium chloride to 140°
(Lothar Meyer, Ber. 27, 2766).

[D.] From glycerol [48] through
allyl iodide (see under isobutyl alcohol
[18; D]), diallyl (i : 5-hexadiene) by
the action of sodium, &c., on the iodide
(Berthelot and De Luca, Ann. 100,
361 ; Wurtz and Leclanche, Ann.
Chim. [4] 3,129; Linnemann, Bull. Soc.
[2] 7, 424; Ann. 140, 180; Oppen-
heira, Ber. 4, 672). Diallyl combines
with hydrogen iodide to form a dihy-
driodide, which by the action of sodium
gives /3-hexylene. The latter combines
with hydrogen iodide to form secondary
hexyl iodide (2-iodohexane) (Wurtz,
Ann. 132, 306), and this yields butane on
heating to 128° with aluminium chlor-
ide (Lothar Meyer, Ber. 26, 2070; 27,
2766).

[E.] From mannitol [5l] through

17 E-L.]

NORMAL BUTYL ALCOHOL

71

secondary hexyl iodide (see under n-pro-
pyl alcohol [15 ; G]) ; from the latter
as above under D.

Or secondary hexyl iodide can be con-
verted into n-hexane (see under n-hexyl
alcohol [23 ; B]). The latter on heating-
with aluminium chloride breaks down
into pentane and the latter into butane
(Friedel and Gorgeu^ Comp. Rend. 127,
590).

Note : — Generators of pentane (see under n-
amyl alcohol [20 ; B ; C ; D]) and of hexane
(see under n-hexyl alcohol [23 ; A ; B ; C ; &c.])
thus become generators of n-butyl alcohol
through butane.

[F.] From formic aldehyde [Ol] and
n-propyl alcohol [13]. Trioxymethylene
(polymerisation product of the aldehyde)
and zinc propyl form a compound which
is decomposed by water with the forma-
tion of n-butyl alcohol (Tischtschenko,
Journ. Russ. Soc. 19, 484: see B, above).

[Q.] From acetic aldehyde [92]
through crotonic aldehyde [102] by
condensation (Lieben, Ann. Suppl. 1,
117; Bauer, Ann. 117, 14T ; Kekule,
Ann. 162, 92 ; Zeit. [2] 5, 572 ; Lieben
and Zeisel, Monats. 1, 820 ; Newbury
and Calkin, Am. Ch. Journ. 12, 523 ;
Orndorff and Newbury, Monats.
13, 513; Lieben, Ibid. 519; Miiller,
Bull. Soc. [3] 6, 796 ; Claisen, Ann.
306, 322 ; Charon, Ann. Chim. [7]
17, 197; Delepine, Comp. Rend. 133,
876). The aldehyde is reduced by iron
and acetic acid to n-butyl alcohol (with
butyric aldehyde and crotonyl = butenyl
alcohol) (Lieben and Zeisel, loc. cit. 825 ;
842).

Or from aldehyde through /3-hydr-
oxybutyric aldehyde (aldol) by conden-
sation with acid or alkaline condensing
agents (Wurtz, Comp. Rend. 74, 1361 ;
76, 1 1 65; 92, 1438; Jahresber. 1872,
449 ; 1881, 599 ; Michael and Kopp,
Am. Ch. Journ. 5, 185; Orndorff and
Newbury, Monats. 13, 516; Claisen,
Ann. 306, 323). Aldol gives ^-butylene-
glycol on reduction with sodium amal-
gam (Wurtz, Comp. Rend. 97, 473 ;
Demjanoff, Ber. 28, 22). From the
glycol through i : 3-dibrombutane and
methylcyclopropane as below under P.

Note : — Aldol gives crotonic aldehyde on
dry distillation (Wurtz, Comp. Rend. 87, 45 ;
Orndorff and Newbury, loc. cit.).

[H.] From butyric aldehyde [94] by
reduction with sodium amalgam (Lieben
and Rossi, Ann. 158, 137; 165, 145).

[I.] From formic acid [Vol. II] and
erythritol [60], which give crotonic
aldehyde [102] on distillation (Hennin-
ger, Ann. Chim. [6] 7, 217), and then
as above under G.

Note : — Other generators of crotonic alde-
hyde are : aldol (from aldehyde ; Wurtz,
Jahresber. 1878, 612; Newbury, Am. Ch. Journ.
5, 112 ; Comp. Rend. 92, 196) : acetylene by the
successive action of sulphuric acid and water
(Lagermarck and Eltekoflf, Ber. 10, 637 ; Ber-
th el ot, Comp. Rend. 128, 336) : vinyl bromide
from ethylene bromide by the same treatment
(Zeisel, Ann. 191, 371) : the lactic acids [Vol. II]
by electrolysis of strong solutions of the sodium
salts (v. Miller and Hofer, Ber. 27, 468) : P-
hydroxybutyric acid [Vol. IIj by electrolysis of
the sodium salt {Ibid. 469).

[J.] From acetic acid [Vol. II] and
ethyl alcohol [14]. Ammonium acetate
is converted into acetamide and aeeto-
nitrile = methyl cyanide (Dumas, Comp.
Rend. 35, 383 ; Buckton and Hofmann,
Journ. Ch. Soc. 9, 242; Henry, Ann.
152, 149; Wallach, Ann. 184, 21 ;
Demar^ay, Bull. Soc. [2] 33, 456).
From methyl cyanide and ethyl iodide
through n-propyl cyanide, n-butylam-
ine, &c., as above under A.

Or from acetic dind. formic ethyl esters
[Vol. II ; and 14], which condense under
the influence of sodium ethoxide to
form formylacetic = oxymethyleneacetic
ester (Wislicenus, Ber. 20, 2930 : see also
V. Pechmann, Ann. 264, 269), which
undergoes further condensation when
liberated from its sodium derivative
to form formylglutaconic ester (Wis-
licenus and Bindemann, Ann. 316, 18).
Formylglutaconic acid gives the lactone,
coumalic acid, and this on heating with
sulphuric acid yields crotonic aldehyde
[102], which can be reduced as above
under G.

[K.] Propionic acid [Vol. II] gives
butane among the products of electro-
lysis of the potassium salt (Bunge,
Journ. Russ. Soc. 21, 551 ; Petersen,
Ch. Centr. 1897, 2,518).

[L.] From butyric acid [Vol. II]
through butyryl chloride, which gives
the alcohol on reduction with sodium
amalgam (Saytzeff, Zeit. [2] 6, 108;
Linnemann, Ann. 161, 178) or with

72

ALCOHOLS

[17 L-18 C.

sodium in moist ethereal solution (W. H.
Perkin, junr., and Sudborough, Proc.
Ch. Soc. 10, 2 1 6).

Or from butyric acid through butyro-
nitrile = n-propyl cyanide by distilling
the ammonium salt or amide with
phosphorus pentoxide (Dumas, Malaguti,
and Leblanc, Comp. Rend. 25, 442 ;
658 ; Ann. 64, 332) or with zinc chloride
(Linnemann and Zotta, Ann. 162, 3;
also Aschan, Ber. 31, 2344). From the
nitrile to n-butylamine, &c., as above
under A.

Butyric acid gives butane by heating
with hydriodic acid (Berthelot; see
under methane [l ; I]).

[M.] Succinic acid [Vol. II] gives
butane on heating with hydriodic acid
(Berthelot, loc. cit.).

[N.] Aflipic acid [Vol. II] gives
butane by distilling the calcium salt
with excess of lime (Hanriot, Bull. Soc.
[2] 45, 80).

[O.] Malic acid [Vol. II] on heating
with strong sulphuric acid or zinc
chloride gives coumalic acid (v. Pech-
mann, Ann. 264, 272). Subsequent
steps through crotonic aldehyde, &c., as
above under J and G. Crotonic aldehyde
is among the products of electrolysis of
a strong solution of sodium malate (v.
Miller and Hofer, Ber. 27, 470).

[P.] From ietramethylenedlamine [pu-
trescine) [Vol. II] through /3-butylene-
glycol by the action of nitrous acid
(Demjanoff, Journ. Buss. Soc. 24, 354),
I : 3-dibrombutane by heating the glycol
with hydrobromic acid {Ibid. 351), and
methylcyclopropane by the action of
zinc dust on the alcoholic solution of
the dibrombutane [Ibid. Ber. 28, 21).
Methylcyclopropane gives n-butyl alco-
hol on treatment with strong sulphuric
acid and distillation of the product with
water {Ibid. 23).

18. Isobutyl Alcohol ; Isopropyl
Carbinol ; 2-Metliyl-l-Fropaiiol.

CH3.CH(CH3).CH,.OH

Natural Sources.

A secondary product of alcoholic fer-
mentation as a constituent of the fusel

oils from beet molasses spirit, potato
spirit, and brandy (Wurtz, Ann. Chim.
[3] 42, 129; Ann. 85, 797; 93, 107;
Comp. Rend. 35, 310; Chapman and
Smith, Ber. 2, 127; Kramer and Pinner,
Ibid. 403 ; 3, 77 ; Rabuteau, Comp.
Rend. 87, 501 ; Claudon and Morin,
Ibid. 104, 1 109 and 11 87; Bull. Soc.
[2] 49, 178).

Isobutyl esters of angelic and other
acids occur in Roman oil of chamomile
from Atithemis nobilis (Demar9ay, Comp.
Rend. 77, 360; 80, 14CO; Fittig and
Kobig, Ann. 195, 79 j 81 ; 92).

Isobutyl alcohol is found in traces
(with the n-alcohol) among the products
of the fermentation' of the various
carbohydrates capable of being attacked
by the Bacillus orthobutylictis of Grim-
bert (Ann. Inst. Past. 7, 353 : see also
under n-butyl alcohol [l7]), the Bacillus
isolated fromfermentingcalcium tartrate
solution.

Synthetical Processes.

[A.] From tertiary hniyl alcohol [19]
through isobutylene by the action of
alcoholic potash on the tertiary butyl
iodide or by heating the alcohol with
dehydrating agents (Butleroff, Ann. 144,
19; Zeit. [2] 6, 236: see also Lermentoff,
Ann. 196, 117). Isobutylene combines
with hypochlorous acid to form chlor-
isobutyl alcohol, and this on reduction
with sodium amalgam gives isobutyl
alcohol (Butleroff, Ann. 144, 24).

Note : — Tertiary butyl alcohol gives a butyl-
ene on heating with anhydrous oxalic acid
(Cahours and Demargay, Comp. Rend. 86,
991).

[B.] From isoamyl alcohol [22], iso-
butylene being among the products of
pyrogenic contact decomposition by
passing the vapour through a hot iron
tube (Ipatieff, Ber. 35, 1053 : see also
Wurtz^ Ann. 104, 249 ; Butleroff, Ann.
145, 277).

[C] From isovaleric acid [Vol. II]
by electrolysis of a solution of the
potassium salt (Kolbe, Ann. 69, 259).
Isobutylene is among the products
formed and can be treated as under A.
Isobutylene is among the products of

18 C-19.]

ISOBUTYL ALCOHOL

73

the dry distillation of calcium isovalerate
(Dilthey, Ber. 34, 2115).

Also from this acid by oxidation with
alkaline permanganate to j8-hydroxyiso-
valerie acid [(CHg)^ : C(OH) . CHg .
COOH] (v. Miller, Ann. 200, 273), 13-
dimethylacrylic acid [(CHg)^ : C : CH .
COOH] by distillation with dilute sul-
phuric acid (Neubauer, Ann. 106, 62 ;
V. Miller, loc. cit. 261), conversion into
isobutylene by heating to 210-220°
(Gorboff and Kessler, Bull. Soc. [2] 41,
392), and then as under A.

/3- Hydroxy isovaleric acid is also con-
verted into /3-dimethylacrylic acid (ethyl
ester) by the action of phosphorus tri-
chloride on ethyl ^-hydroxyisovalerate
(Semljanitzin and SaytzefP, Ann. 197,
72; Ustinoff, Journ. pr. Ch. [2] 34,
478 ; Bull. Soc. [2] 45, 255). Also
from isovaleric acid through the a-
bromo-acid (Borodin, Ann. 119, 122;
Cahours, Ann. Suppl. 2, 78 ; Fittig and
Clark, Ann. 139, 199; Ley and Popoff,
Ann. 174, 63) and the action of sodium
ethylate or ammonia on a-bromisovaleric
ester (Duvillier, Comp. Rend. 88, 913;
1209; 112, 1012; Ann. Chim. [5] 19,
428; Bull. Soc. [3] 5, 848) : /3-dimethyl-
acrylic acid is one of the products formed
and can be converted into isobutylene
as above.

Ethyl /3-dimethylacrylate is obtained,
by the action of diethylaniline or of
quinoline on a-bromisovaleric ester
(Weinig, Ann. 280, 253; W. H. Perkin,
junr.. Trans. Ch. Soc. 69, 1471).

[D.] From acetone [IO6] and glycerol
[48] by converting the latter into allyl
iodide (Berthelot and De Luca, Ann.
Chim. [3] 43, 258 ; Tollens, Bull. Soc.
[2] 9, 396 ; Claus, Ann. 131, 59 ;
Oppenheim, Ann. Suppl. 6, 354 ;
Tollens and Henninger, Ann. 156,
156; Wagner, Ber. 9, 1810; Kanon-
nikoff and Saytzeff, Ann. 185, 191 ;
James, Ann. 226, 206 ; Behal, Bull.
Soc. [2] 47, 875 ; Malbot, Ann. Chim.
[6] 19, 'i^^^ and '>fi'^, and allow-
ing zinc to act upon a mixture of
acetone and allyl iodide so as to form
dimethylallyl carbinol [CH2:CH.CH2.
C(CH3),.0H] (Saytzeff, Ann. 185,
151 and 175); oxidation of the latter
to /3-hydroxyisovaleric acid (Saytzeff,

Ann. 185, 163 ; Schirokoff, Journ.
pr. Ch. [2] 23, 206); then to ^-di-
methylacrylic acid and isobutylene as
under C.

A mixture of acetxDne, malonic acid,
and acetic anhydride gives dimethyl-
acrylic acid on heating (Massot, Ber.
27, 1225). Acetone and ace/^oaee^zc ester
condense under the influence of hydro-
gen chloride to form isopropylidene-
acetoacetic ester, and this on boiling
with barium hydroxide solution yields
dimethylacrylic acid (Pauly, Ber. 30,
481).

Also from acetone and acetic acid by
converting the latter into chloracetic
ethyl ester (Willm, Ann. 102, 109 ;
Conrad, Ann. 188, 218) and allowing
zinc to act upon a mixture of acetone
and the ester so as to form ethyl ^-
hydroxyisovalerate (Ref ormatsky, Journ.
Russ. Soc. 22, 47), which can be hydro-
lysed and treated as above.

The * acetone-chloroform ^ referred to
under tertiary butyl alcohol [19 j D]
gives isobutylene on boiling with alco-
hol and zinc dust (Jocitsch, Journ.
Russ. Soc. 30, 920; Ch. Centr. 1899,
1, 606).

[E.] Isohityric aldehyde [94] gives
isobutyl alcohol (with isobutyric acid)
on heating with barium hydroxide
solution (Lederer, Monats. 22, ^^^).

19. Tertiary Butyl Alcohol ;
Trimethyl Carbinol ;
2 - Methyl-2-Fr opanol.

CH3.C(CH3)(OH).CH3

Natural Source.

Has been said to occur in small
quantity in certain fusel oils (Rabuteau,
Comp. Rend. 87, 501 ; Butleroff, Ann.
144, 34; Trommsdorf, as quoted by
Meyer and Jacobson, 'Lehrb. d. org.
Ch.-* p. 161). It is probable, however,
that the alcohol thus obtained was
formed from isobutyl alcohol during
the process of treatment (Meyer and
Jacobson, loc. cit.).

74

ALCOHOLS

[19 A-B.

Synthetical Processes.

[A.] From acetic acid [Vol. II] and
methyl alcohol [13] through the com-
pound formed by the interaction of
zinc methyl and acetyl chloride and
decomposition of this compound by
water (Butleroff, Jahresber. 1864, 496 ;
Ann. 144^ i ; Wagner and Saytzeff,
Ann. 175, 361 ; Pawloff, Ann. 188,
118). The same intermediate com-
pound is formed from zinc methyl and
carbonyl chloride (Butleroff, Zeit. 1863,
484). Magnesium methyl and acetyl
chloride can be used also in this syn-
thesis (Fleck, Ann. 276, 129). Or
magnesium methiodide and methyl
acetate (Grignard, Comp. Rend. 132,
336); or magnesium methiodide and
acetyl chloride (Tissier and Grignard,
Ibid. 683).

Or from dichloracetic acid through
dichloracetyl chloride (Otto and Bec-
Ivurts, Ber. 14, j6i8), which, by inter-
action with zinc methyl and decompo-
sition of the product with water, gives
dimethylisopropyl carbinol (Bogomo-
letz, Ann. 209, 82). Subsequent steps
through pinacone, pinacolin, trimethyl-
acetic acid, &c., as below under D
and E.

Isobutylene is among the products
formed by dropping acetic acid on to
heated zinc chloride (LeBel and Greene,
Am. Ch. Journ. 2, 26).

[B.] From isohutyl alcohol [is]
through isobutylene by heating with
sulphuric acid (Lermentoff, Ann. 196,
117; Puchot, Ann. Chim. [5] 28, 508 ;
Comp. Rend. 85, 757 : for use of zinc
chloride as a dehydrating agent see
Nevole, Bull. Soc. [2] 24, 122: see
also Konowaloff, Ber, 13, 2395 ; Bull.
Soc. [2] 34, 333, and Scheschukoff,
Journ. Russ. Soc. 16, 51° • with the
ordinary dehydrating agents, Konowa-
loff, loc. cit. ; LeBel and Greene, Bull.
Soc. [2] 29, 306, or with heated plum-
bago crucible material as pyrogenic
contact substance, Ipatieff, Ber. 35,
1061, pseudobutylene is also formed :
see further Faworsky and Desbout,
Journ. pr. Ch. [2] 42, 152; Ipatieff,
loc. cit. : for production of isobutylene by
passing the vapour of the alcohol mixed

with air over heated platinum see
V. Stepski, Monats. 23, 773). Iso-
butylene is formed also by the action
of alcoholic potash on isobutyl iodide
(Butleroff, Ann. 144, 19; Zeit. [2]
6, 278 : see also De Luynes, Comp.
Rend. 56, 1175; Ann. Chim. [4]

2, 385) or chloride (Nef, Ann. 318,
28). Isobutylene on treatment with
sulphuric acid and hydrolysis gives
tertiary butyl alcohol (Butleroff, Ann.
144, 22 ; 180, 246) ; or by combina-
tion with zinc chloride it forms a crys-
talline compound which yields tertiary
butyl alcohol on decomposition with
water (Kondakoff, Journ. Russ. Soc.
25, 345 and 456 ; also Journ. pr. Ch.
[2] 54, 442). Isobutylene is converted
into tertiary butyl alcohol by the action
of aqueous oxalic acid (Miklaschewsky,
Journ. Russ. Soc. 22, 495). On com-
bination with hydrogen iodide iso-
butylene gives tertiary butyl iodide
(Butleroff, Ann. 144, 22 ; Markowni-
koff, Zeit. [2] 6, 29), which can be
converted into the alcohol by the action
of water (Scheschukoff, Bull. Soc. [2]
45, 181 ; Dobbin, Trans. Ch. Soc. 37,
238).

Isobutyl iodide on treatment with
acetic acid and silver oxide gives also
tertiary (with isobutyl) alcohol (Linne-
mann, Ann. 162, 12; Butleroff, Ann.
168, 143).

Isobutyl alcohol can also be con-
verted into isobutyl chloride by the
action of hydrogen chloride, and then
into isobutylene by the action of
aluminium chloride on isobutyl chloride
(Mouneyrat, Ann. Chim. [7] 20, 485).

Also from isobutyl alcohol through
isobutylamine by the action of ammonia
on the iodide or bromide (Reimer, Ber.

3, 756 j Hughes and Romer, Ber. 7,
511) or chloride (Malbot, Bull. Soc.
[2] 47, 957 ; [3] 4, 693 ; Comp. Rend.
104, 6^; 228) and the action of nitrous
acid on isobutylamine (Linnemann,
Ann. 162, 24). Isobutylamine can also
be obtained from the alcohol by heat-
ing with ammonio-zinc chloride (Merz
and Gasiorowski, Ber. 17, 623). Ter-
tiary butyl alcohol is obtained also from
isobutyl iodide through the cyanate
(Brauner, Ber. 12, 1874) and the action

19 B-H.]

TERTIARY BUTYL ALCOHOL

75

of potash on the latter (Linnemann,
Ann. 162, 12).

Also from isobutyl alcohol by heat-
ing with hydrochloric acid and decom-
posing" the tertiary chloride by heating
with water, the isobutyl chloride simul-
taneously formed remaining undecom-
posed (Freund^ Journ. pr. Ch. [2] 12,

25)-

Isobutyl alcohol, when converted into

isobutylsulphuric acid and the barium

salt of the latter heated to 130°, gives

a mixture of isobutylene (|) and pseudo-

butylene (^) (Biron, Joum. Russ. Soc.

29, 697).

[C] From isovaleric acid [Vol. II]
through isobutylamine by the action
of bromine and potash on the amide
(Hofmann, Ber. 15, 769) and then as
under B. Also from isovaleric acid
through isobutylene (see under isobutyl
alcohol [18; C]).

[D.] From acetone [IO6] and glycerol
[48] through j3-dimethylacrylic acid
(see under isobutyl alcohol [18; D]
and isobutylene as above. Or from
acetone and acetic acid through ^-
hydroxyisovaleric ester and isobutylene
as under isobutyl alcohol [l8 ; D].

Also from acetone and chloroform
[1 ; D] through ' acetone chloroform,^
CCl3.C(CH3),.OH (Willgerodt and
Genieser, Journ. pr. Ch. [2] 37, 364 ;
also Willgerodt, Ber. 14, 2451 ; 16,
1585 ; Cameron and Holly, Journ.
Physical Ch. 2, 322), and reduction of
the latter with zinc and hydrochloric
acid at 100° (Willgerodt and Diirr,
Journ. pr. Ch. [2] 39, 387).

Also in small quantity from acetone
and methyl iodide by the action of
sodium on the moist ethereal solution
(Frey, Ber. 28, 2520). Or to the ex-
tent of 70 per cent, from acetone by in-
teraction with magnesium methiodide
(Grignard, Ch. Centr. 1901, 2, 623).

Or from acetone through pinacone
( = tetramethylethylene glycol) by the
action of sodium (Fittig, Ann. 110, 25 ;
114, 54; Stadeler, Ann. Ill, 277;
Friedel, Ann. 124, 329 ; Bull. Soc. [2]
19, 289; Friedel and Silva, Ber. 6,
?,S '} 2*^7 } Jahresber. 1873, 340 ;
Thiele, Ber. 27, 455), or by electro-
lysis (Merck, Germ. Pat. 1 137 19 of

1899; Ch. Centr. 1900, 2, 794), pin-
acolin (= dimethylbutanone) by dis-
tilling pinacone with dilute sulphuric
acid (Fittig, Ann. 114, ^6 : see also
Vorlander, Ber. 30, 2266), trimethyl-
acetic = pivalic acid by the oxidation
of pinacolin (Friedel and Silva, Comp.
Rend. 77, 48; Reformatzky, Ber. 23,
1596). The acid gives trimethyl car-
binol when the potassium salt is electro-
lysed in aqueous solution (Petersen,
Zeit. physik. Ch. 33, 698).

[E.] From isohutyric acid [Vol. II],
the calcium salt of which gives pin-
acolin on distillation (Barbaglia and
Gucci, Ber. 13, 1572), and then as
above.

Or from isobutyric acid and methyl
alcohol through dimethylisopropyl car-
binol, which is formed by the inter-
action of isobutyl chloride and zinc
methyl and decomposition of the product
with water (Prianischnikoff, Zeit. [2]
7, 275). The tertiary hexyl iodide
corresponding to the alcohol on treat-
ment with alcoholic potash gives tetra-
methylethylene (Pawloff, Ann. 196,
124), and the bromide of the latter on
treatment with silver acetate and
hydrolysis yields pinacone {Ibid. 126).
Or the dimethylisopropyl alcohol gives
tetramethylethylene on distillation with
sulphuric acid (Reformatsky and Ples-
canossoff, Ber. 28, 2841).

[P.] From amyl alcohol [22] and
methyl alcohol [13] through trimethyl-
ethylene (see under acetone [IO6 ; E]),
which gives tetramethylethylene on
heating with lead and methyl iodide
at 220-230° (Eltekoff, Journ. Russ.
Soc. 14, 380). Subsequent steps
through pinacone as above. Or from
fusel oil amyl alcohol through iso-
butylene by pyrogenic decomposition
(see under isobutyl alcohol [18 ; B]) and
then as under B above.

[G.] From ethyl [14] and methyl
alcohol [13] through chloral (Liebig,
Ann. 1, 1 89), which by interaction with
zinc methyl gives dimethylisopropyl
carbinol (Rizza, Journ. Russ. Soc. 14,

99)-

[H.] From propionic acid [Vol. II]

and methyl alcohol [l3]. a-Brompro-

pionic acid (Friedel and Machuca, Ann.

76

ALCOHOLS

[19 H-20 H.

120, 286 j Zelinsky, Ber. 20, 2026 ;
Michael and Graves, Ber. 34, 4044)
gives brompropionyl bromide (Kaschir-
sky, Journ. Russ. Soc. 13, 81), which
by interaction with zinc methyl yields
dimethyl isopropyl carbinol (Ibid. 82).

[I.] From lactic acid [Vol. II} and
methyl alcohol [13]. Lactic acid re-
acts with hydrogen bromide to form
a-brompropionie acid (Kekul^, Ann.
130, 16). Subsequent steps as above
under H, &c.

[J.] From diacetyl [113] and methyl
alcohol [13] through pinacone by the
interaction of magnesium methiodide
and the former (Zelinsky, Ber. 35, 2138).
From pinacone through pivalic acid as
above under D.

20. Normal Primary Amyl Alcohol ;

Normal Butyl Carbinol ;

l-Fentauol.

CH, . CH, . CH, . CH, . CHo . OH

Natural Sources.

Said to occur in certain fusel oils
(Wischnegradsky, Ann. 190, 350) and
among the products of fermentation of
glycerol by Bacillus hutylicus (Morin,
Bull. Soc. [2] 48, 803).

Synthetical Processes.

[A.] From normal valeric (pentanoic)
acid [Vol. II] through the aldehyde
[95] by distillation with a formate
(Lieben and Rossi, Ann. 159, 70) and
reduction with-sodiimi amalgam (ibid.).

Note : — The generators of valeric aldehyde
given under this compound are : succinic acid ;
fumaric acid ; adipic acid ; stearic acid (all
through sebacic acid) ; and n-hexoic acid.

[B.] From acetic acid [Vol. II] by
combining acetyl chloride with alu-
minium chloride, decomposing the pro-
duct with water (Combes, Ann. Chim.
[6], 12, 207), and reducing the acetyl-
acetone (2 : 4-pentanedione) thus formed
to n-pentane by heating with hydriodic
acid (Combes, loc. cit. 233). Normal
pentane gives i-chlorpentane (together
with 2-chlorpentane) on chlorination

(Schorlemmer, Ann. 161, 268 ; Lacho-
wicz, Ann. 220, 191), and the corre-
sponding alcohol is obtained by con-
version into amyl acetate and hydrolysis
{Ibid.).

Note : — Normal pentane might also be syn-
thesised from methyl [13] and n-hutyl [17]
alcohols or from ethyl [14] and n-propyl [15]
alcohols by acting upon mixtures of the alkyl
iodides v?ith sodium (Wurtz, Ann. Chim. [3]
44, 275 : see also under heptane [2 ; A]).

[C.} From acetone [IO6], acetic acid
[Vol. II], and ethyl alcohol \1^ through
acetylacetone by the action of sodium
on a mixture of acetone and ethyl
acetate (Claisen and Ehrhardt, Ber. 22,
loii ; Claisen, Ann. 277, 168), reduc-
tion to pentane, &c., as under B.

[D.] From pyridine or piperidine
[Vol. II] through n-pentane by heat-
ing with hydriodic acid to over 300°
(Hofmann, Ber. 16, 590 ; Spindler,
Journ. Russ. Soc. 23, 39) and then as
under B.

[E.] From normal hexoic acid [Vol. II]
by the action of iodine on the silver
salt (Simonini, IMonats. 13, 316) and
hydrolysis of the amyl hexoate formed.

Or from n-hexoic acid through n-
amylamine (i-aminopentane) by the
action of bromine in presence of potash
on the amide of the acid (Hofmann,
Ber. 15, 770), followed by the action of
nitrous acid on the amine (Gartenmeister,
Ann. 233, 253).

[F.] From adipic acid [Vol. II]
through sebacic acid by electrolysis of
potassium ethyl adipate and hydrolysis
of the ester (Crum Brown and Walker,
Ann. 261, 120). Sebacic acid when
distilled with lime is said to give
among other products valeric aldehyde
(Calvi, Ann. 91, no; Petersen, Ann.
103, 184 ; Dale and Schorlemmer, Ann.
199, 149), which can be treated as
under A.

[G.] From mannitol [5l] through
n-hexane (see under n-hexyl alcohol
[23; B]). The latter gives pentane
on heating with aluminium chloride
(Friedel and Gorgeu, Comp. Rend. 127,
590). Subsequent steps as under B
above.

[H.] From glycerol [48] through
diallyl and hexane (see under n-hexyl

20 H-21 D.] NORMAL PRIMARY AMYL ALCOHOL

11

alcohol [23 ; C]) and pentane, &c., as
above.

[I.] From glulario acid [Vol. II]
through suberic acid and hexane (see
under n-hexyl alcohol [23; D]) and
then as above.

Note : — The following generators of suberic
acid referred to under n-hexyl alcohol [23] thus
become generators of hexane and therefore of
pentane and n-amyl alcohol : (xiyl alcohol [33] ;
myristic acid [Vol. II] ; stearic acid [Vol. II] ;
adipic acid [Vol. II] through sebacic acid ;
azelaic acid [Vol. II] through ketocyclo-octane.

For aromatic generators of hexane see under
n-hd'xyl alcohol [23 ; A].

[J.] From n-hutync acid [Vol. II]
through hexane (see under n-hexyl
alcohol [23 ; K]), pentane, &c., as above
under G.

21. Methylpropyl Carbinol ;

Normal Secondary Amyl Alcohol ;

2-Fentanol.

CH3 . CH, . CH^ . CH(OH) . CH3

Natural Source.

Said to occur in fusel oil (especially
Swedish) from potato starch spirit (Ra-
buteau^ Comp. Rend. 87, 501).

Synthetical Processes.

[a.] From acetic and hutyric acids
[Vol. II] through methylpropyl ketone
(a-pentanone) by distillation of the
mixed calcium salts (Semljanitzin,
Journ. pr. Ch, [2] 23, '2,6'3, ; Friedel,
Ann. 108, 124 ; Grimm, Ann. 157, 251)
and reduction with sodium amalgam
(Friedel, Jahresber. 1869, 513; Belo-
houbek, Ber. 9, 924).

[B.] From methyl alcohol [l3] and
hutyric acid [Vol. II] by the action
of zinc methyl on butyryl chloride and
decomposition of the product with water
(Butlerofe, Zeit. [2] 1, 614; Bull. Soc.
[2] 5, 17) and reduction of the methyl-
propyl ketone thus obtained as under A.

[C] From ethyl alcohol [14] by the
action of zinc ethyl on chloroform
(Beilstein and Rieth, Ann. 124, 245).
The amylene thus formed is probably
the symmetrical methylethylethylene

(3-pentene), which can be converted
into 2-chlor- or 2-iodopentane, &c., as
under F.

Or from ethyl alcohol and acetic acid
[Vol. II] through ethylacetoacetic ester
by the action of sodium and ethyl
iodide on acetoacetic ester (Geuther,
Jahresber. 1863, 324; Frankland and
Duppa, Journ. Ch. Soc. 4, 396 ; Wis-
licenus, Ann, 186, 187; IMiller, Ann.
200, 281; Wedel, Ann. 219, 100),
methylpropyl ketone by heating with
potash or baryta (Frankland and Duppa,
Ann. 138, 2 16), and reduction as under
A. Or the ethylacetoacetic ester can
be reduced by sodium amalgam to
a-ethyl-/3-hydroxybutyric (2-pentanol-
3-methylic) acid (Waldschmidt, Ann.
188, 240), the latter decomposed by dry
distillation into a-ethylcrotonic acid
{Ihid. 245) j then through the hydro-
bromide, 3-pentene, 2-chlorpentane, &c.,
as under G.

Also from acetic acid and ethyl alco-
hol through acetoacetic ester [Vol. II],
the y-chloro-derivative which is formed
(with the a-derivative) on chlorination
(Haller and Held, Comp. Rend. 108,
516), the y-cyano-derivative by the
action of potassium cyanide [lUd.), ace-
tonedicarboxylic ester, by the action of
hydrogen chloride on the y-cyano-deri-
vative dissolved in alcohol (Haller and
Held, Comp. Rend. Ill, 682), dimethyl-
acetonedicarboxylic ester, and subse-
quent steps as under H. Also from
ethyleneacetoacetic ester (W. H. Per-
kin, junr., Ber. 16, 2136 ; 17, 1440)
through acetyltrimethylenecarboxylic
acid, acety Itrimethylene (ethanoy 1-cy clo-
propane), and reduction of latter with
sodium amalgam (IMarshall and W. H.
Perkin, junr., Trans. Ch. Soc. 59, 874).

[D.] From acetone [106], acetic acid
[Vol. II], and ethyl alcohol [14] through
acetylacetone (see under n-primary
amyl alcohol [20; B and C]), ethyl-
acetylacetone by the action of ethyl
iodide on the sodium salt (Combes,
Ann. Chim. [6] 12, 247), methylpro-
pyl ketone by the action of potash
[Ibid. 248), and reduction as under A.

Or the acetylacetone can be converted
directly into 2-iodopentane by heating
with hydriodic acid (Combes, Ann.

78

ALCOHOLS

[21 D-I.

Chim. [6] 12j 334) and the iodopentane
into the alcohol by the usual methods.

[E.] From propionic acid [Vol. II]
through diethyl ketone (3-pentanone) by
distillation of the barium salt (Morley,
Ann. 78, 187), the dichloride by heat-
ing* with phosphorus pentaehloride,
methylethylacetylene (3-pentine) by the
action of alcoholic potash on the di-
chloride (Faworsky, Journ. pr. Ch. [a]
37, 387), methylpropyl ketone by heat-
ing the acetylene derivative with water
and mercuric bromide (Kutscheroff,
Ber. 14, 1542), and reduction as under
A.

Also from propionic acid through
diethyl ketone by the action of propionyl
chloride on zinc ethyl (Freund and
Pebal, Ann. 118, 9) and treatment as
above.

[P.] 'Evovci formic acid [Vol. II] and
ethi/l alcohol [l4] through diethyl car-
binol = 3-pentanol by the action of zinc
and ethyl iodide on formic ester and
decomposition of the product with water
(Wagner and Saytzeff, Ann. 175, 351),
diethyl ketone by oxidation of the
alcohol {Ibid. Ann. 179, 322), and then
as under E.

Also by converting the diethyl ear-'
binol into amylene = symmetrical
methylethylethylene = 3-pentene by the
action of alcoholic potash on the iodide
(Wagner and Saytzeff, Ann. 175, 373 ;
179, 302), combining the amylene with
hydrogen chloride to form 2-chlorpen-
tane {Ibid. Ann. 179, 3 2 1 ), and conversion
into the alcohol by the usual methods
(Schorlemmer, Ann. 161, 268). Hydro-
gen iodide combines with the amylene to
form 2-iodopentane (Wurtz, Ann. 148,
132), which can be converted into the
alcohol by the same methods.

[G.] From oxalic acid [Vol. II] and
ethi/l alcohol [14] through diethoxalic
= hydroxydiethacetic = 3-pentanol-3-
carboxylic acid by the action of zinc
ethyl on oxalic ester and decomposition
of the product with water (Frankland,
Proc. Roy. Soc. 12, 396; Frankland
and Duppa, Ibid. 13, 140 ; Ann. 135,
26 ; Geuther, Zeit. [2] 3, 705 ; Fittig,
Ann. 200, 21), diethyl ketone by the
oxidation of diethoxalic acid or by
heating its ester with hydrochloric acid

(Chapman and Smith, Journ. Ch. Soc.
20, 173; Geuther and Wackenroder,
Zeit. [2] 3, 709), and then as under E.

Or from diethoxalic ester through
a-ethylcrotonic ester by the action of
phosphorus trichloride (Frankland and
Duppa, Journ. Ch. Soc. 18, 133 ; Ann.
136, 2 ; Fittig and Howe, Ann. 200,
22 : see also Geuther, Bull. Soc. [2]
10, 34), the hydrobromide of ethylero-
tonic = 2-pentene-3-carboxylic acid by
the direct addition of hydrogen bromide
to the acid (Fittig and Howe, loc. cit. 23),
3-pentene by the decomposition of the
hydrobromide by cold sodium carbonate
solution (Fittig, Ibid. 30), 2-chlor- or
2-iodo-pentane, &c., as under P (see
also under hexoic aldehyde [2-methyl-
pentanol; 96 ; L]).

[H.] From citric acid [Vol. II] and
methyl alcohol [l3] through acetone-
dicarboxylic acid (3-pentanonediacid)
by heating the former with sulphuric
acid (v. Pechmann, Ber. 17, 2543 ;
Ann. 261, 157; Peratoner and Straz-
zeri, Gazz. 21, 295 : see also under
orcinol [75 ; C]), the diethyl ester,
dimethylacetonedicarboxylic (2 : 4-di-
methylpentanonediacid) diethyl ester by
the action of sodium methylate and
methyl iodide on acetonedicarboxylic
ester (Diinsehmann and v. Pechmann,
Ann. 261, 182), diethyl ketone by the
action of hot dilute sulphuric acid on
the dimethylacetonedicarboxylic ester
{Ibid.), and then as under B. Citric
acid gives acetonedicarboxylic acid by
oxidation with potassium permanganate
(Denig^s, Comp. Rend. 130, 32).

Note : — Other generators of diethyl ketone
are : sodiuin ethyl and carbon monoxide (Wank-
lyn, Ann. 140, 211) ; acetyl or propionyl cliloride
acted upon by dry ferric chloride (Hamonet,
Bull. Soc. [2] 50, 356 and 547) ; zinc ethyl and
nitropropane (Bevad, Ch. Centr. 1900, 2, 944).

[I.] From crude (fusel oil) am,j/l
alcohol [22] by conversion into amylene,
amylene bromide, and ' valerylene ' by
the action of alcoholic potash (Reboul,
Ann. 131, 238 ; Eltekoff, Journ. Russ.
Soc. 9, 378). This Walerylene' pro-
bably contains methylethylacetylene (3-
pentine), and can be converted into
methylpropyl ketone, &c., as under E.

Normal primary am^l alcohol [20]

21 1-22.]

METHYLPROPYL CARBINOL

79

can be converted into the n-amyl
chloride (i-chlorpentane), and the latter
on heating with acetic acid and potas-
sium acetate to 30o° gives (with amyl
acetate) normal amylene (propylethy-
lene) (Schorlemmer^ Ann. 161, 269),
which combines with hydrogen iodide
to form 2-iodopentane (Wurtz, Ann.
148, 131 : see also Wagner and Sayt-
zeff, Ann. 179, 313; Wischnegradsky,
Ann. 190, 347), from which the alcohol
can be obtained as under F. Normal
amylene is also among the amylenes
obtained from the amyl alcohols of
fusel oil by the action of zinc chloride
(Wischnegradsky, Journ. Russ. Soc. 9,
192).

[J.] From 7iormal propyl alcohol [15]
and acetic acid [Vol. II] by the action
of zinc propyl (Gladstone and Tribe,
Ber. 6, 1 136; Schtscherbakoff, Bull. Soc.
[2] 37, 345) on acetyl chloride (Mar-
kownikoff, Bull. Soc. [2] 41, 259 ;
Wagner, Journ. Buss. Soc. 16, '>,'>>'^.
Ethyl alcohol is formed at the same
time.

[K.] From normal pentane (see under
n-amyl alcohol [20 ; B ; C ; D, &c.])
by chlorination (Schorlemmer, Ann.
161, 268) and conversion into the al-
cohol by usual methods. The i-chlor-
pentane formed also during chlorination
can be converted into 2-pentanol through
propylethylene as under I.

Note : — All generators of n-hexane are gener-
ators of pentane (see under n-amyl alcohol [20 ;
G]) and therefore of 2-pentanol. The generators
of hexane (see under n-hexyl alcohol [23]
are : mannitol [51] ; glycerol [48] ; glutaric arid
[Vol. II] ; cetyl alcohol [33] ; myristic acid [Vol.
II] ; stearic acid [Vol. II] ; adipic acid [Vol. II] ;
n-butyric acid [Vol. II], and aromatic compounds
(see under n-hexyl alcohol [23 ; A]).

[L.] From tartaric and butyric acids
[Vol. II] through pyroracemic acid (see
under benzyl alcohol [54; N]), the
potassium salt of which mixed with
potassium butyrate gives methylpropyl
ketone on electrolysis (Hofer and Ulil,
Ber. 33, 654). Subsequent steps as
above under A.

Note : — The generators of pyroracemic acid
referred to under benzyl alcohol [54] are thus,
with butyric acid, generators of this amyl
alcohol. These are : ethyl alcohol and hydrogen
cyanide [14 ; 172] ; acetic acid or acetoacetic acid
and hydrogen cyanide ; citric acid ; propionic acid ;
lactic acid ; n- or isopropyl alcohol [15 ; 16].

[M.] From dextrose [154], Icevulose

EI55] or mannose [156], and acetic acid
Vol. II] through Isevulic acid (see
under erythritol [50; H; l]), the
potassium salt of which when electro-
lysed in solution with potassium acetate
gives methylpropyl ketone (Hofer and
Uhl, Ber. 33, 656).

Note ; — The following generators of laevulic
acid referred to under erythritol [50] thus
become with acetic acid generators of this amyl
alcohol : isohexoic acid ; malonic acid and glycerol
[48] ; acetic aldehyde [92] ; methylheptenone [111] ;
dimelhylheptenol [35].

The synthetical methylpropyl carbinol is
inactive, but is resolved into the 1-modification
by Penicillium glaucum (LeBel, Comp. Rend. 89,
31a ; Ber. 12, 2163 ; Jahresber. 1879, 492),

22. Isoamyl Alcohol ; Isobutyl Car-
binol; Inactive Amyl Alcohol
of Fermentation ; 2-Methyl-4-
Butanol.

CH3 . CH(CH3) . CH, . CH2 . OH

Natueal Sources.

Occurs as ester of angelic and tiglic
acids in Roman oil of chamomile from
Anthemis nobilis (see under isobutyl
alcohol [18]) ; occurs also in oil of
JLucalyptus globulus (Bouchardat and
Oliviero, Bull. Soc. [3] 9, 429). An
amyl alcohol (? this one) has been found
in American oil of peppermint (Schim-
meFs Ber. April, 1894 ; Ch. Centr.
1896, 2, 977).

Esters of amyl (probably isoamyl)
alcohol occur in the oils of Eucalyptus
macrorrhyncha, E. aggregata, E. patenti-
nervis, &c. (Smith and Baker, Proc.
Roy. Soc, N. S. Wales, July, 1898;
Smith, Ibid. June, 1900; ^Nature,"* 62,
384 ; SchimmeFs Ber. April, 1901 ; Ch.
Centr. 1901,1, 1007).

A secondary product of alcoholic fer-
mentation, this alcohol being the chief
constituent of various fusel oils (Scheele,
CrelFs Ann. 1785, 1, 61 ; Pelletan,
Ann. Chim. 30, 221 ; Berz. Jahresber.
6, 264 ; Dumas, Ann. Chim. 56, 314 ;
Ann. 13, 80 ; Cahours, Ann. Chim. 70,
81; 75, 193; Ann. 37, 164; Dumas
and Stas, Ann. Chim. 73, 128 ; Balard,
Ibid. [3] 12, 294 ; Ann. 52, 3 n ; Pas-
teur, Comp. Rend. 41, 296 ; Ann. 96,

80

ALCOHOLS

[22-23 A.

2^^ ; Erlenmeyer and Hell, Ann. 160,
'2'75i Ley, Ber. 6, 1363; LeBel,
Bull. Soc. [3] 25, 545 ; Just, Ann.
220, 148 ; Udranszky, Zeit. physiol.
Ch. 13, 251 : for method of separa-
tion of amyl alcohols of fusel oil see
Marekwald, Ber. 34, 479; 485; 35,

1595)-

Its production during fermentation
has been attributed to bacteria asso-
ciated with the yeast ; this alcohol is
not obtained with pure cultures of ellip-
tical yeast (Gentil, Mon. Sci. [4] 11,
II, 568; Ch. Centr. 1897, 2, 622).
SaccJiaromyces anomalus of Hansen pro-
duces amyl acetate during fermentation
(Barker, Ann. Bot. 1900, 215).

An ester (amyl or isoamyl) of valeric
acid is among the products of decom-
position of albumin (peptone) by Bacil-
lus p-cepolletis from the intestine (Maas-
sen, Ch. Centr. 1899, 2, 1059). An
amyl (? isoamyl) alcohol occurs as ester
in rancid fat, probably as a bacterial
product (Nagel, Am. Ch. Journ. 23,
173). An amyl (? isoamyl) alcohol is
among the products of hydrolysis and
fermentation of starch by the Bacillus
amylozymicus of Perdrix (Ann. Inst.
Past. 5, 287).

A ' fusel oil ' (alcohols not identified)
is said to occur in milk from cows fed
with ^ slump ^ (Teichert, Bied. Centr.
31, 210; Journ. Ch. Soc. 82, II, Abst.
348).

Synthetical Processes.

[A.] From isovaleric aldehyde (2-
methyl-4-butanal) [95] by reduction
with sodium amalgam (Friedel, Ann.
124, 326 ; Balbiano, Ber. 9, 1437 and
T692 ; Gazz. 6, 229 ; Erlenmeyer, Ann.
Suppl. 5, 337 ; Wurtz, Ann. 134, 201).
Also from isovaleric aldehyde (with
other products) by heating with lime
(Fittig, Ann. 117, 68).

[B.] From isovaleric acid [Vol. II]
by convei'sion into the chloride and
reduction of the latter with sodium in
moist ethereal solution (W. H. Perkin,
junr., and Sudborough, Proc. Ch. Soc.
10, 216).

23. ITormal Hexyl Alcohol;
1-Hexauol.

CH3.[CH2]4.CH2.0H

Natueal Sources.

As ester of acetic acid in oil from
Heracleum sphondylium (Moslinger, Ber.
9, 998 ; Ann. 185, 26), and as ester
of butyric acid in oil of Heracleum
giganteum (Franchimont and Zincke,
Ber. 4, 822 ; Ann. 163, 193). Hexyl
alcohol (? normal) exists as ester in the
ethereal oil from the root of Aspidium
jilix mas (Ehrenberg, Arch. Pharm.
231, 345). A caproyl (? n-hexyl) al-
cohol occurs as ester in rancid fat,
probably a bacterial product (Nagel,
Am. Ch. Journ. 23, 173). It is not
certain that the alcohol from any of
these sources is the normal alcohol.
A hexyl alcohol occurs in fusel oil from
brandy (Faget, Ann. 88, 325 ; Ordon-
neau, Comp. Rend. 102, 217).

Synthetical Processes.

[A.] From normal propyl alcohol [15]
through n-hexane by the action of
sodium on n-propyl iodide (Schorlem-
mer, Phil. Trans. 162, 118; Ann. 161,
277; Briihl, Ann. 200, 183; Stoh-
mann, Journ. pr. Ch. [2] 43, 7 '> ^i"
chael, Ber. 34, 4036), n-hexyl chloride
which is formed (with secondary hexyl
chloride) by chlorination (Cahours,
Comp. Rend. 10, 1241 ; Jahresber.
1863, 525), and then through the ace-
tate and hydrolysis (Cahours and
Pelouze, Comp. Rend. 54, 1245 ; Schor-
lemmer, Ann. 161, 272).

Normal hexane is capable of being
directly nitrated, and the mononitro-
derivative on reduction gives 7i-hexyl~
amine [Vol. II] (Worstall, Am.Ch. Journ.
20, 202; 21,210; 218), which can be
converted into the alcohol as under Gr.

Note : — Certain aromatic compounds such as
henzme [6] ; styrene [7] ; phenol [60] ; benzoic acid
[Vol. II] ; alizarin [1451, &c., are said to give
hexane among the products of reduction by
strong aqueous hydriodic acid at a high tem-
perature (Berthelot, as under methane [1 ; I] :
see also v. Baeyer, Ann. 155, 266 ; Wredin,

23 AG.]

NORMAL HEXYL ALCOHOL

81

Ann. 187, X53 ; Kishner, Journ. Russ. Soc. 23,
30 ; 24, 451 ; Ann. 278, 88). The identity of
this hexane has not been fully established (see
under active hexyl alcohol [25 ; B ; C, &c.]).

[B.] From mannitol [5l] through,
the secondary hexyl iodide (CH3[CH2]3 .
CHI . CH3 ; 2-iodohexane) by heating
with hydriodic acid solution (Wanklyn
and Erlenmeyer, Zeit. 1861^ 606 ; 1862^
641 ; Ann. 135, 130 ; Domac, Monats.
2,310; Hecht, Ann. 165_, 146; 209,
311; Schorlemmer, Phil. Trans. 171,
45 a), n-hexane by reduction with zinc
and hydrochloric acid (LeBel and Was-
sermann, Comp. Rend. 100, 15H9;
Jahresber. 1885, 121 1 : also Schor-
lemmer, Phil. Trans. 162, 118; Erlen-
meyer and Wanklyn, Journ. Ch. Soc,
16, 237; Ann. 135, 136), and then as
under A.

The secondary hexyl iodide is also
converted into hexane by heating* to
80-90° with aluminium chloride (Lo-
thar Meyer, Ber. 27, 3766). According
to Combes and LeBel (Bull. Soc. [3]
7, 551) the hexyl iodide obtained from
mannitol is 3-iodohexane.

Mannitol gives hexane by heating
with strong aqueous hydriodic acid to
a8o° (Berthelot, as above under A).

[C] From glycerol [48] through
allyl iodide (see under isobutyl alcohol
[I8 ; D]), diallyl (see under normal
butyl alcohol [17 ; DJ), diallyldihydrio-
dide (2 : 5-diiodohexane) by combination
with hydrogen iodide (Wurtz, Ann.
Chim. [4] 3, 129; Sorokin, Journ. pr.
Ch. [2] 23, 18), hexylene by the action
of sodium on the diiodohexane (Wurtz,
loc. cit.), recombination with hydrogen
iodide to form secondary hexyl iodide
(Wurtz, Ann. 132, 306), and then
through n-hexane as under B and A.

Also through diallyl by combining
with sulphuric acid and distilling with
water and heating the hexylene oxide
thus formed with hydriodic acid so as to
form secondary hexyl iodide (Jekyll,
Ch. News, 22, 221).

[D.] From glutaric acid [Vol. II]
through suberic acid by the electrolysis
of potassium ethyl glutarate (Crum
Brown and Walker, Ann. 261, 120),
and hydrolysis, and then distillation of
the suberic acid with baryta (Riche,

Ann. Chim. [3] 59, 432 ; Dale, Journ.
Ch. Soc. 17, 258; Ann. 132, 243).
Hexane is among the products (see
under A).

NoTK : — Myristic acid [Vol. II], stearic acid [Vol.
II], and cetyl alcohol [33] give suberic acid
among the products of their oxidation by nitric
acid (Noerdlinger, Ber. 19, 1896 ; Laurent,
Ann. Chim. [a] 66, 157 ; Bromeis, Ann. 35,
89). Azelatc acid [Vol. II] gives ketocyclo-octane
among the products of distillation of the cal-
cium salt (Mayer, Ann. 275, 364 ; Derlon, Ber,
31, i960; Miiller and Tschitschkin, Ann. 307,
375), and this gives suberic acid by oxidation
(Derlon, loc. cit. 1962).

[E.] From adipic acid [Vol. II]
through sebacic acid by electrolysis or
potassium ethyl adipate and hydrolysis
of the ester (Crum Brown and Walker,
Ch. News, 66, 91 ; Ann. 261, 120),
bromsebacic and hydroxysebacic acid
by bromination and decomposition of
the sodium salt by boiling with water,
oxidation of the hydroxy-acid to suberic
acid by nitric acid (Weger, Ber. 27,
1216), and then as under D.

Or sebacic acid is brominated in pre-
sence of phosphorus (Auwers and Bern-
hardi, Ber. 24, 2232), and the aa-di-
bromo-acid converted into the dihy-
droxy-acid by heating with barium
hydroxide solution. The dihydroxy-
acid on oxidation with lead peroxide
gives octanediol, and this on oxidation
with alkaline permanganate yields
suberic acid (v. Baeyer, Ber. 30, 1962).

[F.] From normal hexoic [caproic)
acid [Vol. II] through the aldehyde by
distillation of the calcium salt with
calcium formate (Lieben and Janecek,
Ann. 187, 130) and reduction of the
aldehyde by sodium amalgam (Lieben
and Rossi, Ann. 133, 178; Lieben and
Janecek, Ann. 187, 135)-

[G.] From normal heptoic {cenatithic)
acid [Vol. II] through n-Jiexylamine by
the action of bromine and potash on
the amide (Hofmann, Ber. 15, 771 ;
Frentzel, Ber. 16, 744) and distillation
of the nitrite with water (Freutzel, loc.
cit.).

n-Hexylamine can also be obtained
from n-heptoic acid and acetic acid
through methyl-n-hexyl ketone (Stade-
ler, Journ. pr. Ch. 72, 246 j Jahresber.
1857, 359), the ketoxime by the actioa

82

ALCOHOLS

[23 G-24 B.

of hydroxylamine, the action of phos-
phorus pentachloride on the ethereal
solution followed by that of water,
and the action of potash on the n-
hexylacetamide thus formed (Hantzsch,
Ber. 24, 4021).

Also from heptoyl chloride through
methylhexyl ketone by the action of
zi7ic methyl (Behal, Bull. Soc. [3] 6,
13a) and then as above.

Or from heptoic acid through the
a-bromo-acid by bromination (Cahours,
Ann. Suppl. 2, 83 ; Hell and Schiile,
Ber. 18, 625), nitrohexane by the inter-
action of sodium nitrite and the sodium
salt (Auger, Bull. Soc. [3] 23, 333),
and then through hexylamine as above.

[H.] From normal butyl alcohol [17]
through n-octane by the action of
sodium on the iodide (Schorlemmer,
Ann. 161, 380). On chlorination n-
octane yields (among other products)
secondary octyl chloride (2-chloroetane),
which is convertible into methylhexyl
carbinol (2-octanol) by the usual method
(Schorlemmer, Ann. 152, 152; Pelouze
and Cahours, Jahresber. 1863, 528).
The secondary alcohol gives methylhexyl
ketone on oxidation (Behal, loc. cit.),
and this can be converted into n-hexyl-
amine, &c., as under G-.

Note : — Among other generators of n-octane
are : sebacic acid (see above under E) by dis-
tillation with baryta (Riche, Ann. 117, 265) ;
ethyl alcohol [14] through the product of the action
of zinc ethyl on titanium chloride and decom-
position with water (Paternd and Peratoner,
Ber. 22, 467).

[I.] From aldehyde [92] through
a-methylpyridine (a-picoline) by the
action of aldehyde on aldehyde ammonia
(Diirkopf and Schlaugk, Ber. 21, 297),
a-pipecoline by reduction (Ladenburg
and Roth, Ber. 18, 47 ; Ann. 247, 62 j
Comp. Rend. 103, 747 ; Bunzel, Ber.
22, 1053). The latter base can be con-
verted into the methiodide and the
ammonium hydroxide base in the usual
way, the latter on heating to 140°
giving ' pentallylcarbindimethylamine,'
CH2 : CH(CH2), . N(CH3)2, which can
again be converted into its methio-
dide and ammonium hydroxide base;
the latter on heating to 160° gives
(among other products) diallyl (Merling,
Ann. 264, 315 : see also Ladenburg,

Mugdan, and Brzostovicz, Ann. 279,
344, &c.), which can be treated as
under C.

[J.] From pyridine [Vol. II] through
a-picoline by heating the methiodide
to 300° in a sealed tube (Ladenburg and
Lange, Ann. 247, 7), and then through
pipecoline, &c., as under J.

[K.] Normal butyric acid [Vol. II]
gives n-hexane among the products of
electrolysis of the potassium salt (Peter-
sen, Ch. Centr. 1897, 2^ 519)^ and this
can be converted into n-hexyl alcohol
as under A.

[L.] From acetone [10 6] through
pinacone (see under tertiary butyl alco-
hol [19 ; D]). The latter gives hexane
on heating with strong hydriodic acid
at 270° (Bouchardat, Zeit. [2] 7, 699).

Note : — The generators of pinacone referred
to under tertiary butyl alcohol [19 ; E ; F ; &c.]
thus become generators of hexane. These are :
isobutyric acid and methyl alcohol ; amyl and
methyl alcohols ; lactic acid and methyl alcohol ;
acetic acid and methyl alcohol ; ethyl and methyl
alcohols ; propionic acid and methyl alcohol ; diacetyl
and methyl alcohol.

24. Isohexyl Alcohol ;
2-Methyl-5-Fentauol.

CH3 . CH(CH3) . CH2 . CH2 . CH2 . OH

Natural Source.

A hexyl alcohol is said to have been
found in fusel oil from brandy (Faget,
Ann. 88, 325 ; Ordonneau, Comp.
Rend. 102, 217). The constitution of
this alcohol has not been determined,
but it is probably as above.

Synthetical Processes.

[A.] From isoamyl alcohol [22] and
trioxymethylene \_ formic aldehyde : 9l]
by the interaction of isoamyl magnesium
bromide and trioxymethylene in ethereal
solution (Grignard and Tissier, Comp.
Rend. 134, 107).

[B.] From isobutylacetic {^\-methyl-
pentanoic) acid [Vol. II] through the
aldehyde (4-methylpentanal) by dis-
tilling the calcium salt with calcium
formate (Rossi, Ann. 133, 178) and
reduction with sodium amalgam {Ibid.
180).

25-27 A.]

ACTIVE HEXYL ALCOHOL

83

25. Active Hezyl Alcohol ;

Methylethylpropyl Alcohol ;

3-Methyl-5-Fentauol.

CH3 . CH, . CH(CH3) . CH2 . CH2 . OH

Natueal Source.

As ester of angelic and tig-lie acids
in Roman oil of chamomile from
Anthemis nohilis (Kobig^ Ann. 195, 79 ;
81 ; 9a : see also Van Romburgh, Rec.
Tr. Ch. 5, 319; Q, 150).

Synthetical Peocesses.

[A.] From isopropyl alcohol [16]
through diisopropyl (2 : 3-dimethyl-
butane) by the action of sodium (Schor-
lemmer, Ann. 144, 1H4), chlorination
(Silva, Bull. Soc. [%] Q, ^6 ; 7, 953),
and conversion of the chlorhexane into
the alcohol by the usual methods {Ibid,

Q> 147)-

[B.] From acetone [IO6] through
pinacone (2 : 3-dimethyl-2 : 3-butane-
diol) by the action of sodium (see under
tertiary butyl alcohol [l9 ; D]), diiso-
propyl by heating with hydriodic acid
(Bouchardat, Comp. Rend. 74, 809),
and then as under A.

Note : — Generators of pinacone are summa-
rised under normal hexyl alcohol (23 ; L).

[C] Normal hepioic (oenanthic) acid
[Vol. II] when its barium salt is
heated to redness gives a hexane which
is said to be diisopropyl (Riche, Ann.
Chim. [3] 59, 432).

[D.] From glycerol [48] through
diallyl (see under normal butyl alcohol
[17; D]) and action of hydriodic acid
in excess on the latter at a high tempera-
ture (Berthelot, Bull. Soc. [2] 9, 268).
The hexane thus obtained is said to be
diisopropyl.

[E.] From mannitol [5l] by heating
with excess of hydriodic acid (Bou-
chardat, Ann. Chim. [5], 6, 1 24 ; Le
Bel and Wassermann, Jahresber. 1885,
1 211). This hexane is also said to be
diisopropyl.

Note : — The identity of Silva's alcohol with
the natural product requires confirmation ; it
is difficult to see how an alcohol having the
constitution 3-methyl-5-pentanol could be
derived from diisopropyl by chlorination and
hydroxylation.

26. Normal Heptyl Alcohol ;
l-Heptanol.

CH3.[CH2]5.CH,.OH

Natueal Souecb.

The heptyl alcohol stated to have
been found in fusel oil from brandy
(see under isoheptyl alcohol [27]) may
be the normal alcohol, as it is said to
give n-heptoic (oenanthic) acid on
oxidation.

Synthetical Peocesses.

[A.] From n-heptane [2] through
i-chlorheptane by chlorination and the
usual method (Schorlemmer, Ann. 127,
315; 161, 278). n-Heptane gives
i-nitroheptane on nitration (Worstall,
Am. Ch. Journ. 20, 2io; 21, 223).
The heptylamine obtained from this by
reduction might give n-heptyl alcohol
by the usual (nitrous acid) method.

[B.] From osnanthol [97] by reduc-
tion (see under n-heptane [2 ; D]).

27. Isoheptyl Alcohol ;
Isohexyl Carliinol ;
2-Methyl-6-Hexauol.

CH3.CH(CH3). [CH2J3.CH2.OH

Natueal Souece.

Heptyl alcohol is said to have been
obtained from fusel oil of brandy
(Faget, Bull. Soc. 1862, 59 ; Ann.
124, '^^^ ; Ordonneau, Comp. Rend.
102, 217). The constitution of this
fermentation heptyl alcohol has not
yet been satisfactorily established, and'
it is only placed here provisionally (see
also above under n-heptyl alcohol [26]).

Synthetical Peocesses.

[A.] From eikyl [l4] and isoamyl
[22] alcohols through isoheptane (5-
methylhexane) by acting with sodium
on the iodides or bromides (Wurtz,
Ann. Chim. [3] 44, 275 ; Grimshavv,
Journ. Ch. Soc. 26, 309; Ann. 166,

g2

84

ALCOHOLS

[27 A-29 B.

163), isobeptyl chloride by ehlorina-
tion, conversion into the alcohol by the
usual method, and separation of the
primary from the secondary alcohol
(Grrimshaw, loc. cit. 313).

[B.] From isobutyl alcohol [isl, acetic
acid [Vol. II], and ethyl alcohol [14] by
combming isobutyl iodide with soclio-
acetoaceti'i ester, decomposing the iso-
butylacetoacetic ester with potash,
reducing the ketone (2-methyl-6-hex-
anone) to the secondary alcohol, con-
verting the latter into the iodide, and
reducing to isoheptane with zinc and
hydrochloric acid (Purdie, Trans. Ch.
Soc. 39, 464 : see also Rohn, Ann.
190, 305). The isoheptane can then
be treated as under A.

Note : — A heptane (possibly identical with
the above) is said to be obtained from certain
cyclic compounds by heating to a high tem-
perature with strong aqueous hydriodic acid
(Berthelot, Comp. Rend. 68, 606 ; Bull. Soc.
[2] 9, 455). The compounds are : tolmne [54]
and the toluidines ; phthalic acid (see under benzyl
alcohol [54 ; B]) and terephthalic acid. The latter
can be obtained by the oxidation of cymene [6]
and cumic aldehyde [116] (Hofmann, Ann. 97,
197; De la Rue and Miiller, Ann. 121, 87;
Schwanert, Ann. 132, 257 ; Homeyer, Arch.
Pharm. [3] 5, 326).

28. Normal Primary Octyl Alcohol ;
1-Octanol.

CH3.[CH:,]e.CH2.0H

Natueal Sources.

As ester of acetic acid in oil of
Heracleum giganteum (Franchimont and
Zincke, Ann. 163, 193) ; as ester of
acetic, hexoic, decoic, and lauric acids
in oil of Heracleum sphonclyUum (Zincke,
Ann. 152, i ; IVIoslinger, Ber. 9, 998 ;
Ann. 185, a6). As ester of n-butyric
acid in fruit of Pastinaca saliva, com-
mon parsnip (Renesse, Ann. 166, 84).
An octyl alcohol occurs as ester in the
ethereal oil from the root of Aspirlium
filix mas (Ehrenberg, Arch. Pharm.

231, 345)-

A capryl (? n-octyl) alcohol occurs in
rancid fat, probably a bacterial product
(Nagel, Am. Ch. Journ. 23, 173).

Synthetical Processes.

[A.] Normal octane (see under n-hexyl
alcohol [23 ; H]) by chlorination and
conversion into the primary and secon-
dary alcohols by the usual methods
gives a product which may contain an
alcohol identical with the natural pro-
duct, but this requires confirmation
(Schorlemmer, Ann. 152, 155).

[B.] Sebacic acid [Vol. II] gives
octane on distillation with baryta
(Riche, Ann. 117, 26$).

Notes: — Certain aromatic compounds (which
can all be synthesised), such as xylene [62 ; A],
ethylbenzene [64 ; A], styrene [7], naphthalene [12],
phthalic acid [54 ; R], &c., according to Berthe-
lot give octane among other products when
heated with strong aqueous hydriodic acid (for
references see under isoheptyl alcohol [27 ; B]).
The constitution of the octanes thus obtained
is unknown.

A secondary octyl alcohol (methylhexyl
carbinol= 2-octanol) has been obtained by dis-
tilling the soap from the oil of Curcas purgans
(Silva, Zeit. [2], 5, 185). The alcohol has been
synthesised (seeundern-hexylalcohol [23 ; H]),
but it is doubtful whether it is at present to be
regarded as a biochemical product.

29. Nonyl Alcohol ; Ennyl Alcohol ;
Nonauol.

CgHjg . OH

Natural Source.

Anonyl alcohol (39«4per cent.)has been
found in the oil of sweet orange (Schim-
mel's Ber. Oct. 1900; Ch. Centr. 1900,
2, 969 ; Stephan, Journ. pr. Ch. [2] 62,

5^3)-

Synthetical Processes.

The constitution of the natural pro-
duct is not known with certainty ; it is
probably the normal alcohol. The fol-
lowing nonyl alcohols are synthetical
products : —

[A.] Pelargonic and formic [Vol. II]
acids give the aldehyde (nonanal) on
distillation of the barium salts. The
aldehyde is reduced to normal nonyl
alcohol by zinc dust and acetic acid
(Krafft, Ber. 19, 2221).

[B.] From isovaleric acid [Vol. II] and
isoamyl alcohol [22]. Isoamyl isova-
lerate on treatment with sodium gives

28 B-31 A]

NONYL ALCOHOL

85

a nonyl alcohol (Louren90 and Aguiar,
Zeit. [2] 6, 404).

[C] From ei/ii/l alcohol [l4] and
oenanthol [97] by the action of zinc
ethyl on the aldehyde and decomposition
of the product by water. The alcohol
is ethylhexyl carbinol = 3 - nonanol
(Wagner, Journ. Russ. Soc. 16, 306;
Bull. Soc. [2] 42, 330).

Or from ethyl alcohol and oenanthol
by converting the latter into n-heptyl
alcohol [26]. A mixture of n-heptyl
and ethyl alcohols gives (among other
products) n-nonyl alcohol when heated
with sodium to 330° (Guerbet, Comp.
■Rend. 135, 17a; Bull. Soc. [3] 27,
1036).

[D.] From ethyl alcohol [14] and
hulyric acid [Vol. III. The latter on
distillation of the calcium salt (Chancel,
Ann. 62, 295; Kurtz, Ann. 161, 305;
Schmidt, Ber. 5, 597), or by the action
of ferric chloride on butyryl chloride
and decomposition of the product with
water (Hamonet, Bull. Soc. [2] 50,
358), gives dipropyl ketone = butyrone
= 4-heptanone. The latter on treat-
ment with zinc and ethyl iodide yields
ethyldipropyl carbinol = 4-ethyl-4-hep-
tanol (Tschebotareff and Saytzeff, Journ.
pr. Ch. [2] 83, 198).

Note : — Dipropyl ketone can also be prepared
from r\-ipropyl alcohol [15] and butyric acid by the
interaction of zinc propyl and butyryl chloride
(Schtscherbakoff, Journ. Russ. Soc. 18, 346). Or
from butyric acid by heating butyric anhydride
with sodium butyrate (Perkin, Trans. Ch. Soc.
49, 325) or (among other products) by the action
of sodium on ethyl butyrate (Briiggemann,
Ann. 246, 140). This ketone is also among
the products of the action of zinc on a mixtiire
of butyryl chloride and ethyl ether (Freund,
Ann. 118, 33).

Secondary Nonyl Alcohol.

A secondary nonyl alcohol (methyl-n-
heptyl carbinol) occurs partly free and
partly as ester of acetic acid in Algerian
oil of rue (v. Soden and Henle, Pharm.
Zeit. 46, 1026; Ch. Centr. 1902, 1,
1^6', Ch. Drug., 60, 304; Power
and Lees, Trans. Ch. Soc. 81, 1592).
This alcohol has been obtained by re-
ducing the corresponding ketone [IO8]
(Mannich, Ber. 35, 2144; Houben,
Ibid. 3589).

30. Secondary Eendecatyl or

Heudecyl Alcohol ; Methyl-n-nonyl

Carbinol.

CHsX /H

C„H,/ ^GH

Natural Source.

Occurs partly free and partly as ester
of acetic acid in Algerian oil of rue (v.
Soden and Henle, Pharm. Zeit. 46,
1026; Ch. Centr. 1902, 1, 256;
Ch. Drug., 60, 304; Power and Lees,
Trans. Ch. Soc. 81, 1593).

Synthetical Process.

[A.] From methylnonyl ketone [109]
by reduction with sodium amalgam
(Giesecke, Zeit. [2] 6, 428 ; Mannich,
Ber. 35, 2144; Houben, Ibid, 3590).

31. Normal Primary Dodecyl
Alcohol; l-Sodecanol.

CH3.[CH,],o.CH2.0H

Natural Sources.

Esters of this alcohol (probably stea-
rate and palmitate of the normal alcohol)
exist in Cascara sagrada (Dohme and
Engelhardt, Journ. Am. Ch. Soc. 20,
539). Occurs also as ester (of oleic
and doeglic acids) in sperm oil and in
oil from the bottle-nose whale, and to a
small extent in spermaceti [33] (Heintz,
Ann. 84, 306; 92, 299; Allen, in
Thorpe's ' Diet, of Applied Chem.' Ill,
20 j Hammarsten's 'Lehrb. d. physiol.
Chem.' 1895, p. 76).

Synthetical Process.

[A.] From lauric acid [Vol. II] through
the aldehyde by distilling the barium salt
with barium formate (Krafft, Ber. 13,
1 4 14), reduction with zinc dust and
acetic acid, and hydrolysis of the acetate
thus formed {Ibid. 16, 1718).

Note : — The identity of the natural and syn-
thetical products requires confirmation.

86

ALCOHOLS

[32-35 B.

32. normal Primary Tetradecyl
Alcohol ; 1-Tetradecanol.

CH3.[CH,]i,.CH2.0H

Natural Source.

Occurs in small quantity as ester in
spermaceti [33] (Heintz^ Ann. 84^ 306 ;
92^ 299 ; Hammarsten's ' Lehrb. d.
physiol. Chem.'' 1895, p. 76).

Synthetical Process.

[A.] From wyrisiic acid [Vol. II]
through the aldehyde by distilling the
barium salt with harium formate (Krafft,
Ber. 13; 14 15), and reduction of the alde-
hyde with sodium in alcoholic solution
{Ibid. 16, 1720; 23, 2360).

Note : — The identity of the natural and syn-
thetical products requires confirmation.

33. Cetyl Alcohol ; JEthal ; 1-Heza-
decanol.

CH3.[CHJi4.CH2.0H

Natural Sources.

As ester of palmitic acid in spermaceti
from the cranial cavity and blubber of
the sperm vf\ia[e{Phf/setermacrocephahs),
from Delp/iinus tursio and D. edentuhis.
Occurs also in oil from the dolphin
(Delp/iinns fflobiceps)aindin blubber of the
bottle-nose whale [Ili/peroddon rostratus
and H. bid ens). Cetyl acetate, laurate,
myristate, and stearate are present to a
small extent in some kinds of sperma-
ceti (Chevreul, * Recherches sur les
Corps Gras/ p. 171; Ann. Chim. 7,
157 ; Dumas and Pehgot, Ibid. [2] 62,
4; Dumas and Stas, Ibid. 73, 124;
Smith, Ibid. [3] 6, 40 ; Ann. 42, 247 ;
Berthelot and P^an, Ann. Chim. [3]
58, 413; Heintz, Ann. 84, 306; 92,
299; Pogg. Ann. 87, 2i ; 267; 92,
429; 588; Krafft, Ber. 17, 1627).
The alcohol is said to occur (as ester) in
the caudal glands of certain birds (ducks
and geese) (De Jonge, Zeit. physiol. Ch.
3, 225) ; also in the fat of ovarian
cysts (Ludwig, Zeit. physiol. Ch. 23,
38 ; V. Zeynek, Ibid. 48).

Synthetical Processes.

[A.] From adijnc acid [Vol. II]
through sebacic acid (see under n-
hexyl alcohol [23 ; E]) by distilling the
barium salt of the latter (Schorlemmer,
Proc. Roy. Soc. 19, 22; Ber. 3, 616).

[B.] From palmitic acid [Vol. II]
through the aldehyde by distilling the
barium salt with barium formate (Krafft,
Ber. 13, 1416), reduction of the alde-
hyde with zinc dust and acetic acid, and
hydrolysis of the acetate thus formed
{Ibid. 16, 172IJ 17, 1627).

34. Octadecyl Alcohol ;
1-Octadecanol,

CH3.[CHJieCH2.0H

Natural Source.

An ester of this alcohol occurs in
spermaceti (Heintz, Ann. 84, 306 ; 92,
299; Krafft, Ber. 17, 1628).

Synthetical Process.

[A.] From stearic and formic acids
[Vol. II] through stearic aldehyde
(Krafft, Ber. 13, 141 7) and reduction
of the aldehyde in the usual way {Ibid.
16, 1722; 17, 1627).

35. 2-6-Diinethyl-2>Heptenol-6.

(CH3),:C:CH.CH2.CH2.

C(CH3)(OH).CH3

Natural Source.

Said to occur in small quantity in oil
of linaloe (Barbier, Comp. Rend. 126,
1423)-

Synthetical Processes.

[A.] From geraniol [36] by the action
of strong alcoholic potash at 150°
(Barbier, loc. cit.).

Note : — According to Tiemann (Ber. 31, 2991)
this product is methylheptenol corresponding
to methylheptenone.

[B.] From methylheptenone [ill] and
methyl alcohol [13] by the action of

35 B-3e A.]

2-6-DIMETHYL-2-HEPTENOL-6

87

magnesium methiodide on the ketone
(in ethereal solution) and decomposition
of the magnesium compound by acid
(Barbier, Comp. Rend. 128j iio; Sand
and Singer, Ber. 35, 3183).

Note : — The dimethylheptenol obtained by
th is method is (CH3), : C : CH . [CHjlj . CCCHa), .
OH.

36. Gerauiol ; Lemonol ;
2 : 6-Dimetliyl-2 : 6-Octadienol-8.

(CH3)2:C:CH.CH2.CH2.

C(CH3):CH.CH2.0H

Natural Sources.

In East Indian geranium or palma-
rosa oil from Andropogon schoenanthus
(Jaeobsen, Ann. 157, ^132); in oil of
citronella from Andropogo^i nardus, Pun-
jaub, Ceylon, Singapore, &e. (Sehim-
mel's Ber. Oct. 1893) ; in African,
Spanish, French, and Reunion geranium
oils from Pelargonium odoratissimnm,
P. capitatum, P. radula, &c. (Gintl,
Jahresber, 1879, 942 ; Bertram and
Gildemeister, Journ. pr. Ch. [2] 49,
191 ; Tiemann and Schmidt, Ber. 29,
924) ; and in German and Turkish oils
of rose from Rosa damascena, R. alba,
&c. (Bertram and Gildemeister, lac.
cit. : see also Eckart, Ber. 24, 4205 ;
Arch. Pharm. 229, 355; Barbier,
Comp. Rend. 117, 177 ; Bull. Soc. [3]
9, 999).

Geraniol occurs in ylang-ylang oil
from Cananga odorata (Reychler, Bull.
Soc. [3] 11, 407; 576; 1045; 13,
140) j in French oil of lavender from
Lavandula sp. (Schimmel's Ber. April,
1898) ; in oil of neroli from the flowers
of the bitter orange. Citrus higaradia,
and in the ' orange-flower water ' (Tie-
mann and Semmler, Ber. 26, 271 1 ;
Hesse and Zeitschel, Journ. pr. Ch. [2]
64, 245) ; in petit-grain oil from the
leaves, shoots, and fruit of the same
plant (Passy, Bull. Soc. [3] 17, 519;
Charabot and Pillet, Ibid. 21, 74) ; in
petit-grain oil from Paraguay (Schim-
mel's Ber. Oct. 1902; Ch. Centr. 1902,
2, 1 208) ; in lemon-grass oil from the
Indian Andropogon citratus (SchimmeFs
Ber. Oct. 1894; also Oct. 1898; Ch.

Centr. 1898, 2, 985: compare Stiehl,
Journ. pr. Ch. [2] 58, 51 ; Tiemann,
Ber. 32, 835; Labbe, Bull. Soc. [3]
21, 77); and in oil of linaloe from the
wood of the Mexican Bnrsera delpe-
chiana or B. aloexylmi (SchimmeVs Ber.
April, 1892; Oct. 1894; Oct. 1900).

Occurs also in oil of sassafras leaves
(Power and Kleber, Pharm. Rev. 14,
103; Ch. Centr. 1897, 2, 42); in oil
of balm mint from Melissa officinalis
(Flatau and Labbe, Comp. Rend. 126,
1725; Bull. Soc. [3] 19, 636); in
lemon oil from Citrus limomm, Messina
and Palermo (Umney and Swinton,
Pharm. Journ. 61, 196; 370), and in
the oil from the leaves of Verbena tri-
pki/lla, Grasse (Theulier, Rev. gen. de
Chim. 6, 324; Ch. Centr. 1902, 2,
1208).

The oil from Barwinia fascicularis of
Port Jackson contains geraniol and
60-65 per cent, of geranyl acetate
(Baker and Smith, Journ. and Proc.Roy.
Soc. of N. S. Wales, 33, 163; Journ.
Soc. Ch. Ind. 19, 848). Certain citron-
ella oils (Javan and Cingalese ' Lana-
Batu ') contain 32-38 per cent, geraniol
(Schimmel's Ber. Oct. 1899; Journ.
Soc. Ch. Ind. 19, j^S).

The oil from the leaves and twigs of
Bucalyptus macarthiri contains 60 per
cent, of geranyl acetate (Smith, Ch.
News, 83, 5). Geraniol is probably
contained in the oil of Bucalyptus
patentinervis (SchimmeFs Ber. April,
1901 ; Ch. Centr. 1901, 1, 1007). The
oil from the rhizome of Asartim cana-
defise contains geraniol (Power, Pharm.
Rund. 6, loi j Power and Lees, Proc.
Ch. Soc. 17, 210 ; Trans. 81, 66).

Note : — ^The geraniol is contained in the above
oils sometimes free, sometimes combined as an
ester, and in some cases both free and com-
bined. The acid most frequently combined
with geranyl is acetic, but other acids, such as
tiglic, valeric, &c., are sometimes present.
Suggestions concerning the origin of geraniol
andalliedalcohols in plants have beenadvanced
by Charabot (Ann. Chim. [7] 21, 207, &c.).

Synthetical Processes.

[A.] From citral [104] by reduction
in alcoholic solution with sodium
amalgam and acetic acid (Tiemann,
Ber. 31, 828).

88

ALCOHOLS

[36 B-37.

[B.] lAnalobl [37] gives geraniol on
heating with acetic anhydride or with
sulphuric and acetic acids and hydro-
lysis of the acetate (Barbier^ Comp.
Rend. 116, I200j 117, ill; Bouchar-
dat, Comp. Rend. 116, 1253; Bertram
and Gildemeister, Journ. pr. Ch. [2]
49, 192 ; Tiemann and Semmler, Ber.
26, 2714; Bertram, Germ. Pat. 807 ii
of 1893, Ber. 28, Ref. 58a).

NoTK : — The product ' licarhodol ' obtained
by Barbier (Comp. Rend. 116, 1200) by heating
l-linalo8l with acetic anhydride and hydro-
lysis is said to be a mixture of geraniol and
d-terpineol (Stephan, JouVn. pr. Ch. [2], 58,
109 : see also Barbier and L6ser, Bull. Soc. [3]
17, 590)-

37. Liualo51; Licareol.

(CH,)2:C:CH.CH2.CH2.

C(CH3)(0H) . CH : CH2
or
CH„ : C(CH3) . CH2 . CH2 . CH2 .

C(CH3)(OH).CH:CH2

Note : — For references to constitution see
paper by Harries and Schauwecker, Ber. 34,
2981 ; also Barbier, Bull. Soc. [3] 25, 687 ; 828.
According to Barbier the first of these formulae
represents myrcenol.

Natural Sources.

1-Linalool is contained in oil of linaloe
from Guiana, probably from the wood
of Ocotea caudata (Morin, Comp. Rend.

02, 998 J 94, 733 ; Ann.^ Chim. [5]
25, 427 ; Theulier, Rev. Gen. de Chim.

3, a62; Bull. Soc. [3] 25, 468;
SchimmeFs Ber. April, 1901), and in
Mexican oil of linaloe (see above under
geraniol [36] : Semmler, Ber. 24, 207 ;
Barbier, Comp. Rend. 114, 674; 116,
883; 121, 168).

Oil of neroli (see under geraniol)
contains 1-linalool (Tiemann and Semm-
ler, Ber. 26, 271 1 ; Hesse and Zeitschel,
Journ. pr. Ch. [2] 64, 245) ; so also
does oil of bergamot from Citrus ber-
gamia (Semmler and Tiemann, Ber. 25,
1 1 82; Bertram and Walbaum, Journ.
pr. Ch. [2] 45, 602; Charabot, Comp.
Rend. 129, 728 ; Fabris, Abst. in
Journ. Soc. Ch. Ind. 19, 772), man-
darin oil from Citrus madurensis (Schim-
meFs Ber. Oct. 1901), oil of limette

from the fruit of the Italian Citrus
limetta (Gildemeister, Arch. Pharm.
233, 174), and oil of lemon from Citrus
livionum from Palermo (Umney and
Swinton, Pharm. Journ. 61, 196 ; 370).

Oil of petit-grain (see under geraniol)
contains d- and 1-linalool (Semmler
and Tiemann, Ber. 25, 11 86 ; Chara-
bot and Piliet, Bull. Soc. [3] 21, 74 :
1-linalool in Paraguay petit-grain oil,
SchimmeFs Ber. Oct. 1902 ; Ch. Centr.
1902, 2, 1208).

l-Linalo6l is contained also in oil of
spike lavender from Lavandula spica
(Bouchardat and Voiry, Comp. Rend.
106, 551; Bouchardat, Ibid. 117, ^"^f',
1094), in French lavender oil (Bertram
and Walbaum, Journ. pr. Ch. [2] 45,
590) ; in ylang-ylang oil (see under
geraniol; Reychler, Bull. Soc. [3] 11,
407 ; 576 ; 1045 ; 13, 140) j in oil of
Origanum smyrnce-vm from Smyrna
(Gildemeister, Arch. Pharm. 231, 182) ;
in oil of balm mint from Melissa
officinalis (see under geraniol) ; in
Russian oil of spearmint from Mentha
viiidis (SchimmeFs Ber. April, 1898;
Ch. Centr. 1898, 1, 991); and in oil
of thyme from Thymus vulgaris (Labb^,
Bull. Soc. [3] 19, 1009).

Also in lemon-grass oil (see under
geraniol : Tiemann, Ber. 32, 835) ; in
oil of jasmine from the flowers of
Jasminum grandijiorum with linalyl
acetate (Hesse and Miiller, Ber. 32,
574; 765 ; Hesse, Ibid. 2619 : see also
Erdmann, Ber. 34, 2281, note) ; in
German oil of rose (Walbaum and
Stephan, Ber. 33, 2304) ; (trace) in
citronella oil (see under geraniol :
SchimmeFs Ber. Oct. 1899; Ch. Centr.
1899, 2, 880) ; in oil of sassafras
leaves (Power and Kleber, Pharm. Rev.
14, 403; Ch. Centr. 1897, 2, 42); in
French oil of sweet basil from Ocymum,
basilicum (Dupont and Guerlain, Comp.
Rend. 124, 300 ; Bull. Soc. [3] 19,
151) ; and probably in oil from Eaca-
lyptus patentinervis (see under geraniol),
and in oil from the leaves of Dartvinia
taxifolia (Baker and Smith : see under
geraniol and SchimmeFs Ber. Oct.
1900 j Ch. Centr. 1900, 2, 969).

Linalyl acetate is possibly contained
in the oil from Salvia sclarea (Schim-

37-38 B.]

linaloOl

89

mel's Ber. April, 1889; Oct. 1894).
l-Linalo6l is contained in Ceylon oil
of cinnamon {Ibid. April^ 1902; Wal-
baum and Hiithig-, Journ. pr. Ch. [2]
66^ 47), and in oil of cinnamon leaf
(SchimmeFs Ber. Oct. 1902 ; Ch.
Centr. 1902, 2, 1208). Linalool and
linalyl acetate are present in oil of
Gardenia (Parone, Boll. Ch. Farm. 41,
489 ; Ch. Centr. 1902, 2, 703).

d-Linalool = coriandrol occurs in oil
of coriander from the fruit of Corian-
drum sativum (Kawalier, Ann. 84, 351 ;
Journ. pr. Ch. 58, 226; Grosser, Ber.
14, 2485; Semmler, Ber. 24, 206;
Barbier, Comp. Rend. 116, 1460) ; in
' wartara ' oil from the fruit of Xantho-
xylon alahim and X. acanthopodium
(SchimmeFs Ber. April, 1900; Ch.
Centr. 1900, 1, 908); in oil of sweet
(Portugal) orange from the rind of the
fruit of Citms aurantium (Parry, Ch.
Drug-. 1900, pp. 462 and 722 ; Stephan,
Journ. pr. Ch. [2] 62, 523) ; in the
n^roli oil from the flowers of the same
plant (Theulier, Bull. Soc. [3] 27, 278 :
a French neroli oil examined by Schim-
mel & Co. probably contained 1-lina-
lool ; Ch. Centr. 1902, 2, 1208), in
Chinese neroli oil from Citrus triptera
(Umney and Bennett, Pharm. Journ.
[4] 15, 146), and in oil of Asarum
canadense (Power and Lees, Proc. Ch.
Soc. 17, 210 ; Trans. 81, d'^.

Inactive linalool and linalyl isono-
noate are present in oil of hops (Chap-
man, Proc. Ch. Soc. 19, 72).

Note : — For remarks on general transforma-
tion and miigration of linalool and other terpene
alcoholic compounds in plants, see papers by
Charabot, Bull. Soc. [3] 23, 189 ; Ann. Chim.
[7] 21, 307, &c. ; Charabot and Hebert, Comp.
Rend. 133, 390 ; Bull. Soc. [3] 25, 884 ; 955).
Linalool occurs in the above oils in some cases
in the free state and in other cases combined
as linalyl acetate, &c.

Synthetical Peocess.

[A.] Geraniol [36] by the action of
hydrochloric acid gives geranyl chloride
(Jacobsen, Ann. 157, 236), and this by
the action of alcoholic potash is con-
verted partially into inactive linalool
(Semmler and Tiemann, Ber. 31, 832).
A similar transformation is broug-ht
about by heating- geraniol with water
to 200° (SchimmeFs Ber. April, 1898).

Or sodium geranyl phthalate (from
geranyl chloride and phthalic acid [54 j
B]) gives i-linalo6l on steam distillation
of the neutral solution (Stephan, Journ.
pr. Ch. [2] 60, 244).

Note: — No method for resolving i-linaloOl
into its optical iBomerides has yet been dis-
covered.

38. Citronellol; Bhodluol (?) ;
2 : 6-Duixeth7l-2-Octenol-8.

(CH3)2:C:CH.CH2.CH2.

CH(CH3).CH2.CH2.0H

Natural Sources.

1-Citronellol occurs in Bulgarian and
German oil of rose and d- and 1-citron-
ellol in Spanish, African, and Reunion
oils of geranium from Pelargonium
odoratissimum, &c. (see under geraniol :
Hesse, Journ. pr. Ch. [a] 50, 478 ; 53,
238; Tiemann and Schmidt, Ber. 29,
922 ; Barbier and Bouveault, Comp.
Rend. 122, 737 ; Walbaum and Stephan,
Ber. 33, 2306 ; Schimmel's Ber. May,
1901 ; Journ. Soc. Ch. Ind. 20, p. 744).

Citronellol is also said to be contained
in Indian geranium (palmarosa) oil
(Flatau and Labbe, Comp. Rend. 126,
1725; Bull. Soc. [3] 19, 6'3^'^ : compare
SchimmeFs Ber. Oct. 1898, p. 67).
Javan (but not Ceylon) oil of citronella
contains d-citronellol (SchimmeFs Ber.
April, 1902).

Synthetical Processes.

[A.] From citronellal [l05] by re-
duction with sodium amalgam and
acetic acid (Dodge, Am. Ch. Journ. 11,
463 ; Tiemann and Schmidt, Ber. 29,
906).

Note : — The aldehyde corresponding to the
above formula of citronellol is probably not
identical vy^ith 1-citronellal but with the iso-
meric ' rhodinal ' of Bouveault (Bull. Soc. [3]
23,458 ; 463 : see also under citronellal [105]).
The above synthetical process may therefore
lead to the production of an alcohol isomeric
vrith the natural 1-citronellol (see also Harries
and Schauwecker, Ber. 34, 2981).

[B.] From mentkone [129] through
the oxime, nitrile, and aldehyde = men-
thocitronellal (Wallach, Ann. 277,
154; 278, 316; 296, 129). The latter
should be Bouveault's 'rhodinal,' and

90

ALCOHOLS

[38 B-39 A.

would therefore give citronellol on re-
duction (Harries and Schauwecker^ loc,
cit.).

Note : — According to Bouveault citronellol
and rhodinol are isomerides (see for summary
Bull. Soc. [3] 23, 458 J also under menthone
[129]).

39. Terpineol; Terpilenol; Terpene
Hydrate ; Menthenol ;
A^-8-Hydroxytetrahydrocymene ;
A^-Terpen-8-ol.

CH3

/\

HaC CH

I I
\/

CH
CH3.C(0H).CHs

Note : — For constitutional formula see Wag-
ner, Ber. 27, 1652.

Natural Soueces.

i-Terpineol (and acetate) occurs in
oil o£ cajeput from Melaleuca leucaden-
dron and var. minor (Voiry, Comp.
Rend. 106, 1538; Bull. Soc. [a] 50,
108), and in niauli oil from Melaleuca
viridifolia, New Caledonia (Bertrand,
Bull. Soc. [3] 0, 433 ; Comp. Rend.
116, 1070); in oil of Ceylon cardamom
from Elettaria cardamomum, var. major,
Smith (Weber, Ann. 238, 98) ; and in
oil of Malabar cardamom (d-terpineol)
from E. cardamomum (SchimmeFs Ber.
Oct. 1897; Parry, Pharm. Journ. 9,

Oil of sweet marjoram from Origanum
majorana contains d-terpineol (Biltz,
Ber. 32, 995). Terpineol is contained
in the oil of Lindera sericea, the ' kuro-
moji' oil of Japan (Kwasnik, Arch.
Pharm. 230, 265); in the Japanese
' kesso ' oil from the root of Valeriana
officinalis, var. angndifolia (Bertram and
Gildemeister, Arch. Pharm. 228, 483) ;
and in oil of fleabane from the N.
American Erigeron canadensis (Kremers
and Hunkel, Pharm. Bund. 13, 137).

1-Terpineol is probably present in
lemon-grass oil (Tiemann, Ber. 32, 835).

d-Terpineol is contained in oil of lovage
from the root of Levisticum officinale
(Schimmel's Ber. April, 1897, p. 37,
and Oct. 1897, p. 9, note). The oil
from Calif ornian bay ( lJr)ihellularia cali-
forniea) contains a mixture, 'terpinol,'
of which terpineol is one of the con-
stituents (Stillmann, Ber. 13, 630;
Wallach, Ann. 230, 251). Oil of Gar-
denia contains terpineol (Parone, Boll.
Ch. Farm. 41, 489; Ch. Centr. 1902,

The oil of the rind of the sweet
orange (see under linalool [37] : Stephan,
Journ. pr. Ch. [2] 62, 523 and Schim-
mel's Ber. Oct. 1900) contains 39-4 per
cent, of d-terpineol. Oil of Mexican lina-
loe (see under geraniol [36] : SchimmeFs
Ber. Oct. 1900; Ch. Centr. 19CO, 2, 970)
contains terpineol. So also does man-
darin oil from Citrus madurensis (Schim-
meFs Ber. Oct. 1901 ; Ch. Centr. 1901,
2, 1007). Oil of spike from Lavandula
spica may contain terpineol (Bouchardat,
Comp. Rend. 117, 53; 1094).

1-Terpineol is contained in the oil of
Asarum canadense (Power and Lees,
Proc. Ch. Soc. 17, 210 ; Trans. 81, 6^).
Camphor oil from Lanrus camphora pro-
bably contains terpineol (Schimmel's
Ber. Oct. 1888). d-Terpineol is pre-
sent in oil of lemon (SchimmePs Ber.
Oct. 1902; Ch. Centr. 1902, 2, 1207),
in French neroli oil {Ibid.), and in petit-
grain oil from Paraguay [Ibid.).

Note : — No method for resolving inactive
terpineol into its optical isomerides ia at
present known.

Synthetical Processes.

[A.] \-Linalodl [37] gives d-terpineol
and its acetate with geraniol on heating
with acetic anhydride to 150-160°'
(Schimmel's Ber. April, 1898 ; Stephan,
Journ. pr. Ch. [2] 58, 109). The
crude product thus obtained is the
' licarhodol ' of Barbier (see under
geraniol [36 ; B]).

Or linalool on treatment (below 20°)
with acetic acid containing \ per cent, of
sulphuric acid gives 45 per cent, of its
weight of d-terpineol and 10 percent, of
geraniol (Stephan, loc. cit.). d-Linaloolon
treatment with strong formic acid below
20° is largely converted into 1-terpineol,

39 A-40.]

TERPINEOL

91

and 1-linalool by the same reagent into
d-terpineol (Stephan, loc. cit.).

Or from linalool through terpin hydrate
(see under dipentene [9; D]), which on
boiling with dilute mineral acid or with
acetic acid gives terpineol among other
products (Wallach, Ann. 230^ ^64).

[B.] From geraniol [36] through
terpin hydrate (see under dipentene
[9; C]) and then as above (Stephan,
Journ. pr. Ch. [2] 60;, 244). Geraniol
is also converted by strong formic acid
at ordinary temperatures into terpinyl
formate in lo-ia days. Terpinyl ace-
tate is produced in small quantity from
geraniol by heating the latter to 60-
70° with acetic acid containing a little
sulphuric acid (Stephan, loc. cit.).

Note : — The liquid terpineol prepared on the
large scale by boiling terpin hydrate with
dilute acids contains a mixture of isomerides
among which, together with the natural i-ter-
pineol, is a terpineol (A^-'-terpen-i-ol) isomeric
with the foregoing natural and synthetical pro-
ducts (Schimmel's Ber. April, 1901 ; Stephan
and Helle, Ber. 35, 2147).

[C] From limonene [9] by the action
of silver or lead oxide on the hydro-
bromide, or by the action of acetic acid
containing sulphuric acid on the hydro-
carbon (Semmler, Ber. 28, 3189).
Both d- and 1-limonene give terpineol
by this method.

Dipentene gives terpinyl acetate on
heating with glacial acetic acid to 100°
(Bouchardat and Lafont, Comp. Rend.
102, 1555).

Note: — It is not certain that the constitutional
formula given above expresses the structure
of all the synthetical terpineols obtained by
the foregoing processes.

40, Cineole ; Cajepntole ; Eucalyp-
tole.

CH,

H,C O CHa

I ' I

I CHj.C.CHj I

H

Note :— For constitutional formula see Wal-
lach, Ann. 201, 350.

Natueal Sources.

The chief constituent of oil of worm-
seed from the flower heads and stalks
of Artemisia maritima and vars. (Kraut,
Jahresber. 1862, 460 ; Kraut and
Wahlforss, Ann. 128, 293 ; Hell and
Stiircke, Ber. 17, 1970; Wallach
and Brass, Ann. 225, 291).

Occurs also in oil of Artemisia vulgaris
(Schimmelj Gildemeister and Hoff-
mann, p. 891); in oil of cajeput
(Wallach, loc. cit. 315) ; in niauli oil
{66 per cent., Bertrand, Bull. Soc. [3]
9, 435 ; Comp. Rend. 116, 1070) ; in
oil of Melaleuca acuminata (SchimmeFs
Ber. April, 1892); and in oil oiM. leuca-
dendron, var. lancifolia {Ibid.).

Cineole has been found also in oil
from the leaves of Laurus nohilis {Ibid.
April, 1899); in American oil of
peppermint (Power and Kleber, Pharm.
Rund. 12, 157; Arch. Pharm. 232,
639) j in camphor oil from Laurus
{Cinnamomtim) camphora (SchimmeFs
Ber. Oct. 1888; Oct. 1902); in oil of
sage from Salvia officitialis (Wallach,
Ann. 252, 103) ; in oil of spike laven-
der (Bouchardat and Voiry ; see under
linalool [37]) ; in oil of lavender (traces)
(Schimmel's Ber. Oct. 1893), and in
Portuguese oil of lavender from Lavan-
dula pedunculata {Ibid. Oct. 1898).

Occurs also in German oil of sweet
basil from Ocymum basilicum (Bertram
and Walbaum, Arch. Pharm. 235, 176 ;
SchimmeFs Ber. April, 1897 : see also
Hirschsohn as quoted by Gildemeister
and Hoffmann, p. 860, note) ; in oil of
rosemary from Rosmarinus o^cinalis
(Weber, Ann. 238, 89) j in oil from
the root of the ^Chinese galangal/
Alpinia officinarum (SchimmeFs Ber.
April, 1890 ; Schindelmeiser, Ch. Zeit.
26, 335)j and from the root of Kaemp-
feria rotunda (SchimmeFs Ber. April,
1894) ; in oil of Bengal cardamom
from Amomum {Elettaria) aromaticum
(SchimmeFs Ber. April, 1897); in a
Camaroon cardamom oil from (?) Amo-
mum danielli {Ibid. Oct. 1897), and in
Malabar cardamom oil from Elettaria
cardamomiim {Ibid. Oct. 1897; Parry,
Pharm. Rev. 9, 105).

Cineole is contained also in oil of

92

ALCOHOLS

[40-41.

saffron (Hilger, Ch. Centr. 19C0, 2,
576) ; in the Brazilian ' carqueia ' oil
from Geimta tiideiitata (Schimmel^s
Ber. April, 1896); in oil from the
leaves of the Indian Yxiex trifolia {Ibid.
Oct. 1894) ; possibly in oil of penny-
royal from Mentha jmlegiurn (T^try,
Bull. Soc. [3] 27, 186); in oil of rue,
probably Algerian (Power and Lees,
Trans. Ch. Soc. 81, 1590) ; and in oil of
Russian spearmint (see under linalool
[37]; SchimmeFs Ber. April, 1898).

Occurs also in oil from the leaves of
the Chiliaji M^rti/g cheken (Weiss, Arch.
Pharm. 226, 666) ; in oil of myrtle
from Myrlus communig (Jahns, Arch.
Pharm. 227, 174; Schimmel's Ber.
April, 1889) j in oil from Curcuma
zedoaria (Schimmel's Ber. Oct. 1 890) ;
in oil of the W. Indian white cinnamon
from the bark of Canella alba (Schim-
mel's Ber. Oct. 1890); in Japanese
* badiana ' or star-anise oil from Illicium
religiotum (Tardy, Bull. Soc. [3] 27,
987), and also (as ' eucalyptol ') in the
oil from many species of Eucalyptus : —

E. globulus (Jahns, Ber. 17, 2941 ;
Archir. Pharm. 223, 52) ; i. oleosa
(Maiden's ' Useful Native Plants of
Australia,' p. 372) ; E. dumosa (Schim-
mel's Ber. Oct. 1889); E. amygdalina
(Wallach and Gildemeister, Ann. 246,
278; Schimmel's Ber. Oct. 1889);
E. rostrata {Ibid. Oct. 1891) ; E.populi-
folia {Ibid. April, 1893) ; E. corymbosa
{Ibid.); E. resinifera {Ibid. Oct. 1898);
E. baileyana {Ibid. April, 1888); E. mi-
crocorys {Ibid.) ; E. risdonia {Ibid. April,
1894); E. hemiphloia {Ibid. April,
1892); E. crebra {Ibid. April, 1893);
E. macrorrhyncha (Baker and Smith,
Joum.and Proc. Roy. Soc. of N. S.Wales,
32, 104, &c.); E. capilellata {Ibid.);
E. eugenioides (ibid.); E. obliqua (Schim-
mel's Ber. Oct. 1898); E. punctata
(Baker and Smith, loc. cit. 31, 259,
&c. ; Schimmel's Ber. Oct. 1898);
E. loxopkleba (Parry, Pharm. Joum.
61, 198) ; E. dexiropinea and E. lavo-
jjinea (Baker, loc. cit. 27, 414 ; Baker
and Smith, Ibid. 32, 195) ; E. hama-
itoma (Schimmel's Ber. April, 1888);
E. piperita (Baker and Smith, loc. cit.
31, 195) ; E. maculosa (Baker, Proc.
Linn. Soc. N. S. Wales, 1899, p. 596;

Schimmel's Ber. Oct. 19CO ; Ch. Centr.
19CO, 2, 970) ; E. bicolor = E. largi'
jxorens (Schimmel's Ber. loc. cit. ; Journ.
Soc. Ch. Ind. 19, 1140); oil of 'red
gum ' of Tenterfield (? sp. ; Ibid.) ;
E. smithii and E. camphora (Baker,
Proc. Linn. Soc. N. S. Wales, 1899,
p. 292, &c.) ; E. goniocalyx (Smith,
Journ. and Proc. Roy. Soc. of N. S. Wales,
38, 86, &c. ; Journ. Soc. Ch. Ind.
19, 68) ; E. intertexta (spotted gum) ;
E. nioriisii (grey mallee) ; E. viridis
(green, red, or brown mallee) ; and
E. vitreea (white-top messmate) (Baker,
loc. cit. 1900, p. 303, &c. ; Ch. Centr.
1 901, 2, IC06) ; E. melliodora (Parry,
Ch. Drug. 68, 588) ; E. pulverulenta
(Schimmel's Ber. April, 1902) ; E. poly-
bractea (blue mallee) ; a little in oils
from E. angophorcides (apple-top box),
E. intermedia (bastard bloodwood),
E. lactea (spotted gum), E. ovalifolia
(red box), E. umbra (stringy bark or
bastard white mahogany), E. icilkin-
sonia = E. hcBmastoma var. = E. lavo-
pinea var. minor, E. jietcheri (lignum
vitae or black box), and from E. wooll-
siana (mallee box) (Baker, Proc. Linn.
Soc. N. S. Wales, 1 900, part IV).

Synthetical Process.

[A.] Terpineol [39] gives cineole
among other products when boiled
with dilute sulphuric or phosphoric
acid (Wallach, Ann. 239, 21 ; 275,

105)-

Note : — No method for resolving terpineol
into its optical isomerides is at present known.

41. Menthol; Terpanol;
Peppermint Camphor ;
Methylisopropyl-hezahydrophenol.
CH,
CH

H,C

CH»

H,C CH(OH)

\/

CH

CH(CH,),

Natural Sources.

In oil of peppermint from Mentha
piperita (Et ^^and, Germany, and

41-43 A.]

MENTHOL

93

America), M. arvensU var. piperascens
(Japan), and var. glabrata (China)
(Dumas, Ann. Chim. 50, 333; Ann.
e, 252 ; Blanchet and Sell, Ann. 6, 293 ;
Walter, Ann. 28, 312 ; 32, 288 ; Kane,
Phil. Mag. 16,418 ; Ann. 32, 285 ; Lau-
rent, Rev. Sei. 14, 341 ; Oppenheim, Ann.
120, 350 ; 130, 176 ; Journ. Ch. Soe.
15, 24). In oil of pennyroyal from
Mentha pulegium (Tetry, Bull. Soe. [3]
27, 186).

Note : — The natural product is 1-menthol.
For observations on the genesis of menthol
compounds in llentha piperita during the growth
of the plant see papers by Charabot, Gomp.
Rend. 130, 518 ; 131, 806.

Synthetical Processes.

[A.] From puleffOTie [128] by reduc-
tion with sodium in ethereal solution
(Beckmann and Pleissner, Ann. 262,

32)-

[B.] From menthone [129J as above
{Ibid.).

42. IsopulegoL

HjG CH . G Hj

CH,
CH

/\

HaC CH,

I I or(?)HO.HC CH,

HaC CH(OH) \y

\/ «.=

C CH

C(CH,), C(CH,),

Natural Source.

Said to occur in citronella oil (Tie-
mann, Ber. 32, 825; compare Labbe,
Bull. Soe. [3] 21, 1023).

Synthetical Process.

[A.] From citronellal [105] by the
action of acids or of acetic anhydride
(Tiemann and Schmidt, Ber. 29, 913;
30, 27). The transformation of pure
citronellal into isopulegol takes place
spontaneously (Labb6, loc. cit.).

Note : — The foregoing cyclic alcohols are included here on account
of their relationship to geraniol, linalodl, citronellol, &:c.

KETONE ALCOHOLS.

43. Acetol ; Acetyl Carbinol ;

Fyroracemic Alcohol ; Methylketol ;

Hydroicyacetone ; Fropanonol ;

Fropanolone.

CH, . CO . CH, . OH or CH, . C(OH) . CH,

Natural Sources.

From propylene glycol by the action
of the sorbose Bacterium in presence of
beer yeast infusion (Kling, Comp. Rend.
128, 244; 129, 1252). Certain varieties
of Mycoderma aceti produce the same
compound from propylene glycol [Ibid.
133, 231).

Synthetical Processes.

[A.] From normal or isopropyl alcohol
[15 ; 16] through propylene and pro-
pylene chloride and a-chlorpropylene by
the action of alcoholic potash on the

latter. a-Chlorpropylene by chlorina-
tion gives aS (with o)/3) dichlorpropylene
= a-chlorallyl chloride (Friedel and
Silva, Comp. Rend. 73, 957 ; 74, 8o5 ;
75, 81 j Fittig, Ann. 135, 359). The
latter on boiling with potassium car-
bonate solution yields a-chlorallyl al-
cohol (Henry, Comp. Rend. 95, 849),
which, on being dissolved in sulphuric
acid and on distilling the product with
water, gives acetol (Henry, Bull. Soe.
[2] 39, 526).

Or from propylene through propylene
chloride and 1:2: 3-trichlorpropane (see
under glycerol [48 ; A]). The latter by
the action of potassium hydroxide or tri-
ethylamine gives a^-dichlorpropylene
(Reboul, Comp. Rend. 95, 993; Ann.
Suppl. 1, 229), which can be converted
into a-chlorallyl alcohol and acetol as
above.

Or from propylene through the glycol
and the action of bromine in presence of

94

KETONE ALCOHOLS

[43 A- 44.

sunlig-lit on the latter (Kling, Comp.

Rend. 129, 319).

Note : — Generators of propylene (see under
glycerol [48]) thus become generators of
acetoL

[B.] From acetone [106] through
chloracetone (Riche, Ann. 112, 321 ;
Mulder, Ber. b, 1010). The latter on
heating with potassium acetate in al-
coholic solution gives acetol acetate
(Henry, Ber. 5, 966), which can be
hydro] ysed by boiling with water and
barium carbonate (W. H. Perkin, junr..
Trans. Ch. Soc. 59, 791).

Bromacetone (Sokolowsky, Journ.
Russ. Soc. 8, 330; Emmerling and
Wagner, Ann. 204, 29) on boiling with
potassium carbonate solution gives acetol
(E. and W. loc. c'd. 40 : compare Simon-
cini, Gazz. 31, 496).

Or acetone can be converted into % : %~
dichlorpropane by phosphorus penta-
chloride (Friedel, Ann. 112, 236), and
this by alcoholic potash gives a-chlor-
propylene, which can be converted into
a/3-dichlorpropylene, &c., as above
under A.

Or acetone by the action of sodium
and ethyl acetate gives acetylacetone
(Claisen and Ehrhardt, Ber. 22, loii),
which by the action of sulphuryl dichlor-
ide yields chloracetylacetone (Combes,
Comp. Rend. Ill, 292). The latter on
heating with potassium acetate in alco-
holic solution gives acetol acetate {Ibid.).

Or from acetone through mesityl
oxide (see under aldehyde [92 ; S]) and
trimethyltriose by oxidation of the
latter with potassium permanganate.
The triose decomposes readily into acetol
and acetone (Harries and Pappos, Ber.
34, 2979).

Or from acetone dmdi formic acid [Vol.
II] through formopyroracemic ester (H .
CO2 . CH^ . CO . CHg) from chloracetone
and potassium formate. The ester on
heating with methyl alcohol gives me-
thyl formate and acetol (Henry, Bull.
Acad. Roy. Belg. 1902, p. 445; Ch.
Centr. 1902, 2, 928).

Note: — Allylene by the action of fuming
hydrochloric acid gives 2 : 2-dichlorpropane
(Keboul, Ann. Chim. [5] 14, 453), which can
be treated as above. The generators of allylene
referred to under benzyl alcohol [54] thus
become generators of acetol.

[C] Glycerol [48] by the action of
dry hydrogen chloride gives dichlor-
hydrin = dichlorisopropyl alcohol (see
under isopropyl alcohol [16 ; G]), and
this by the action of phosphorus penta-
chloride yields i : 2 : 3-trichlorpropane
(Berthelot and De Luca, Ann. Chim.
[3] 48, 304; 52, 433; Fittig and
Pfeffer, Ann. 135, 359), which can be
treated as above under A.

Or from glycerol through allyl iodide,
which gives l : 2 : 3-trichlorpropane by
chlorination (Oppenheim, Bull. Soc. [2]
2. 97).

Note : — Propane gives 1:2: 3-trichlorpropane
by direct chlorination, so that generators of
propane thus become generators of acetol (see
under glycerol [48 ; A]).

[D.] From acetic acid [Vol. II]
through the compound formed from
acetyl chloride and aluminium chloride,
which compound on decomposition with
water gives acetylacetone (Combes,
Ann. Chim. [6] 12, 207). The latter
can be treated as above under B.

Or from acetic acid and isohutyl or
tertiary hutyl alcohol [18; 19] through
mesityl oxide by the condensation of
isobutylene with acetyl chloride or acetic
anhydride (see under acetic aldehyde
[92 ; FF]), and then as above under B.

[B.] From dextrose [l54], acetol being
among the products formed by fusion
with caustic potash (Emmerling and
Loges, Ber. 16, 837).

[F.] From acetoacetic ester [Vol. II]
through mesityl oxide (see under alde-
hyde [92; L]), and then as above
under B.

44. Methylacetyl Carbinol ;
Dimethylketol ; 3-Btitanol-2-one.

CH3.CH(OH).CO.CH3

Natural Souecb.

A product of the action of Bacillus
tartricits (Grimbert and Ficquet, Comp.
Rend. Soc. Biol. 1897, p. 962) on the
ammonium or calcium salt of tartaric
acid (Grimbertj Comp. Rend. 132,
706).

44 A-46 A.]

METHYLACETYL CARBINOL

95

Synthetical Processes.

[A.] From diacetyl [113] by reduc-
tion with zinc and dilute sulphuric
acid (v. Pechmann and Dahl, Ber. 23^

2421)-

[B.] From acetoacetic ester [Vol. II]
and methyl alcohol [13] through methyl-
acetoacetic ester by the interaction of
methyl iodide and sodio-acetoacetic ester.
The methylacetoacetic ester on hydroly-
sis gives methylethyl ketone (Frankland
and Duppa^ Ann. 138, '>^'^6', Booking,
Ann. 204, 17), and this on chlorination
yields methyl-a-chlorethyl ketone (Vla-
desco, Bull. Soc. [3] 6, 408; 807).
The latter gives methylacetyl carbinol
on treatment with alcoholic sodium
hydroxide {Ibid. 810).

[C] From acetic 2.xA propionic acids
[Vol. II] through methylethyl ketone
by distilling a mixture of the calcium
salts (Schramm, Ber. 16, 1581). Sub-
sequent steps as under B.

[D.] From acetic and butyric acids
[Vol. II] through methylethyl ketone

by distilling a mixture of the calcium
salts (Grimm, Ann. 157, 258).

Note : — Other generators of methylethyl ke-
tone are : sine methyl and propionyl chloride
(Popoff, Ann. 145, 289) ; sine ethyl and acetyl
chloride (Freund, Ann. 118, 3) or acetic anhy-
dride (Granichstadten and Werner, Monats. 32,
315) ; ethyl iodide and acetic anhydride in presence
of zinc-sodium alloy (Saytzefif, Zeit. [2] 6, 104") ;
2 : 2-dibrombutane by heating with water or 2 : 3-
dibrombutane by heating with lead oxide and
water (H<5lz, Ann. 250, 234 ; Eltekoff, Journ.
Russ. Soc. 10, 219 ; Meyer and Petrenko, Ber.
25, 3309) ; crotonylene by the action of sulphuric
acid (Lwoflf and Alm^dingen, Bull. Soc. [2] 37,
493); secondarybuft/iaZco/ioZ (methylethyl carbinol)
by passing the vapour over a heated platinum
spiral (Trillat, Comp. Rend. 132, 1495), or by
oxidation (Kanonnikoff and Saytzeff, Ann. 175,

377).

Methylethyl ketone is also obtained from the
generators of pseudobutylene, the latter giving
with hypochlorous acid a chlorhydrin which
yields the ketone on heating with water (Kras-
suski, Journ. Russ. Soc. 34, 287). Generators
of pseudobutylene are : n-propyl alcohol [15]
through hexane ; n-butyl alcohol [17] ; secondary
butyl alcohol,{rom the n-alcohol through n-butyl-
ene and the secondary iodide ; isobuiyl alcohol
[18] ; methyl alcohol [13] and glycerol [48] ; alde-
hyde [92] ; angelic and tiglic acids [Vol. II] ;
isovaleric acid [Vol. II] ; isoamyl alcohol [22]. For
references see under secondary butyl isothio-
cyanate [165 ; A ; B ; C ; D, &c.].

POLYHYDEIC ALCOHOLS.

45. Ethylene Glycol ; Ethanediol.
CH2(OH).CH2(OH)

Natural Source.

Said to be a product of oxidation of
glycerol by a micro-organism found in
wine (Rensch, Pharm. Zeit. 39, 864).

Synthetical Processes.

[A.] From et/iyl alcohol [l4] through
ethylene (see under isopropyl alcohol
[16 ; C]).

Note : — All generators of ethylene are thus
generators of glycol (see under methane [1 ;
D], and under ethyl alcohol [14 ; A ; C ; E ;
J;N;0;T;V5r;X;Y, &c.]).

[B.] From choline [Vol. II] by boil-
ing the aqueous solution (Wurtz, Ann.
Suppl. 6, 200).

46. Trimethylene Glycol ;

Normal Propylene Glycol ;

1 : 3-Propanediol.

CH2(OH).CH2.CH2(OH)

Natural Sources.

A product of the bacterial fermenta-
tion of glycerol in presence of chalk
(Freund, Monats. 2, 638 ; Fitz, Ber.
15, 876). Fitz's organism was probably
Bacilhcs hutylicus (see under n-butyl
alcohol [17]). Propylene glycol occurs
as a product of hydrolysis of the fats
used for soap manufacture (Noyes and
Watkins, Journ. Am. Ch. Soc. 17,
890).

Synthetical Processes.

[A.] Vvom glycerol [48] through allyl
bromide (n-propyl alcohol [15; E]),
trimethylene bromide by combination

96

POLYHYDRIC ALCOHOLS

[46 A-48.

with hydrogen bromide (G^romont^
Ann. 158, 37^ j Reboul, Ann. Chim.
[5] 14, 47 a; Lermontoff, Ann. 182,
358 ; Erlenmeyer, Ber. 12, 1354 ; Ann.
197, 184; Roth, Ber. 14, 1351; Bogo-
molitz. Bull. Soc. [2] 30, 23) and con-
version into the glycol by the action of
moist silver oxide, or by forming the
diacetate and hydrolysing (Reboul, loc.
cit. 491 j Beilstein and Wiegand, Ber.
16, 1497; Zander, Ann. 214, 178;
Niederist, Monats. 3, 839). The hydro-
lysis is best effected by barium or
calcium hydroxide (Henry, Bull. Acad.
Roy. Belg. [3] 36, 9).

Or from glycerol through allyl
alcohol (ethyl alcohol [14; G]), the
monochlorhydrin by combination with
hypochlorous acid, and reduction with
sodium amalgam (Henry, Rec. Tr. Ch.
16, 308).

47. Isobutylene Glycol ;
2-Meth7l-2 : 3-Fropanediol.

CH3 . C(CH3)(0H) . CH2 . OH

Natural Source.

Among the products of fermentation
of saccharose by Saccharoynyces ellip-
soideus (Claudon and Morin, Comp.
Rend. 104, 1109; Bull. Soc. [a] 49,
178 ; Henninger and Sanson, Comp.
Rend. 106, 208).

Synthetical Processes.

[A.] From isobutyl alcohol [I8]
through isobutylene (tertiary butyl alco-
hol [19 ; B]), the bromide (2-methyl-2 :
3-dibrompropane) by combination with
bromine (Linnemann, Ann. 162, 36),
and decomposition of the bromide by
heating with potassium carbonate solu-
tion (Nevol6, Bull. Soc. [2] 27, 6^;
Comp. Rend. 83, 65; 146).

Isobutylene bromide can also be
obtained from isobutyl alcohol by heat-
ing isobutyl chloride or bromide with
bromine in the presence of iron (Meyer
and Miiller, Journ. pr. Ch. 46, 161 ;
Herzfelder, Ber. 27, 1 260). The glycol
can be prepared also direct^ iso-

butyl alcohol by the action 0^ ^ ""s)

hydrochloric acid (Lwoff, Bull. Soc. [2]
43, 112).

Isobutylene gives this glycol by
oxidation with potassium permanganate
(Wagner, Ber. 21, 1232). Isobutylene
bromide is also converted into the glycol
by heating with water and lead oxide
to 50° (Krassusky, Journ. Russ. Soc.
33, 791).

[B.] From tertiary butyl alcohol [19]
through isobutylene (see under isobutyl
alcohol [I8 ; A]), and then as under
A above. Or by conversion into tertiary
butyl chloride or bromide and then into
isobutylene bromide by heating with
bromine and iron (Herzfelder, loc. cit.
1261 : see also Meyer and Miiller,
Journ. pr. Ch. 46, 161).

Also from tertiary butyl alcohol
through isobutylene bromide by the
action of bromine (fitard, Comp. Rend.
114, 753), and then as under A.

Note : — All generators of isobutylene given
under isobutyl [18] and tertiary butyl alcohol
[19] are generators of this glycol. These are:
isoamyl alcohol [18 ; B] ; isovaleric acid [18 ; C] ;
acetone and glycerol or acetic acid via /S-dimethyl-
acrylic acid [18 ; 0], &c.

48. Glycerol ; 1 : 2 : 3-Propauetriol,
CH2(0H) . CH(OH) . CH2(0H)

Natural Sources.

Widely distributed in vegetable and
animal kingdoms, glyceryl esters of
acids of the fatty and other series being
found in most saponifiable fats and
fixed oils (Scheele, 1779, Crell's Ch.
Journ. 4, 190 ; CrelFs Ch. Ann. 1, 99 ;
Chevreul, ' Recherches sur les Corps,
Gras'; Pelouze, Ann. 19, 210; 20,
46; Comp. Rend. 21, 718: for list of
oils and fats see A. H. Allen^s tables
in Thorpe^s 'Dictionary of Applied
Chemistry/ III, 28-34).

Glyceryl esters occur also in certain
waxes, such as Japan wax from Rhus
succeclanea and other species, the wax
from species of Balanophora (Java),
myrtle-berry wax from Myric.a cerifera
(N. America), and other species of
■-a found in N. and S. America,
^^~j -.-.uia, and the Cape of Good Hope.

48-C.l

GLYCEROL

97

Note :— For further informaHon on distribu-
tion of esters of glycerol see under the respective
fatty acids in Vol. II of this work. For synthesis
of esters see paper by Scheij, Eec. Tr. Ch. 18,
169 ; Ch. Centr. 1899, 2, 20.

Glycerol is formed as a secondary
product of the alcoholic fermentation
of sugars by Saccharomycetes (Pasteur,
Comp. Rend. 46, 857 ; 47, 224), and
also of dextrose, Isevulose, and maltose
by Ouliu7n albicans (Linossier and Roux,
Comp. Rend. 110, '^S5 and 868).
According to Udranszky (Zeit. physiol.
Ch. 13, 549) glycerol can be formed by
yeast independently of alcoholic fer-
mentation.

Glycerol is formed from cane-sugar
by fermentation with the mould Mucor
racemosus (Emmerling, Ber. 30, 454).

The quantity of glycerol produced
from various sugars during alcoholic
fermentation appears to be inversely
proportional to the activity of the yeast
(Laborde, Comp. Rend. 129, 344 : this
paper discusses the various conditions
determining the fluctuation in the
quantity of glycerol).

The glycerol found in fermented
liquids may in part arise from the
action of an oleolytic enzyme present
in yeast on the fats of the yeast itself
(Delbriick, Abst. in Journ. Fed. Inst.
8, 343)-

Glycerol is among the products of
fermentation by the mould-fungus
Eiirotiopis gayoni (Duclaux, Journ. Fed.
Inst. 6, 412).

Mycodenrm vini 1 can produce gly-
cerol (1-5 per cent, in fourteen weeks)
in a nutrient solution containing alcohol
and malic acid (Seifert, as quoted by
Klocker, ' Die Garungsorganismen, &c.^
p. 242).

According to Schultz Mycoderma vini
can transform 7 per cent, of alcohol
into glycerol in appropriate solution
(Van Laer, Journ. Fed. Inst. 7, 351).
Species of Mycoderma grown in nutrient
solutions containing saccharose and
maltose produce traces of glycerol
{Ibid.).

The mannitol ferment of Gayon and
Dubourg can produce glycerol from
most sugars (Ann. Inst. Pasteur, 15,

527).

Glycerol is found in the gastric juice

(? hydrolysis of fats ; Nencki and Sieber,
Zeit. physiol. Ch. 32, 291).

Synthetical Pkocesses.

[A.] From normal [15] or isopropyl
alcohol [16] through propylene (see
under isopropyl alcohol [16 ; B] : also
LeBel and Greene, Am. Ch, Journ. 2,
23; Beilstein and Wiegand, Ber. 15,
1498 j Friedel and Silva, Jahresber.
1873, 322; Mouneyrat, Bull. Soc. [3]
21, 616: for pyrogenic contact pro-
duction of propylene from isopropyl
alcohol see Ipatieff, Ber. 35, 1056),
propylene chloride by combination with
chlorine, 1:2: 3-trichlorpropane (tri-
chlorhydrin) by heating with iodine
chloride (Friedel and Silva, Zeit. [2]
7, 683), and the action of water at 180
on the trichlorpropane {Tbid. Comp.
Rend. 74, 805; 76, 1594; Bull. Soc.
[2] 20, 98). Also from propylene
through propylene bromide, 1:2:3-
tribrompropane (tribromhydrin) by
heating the latter with bromine in the
presence of iron (Kronstein, Ber. 24,
4246), triacetin by the action of silver
acetate, and hydrolysis (Wurtz, Ann.
102, 340).

According to Schorlemmer propylene
chloride and i : 2 : 3-trichlorpropane can
be obtained by the direct chlorination
of propane (Proc. Roy. Soc, 17, 372;
Ann. 150, 214; 152, 159), so that
generators of the latter (see under
n-propyl alcohol [15; A; B; C; D,
&c.]) become generators of glycerol.

According to Mouneyrat tribrom-
hydrin is among the products of the
action of bromine on propylene bromide
in presence of aluminium bromide (Bull.
Soc. [3] 19, 805).

The following synthetical products
are generators of propylene, and there-
fore of glycerol by the above methods : —

[B,] Amyl alcohols of fusel oil [22]
by passing the vapour through a hot
tube (Reynolds, Journ. Ch. Soc, 3, i ii ;
Ann, 77, 118; Wurtz, Ann. 104,242),
or by pyrogenic contact decomposition
(Ipatieff. "Rer. 35, 1053).

[C '- and oxalic acids [Vol. II]

by ' .^ ci mixture of calcium oxalate

H

98

POLYHYDRIC ALCOHOLS

[48 C-L.

and potassium acetate (Dusart, Ann.
97, 127). Also among the products
obtained by passing the vapour of acetic
acid over heated zinc dust (Jahn, Ber.
13, 2111).

[D.] Ethyl alcohol [14] by the inter-
action of zinc ethyl and carhov, tetra-
chloride [methane; 1; L; O, &c.] (Beil-
stein and Rieth, Ann. 124, 242), or of
bromoform and zinc ethyl (Beilstein
and Alexejeff, Jahresber. 1864, 470).

Also from dichloracetal (Lieben, Ann.
104, 114; Jacobsen, Ber. 4, 217;
Pinner, Ber. 5, 148; Krey, Jahresber.
1876, 474) by the action of zinc ethyl
(Paternb, Comp. Rend. 77, 458).

[E.] Acetone [IO6] through 2 : 2-
dichlorpropane by the action of phos-
phorus pentachloride (Friedel, Ann. 112,
236) and the action of sodium at 130-
150° (Friedel and Ladenburg, Zeit. [2]
4, 48). Also from 2 : 2-dibrompropane
by the same process (Reboul, Ann. Chim.
[5] 14, 488).

Acetone combines with bromine to
form an unstable dibromide (Linnemann,
Ann. 125, 307) which gives acrolein
[101] on distillation {Ibid. 310) ; or, by
the action of iodine trichloride on acetone,
diiodacetone is formed (Simpson, Journ.
pr. Ch. 102, 380), and this yields acrolein
on treatment with silver cyanide {Ibid.).
Acrolein when reduced with zinc and
hydrochloric acid gives allyl alcohol
(Linnemann, Ann. Suppl. 3, 260), and
the latter yields glycerol by oxidation
with potassium permanganate (Wagner,
Ber. 21, 1237).

Or allyl alcohol can be converted into
allyl iodide (Tollens, Bull. Soc. [2] 9,
3q6), or allyl carbonimide (Cahours and
Hofmann, Phil. Trans. 1857, p. ^^^) and
allylamine {Ibid. Ann. 102, 301). The
latter on acetylation and bromination
gives acetyl-^y-dibrompropylamine and
the dibrompropylamine by hydrolysis,
y-amino-a/3-propyleneglycol by heating
the latter with water, and glycerol by the
action of nitrous acid (Chiari, Monats.

19,571)-

[p.] Butyric and isobutyric [Vol. II]

acids ; propylene is among the products

of electrolysis of the potassium salts

(Bunge, Journ. Russ. Soc. 21, 552;

liamonet, Comp. Rend. 123, 252 ;

Petersen, Ch. Centr. 1897, 2, 519).
Propylene is also among the products
formed by passing butyric acid vapour
over heated zinc dust (Jahn, Ber. 13,
2115).

[G.] Isovaleric acid [Vol. II] ; pro-
pylene is among the products (ethylene,
butylene, &c.) formed by passing the
vapour through a hot tube (Hofmann,
Journ, Ch. Soc. 3, 121) ; also among the
products of dry distillation of calcium
isovalerate (Dilthey, Ber. 34, 21 15).

[H.] Lactic acid [Vol. II] ; propylene
is among the products (ethylene, &c.)
formed by distilling calcium lactate
(Gossin, Bull, Soc. [2] 43, 49).

[I.] Azela'ic acid [Vol. II] ; propylene
is among the products of distillation
with soda-lime (Miller andTschitschkin,
Journ. Russ. Soc. 31, 414; Ann. 307,

375)'

[J.] Thymol [67] gives propylene on
heating with phosphorus pentoxide
(Engelhardt and Latschinoff, Zeit. [2]
5, 616).

[K.] From acetic acid [Vol. II] and
ethyl alcohol [14] through ethoxychlor-
acetoacetic ester by the action of sodium
on ethylchloracetate in ethereal solution
and decomposition of the product by dilute
hydrochloric acid (Fittig and Erlenbach,
Ann. 269, 15). The ester on heating
with dilute hydrochloric acid gives sym-
metrical dichloracetone = i : 3-dichlor-
propanone (^Ibid. 18), and this yields
diiodacetone on heating with potassium
iodide solution (Volker, Ann. 192, 89).
Diiodacetone can be converted into acro-
lein, &c., as under E.

Or acetic acid can be converted into
chloracetic acid and nitromethane by
distilling potassium chloracetate with
potassium nitrite (Preibisch, Journ. pr.
Ch. [2] 8, 316). Nitromethane gives
glycerol as below under L.

[L.] From methyl alcohol [l3] and
formic aldehyde [9l] by converting the
alcohol into methyl iodide and nitro-
methane by the action of silver nitrite
(Bewad, Journ. Russ. Soc. 24, 1 26; Meyer,
Ann. 171, 32) ; the sodium or barium
compound of nitromethane gives brom-
nitromethane by the action of bromine
(Tscherniak, Ber. 7, 916; Ann. 180,
128 ; Ber. 30, 2588), and this condenses

48 L-49 A.]

GLYCEROL

99

with formic aldehyde (2 mols.) to give
trimethylenebromnitrog-lycolj which by
reduction yields trimethyleneaminogly-
colj and the latter by the action of nitrous
acid is converted into glycerol (Henry,
Rec. Tr. Ch. 16, 250; Bull. Acad. Roy.
Belg. 30, 25).

Or nitromethane and formic aldehyde
may be combined so as to form ' nitro-
isobutylglycerol/ (CHg . OH)^ C . NO^
(Henry, loc. cit. ; Piloty and Ruff, Ber.
SO, 1656), from which the correspond-
ing hydroxylamine derivative can be
obtained and converted by oxidation
with mercuric oxide into the oxime of
dihydroxy acetone. Bromine converts
the latter into dihydroxyacetone [l5l],
and this by reduction with sodium
amalgam in presence of aluminium
sulphate gives glycerol (Piloty, Ber.
30, 3161).

Note : — Methyl alcohol gives nitromethane
also by the interaction of dimethyl sulphate
and a nitrite (Kaufler and Pomeranz, Monats.
22, 492).

[M.] Citric acid [Vol. II] by the
action of sulphuric acid gives acetone-
dicarboxylic acid (v. Pechmann, Ber.
17, 2543; Ann. 261, 157: see also
Peratoner and Strazzeri, Gazz. 21, 295,
and under, orcinol [75 ; C]), which by the
action of sodium nitrite yields diisonitro-
soacetone (v. Pechmann and Wehsarg,
Ber. 19, 2465). The latter on reduction
gives diaminoacetone (Gabriel, Ber. 27,
1043; Kalischer, Ber. 28, 1519), which
by the action of nitrous acid is con-
verted into dihydroxyacetone {Ibid.
152 1 ), and this can be reduced to
glycerol as under L above.

[N.] llippuric acid [Vol. II] when
its ethyl ester is heated with dry sodium
ethoxide gives with another product
' dibeuzaminodioxytetrol ■" (Riigheimer,
Ber. 21, 3325), which on heating with
sulphuric and acetic acids and water
yields diaminoacetone {Ibid. 3328). The
latter can be converted into dihydroxy-
acetone and glycerol as above. The
other product, ' a-oxy-/3-benzamino-/3-
oxypyrroline,^ also gives diaminoacetone
by the same method {Ibid. 22, 1955).

[O.] From mannitol [51], which gives
acrolein [lOl] among the products of
oxidation by sulphuric acid and man-

H

ganese dioxide (Backhaus, Jahresber.
1860, 522). Subsequent steps through
allyl alcohol, &c., as above under E.
Or through n-hexane and propylene (as
under isopropyl alcohol [I6 ; I]).

Note :— All generators of n-hexane (see iinder
n-hexyl alcohol [23 ; A, &c.]) thus become
generators of glycerol.

[P.] Uric acid [Vol. II] gives glycerol
among the products of reduction by
heating with aqueous hydriodic acid
(Strecker, Zeit. [2] 4, 215).

[Q.] From isobufyl alcoliol [I8]
through isobutyl chloride or bromide.
The haloids give propylene among other
products when passed over lime heated
above 600° (Nef, Ann. 318, 22).

Or from isobutyl or tertiary butyl
alcohol [19] through isobutylene and
propylene (see under isopropyl alcohol
[16 ; D ; E]). Isobutyl alcohol gives
propylene and isobutylene among the
products of partial combustion by air
in contact with heated platinum (v.
Stepski, Monats. 23, ']'J^).

49. Glycerophosphoric Acid.

CH^COH) . CH(OH) . CH2 . 0 . P . 0(0H)2

Natural Sources.

Has been found in small quantity in
human urine, in certain (animal) gall-
stones, in the juices of the spleen and
other organs and tissues. In all cases
it is probably a product of decomposi-
tion of lecithin (Sotnitschewsky, Zeit.
physiol. Ch.4,214; Robin, Arch. Pharm.
2,532; Ch. Centr. 1888, 186; Lepine,
Eymonnet, and Aubert, Comp. Rend.
98, 238; in leucaemic blood, Salamon
and Kossel as quoted by Hammarsten,
'Lehrb. d. physiol. Ch.'' 1895, p. 152).

Lecithin, a complex substance related
to natural fats and obtained from many
animal and vegetable sources, is a choline
ester of palmito-stearo-glycerophos-
phoric acid.

Synthetical Process.

[A.] From glycerol [48] by heating
with metaphosphoric acid or phosphoric
anhydride (Pelouze, Journ. pr. Chem.

100

POLYHYDRIC ALCOHOLS

[49 A-50 C.

36, 257 ; Comp. Rend. 21, 720; Fortes
and Brunier, Bull. Soc. [3] 13, 96 ;
Imber and Belugou, Ibid. 21, 935 : for
technical production, Guedras, Monit.
Sci. 13,577; Ch. Centr. 1899, 2, 60.6).

50. Erythritol; Er3rfcIiroglacin ;

Erythromannite ; Fhycite ;

1:2:3: 4-Butanetetrol.

H H

I I
HO . HjC— C— C— CHa . OH

I I
HO HO

(Inactive modification).

Natural Sources.

Occurs in the free state in Proto-
coccus vulgaris (Lamy, Ann. Chim. [3]
35, 138 ; 51, 232 ; Comp. Rend. 36,
6^^) and as an ester of a complex acid
(orcellic acid) in erytlirin and /3-erythrin,
which are found in the lichens UoccelLa
iinctoria^ R. montagnei, and R. fiici-
formis. (For distribution of erythrin
= erythric acid in lichens see also
under orcinol [75] : for /3-erythrin see
j8-orcinol [77].) Hesse (Journ. pr. Ch.
[2] 57, 258) regards erythrin as a con-
densation product of erythritol and
lecanoric acid.

Erythritol has been found in the alga
Trentepohlia joUthus (Bamberger and
Landsiedl, Monats. 21, 571).

Synthetical Processes.

[A.] From acetylene and ethylene (see
under methane [l ; A ; D, &c.]). When
these gases are passed through a hot
tube a hydrocarbon is formed which is
apparently identical with erythrene or
pyrrolylene (divinyl ; 1 : 3-butadiene ;
CH2 : CH . CH : CH2) (Berthelot, Ann.
Chim. [4] 9, 466), and this can be
converted into an unstable dibromide
by bromination in chloroform solution
at —21°, then into a stable isomeric
dibromide which, with silver acetate,
forms a diacetin. The latter is again
brominated, the dibromdiacetin con-
verted into a tetracetin by further
treatment with silver acetate, and the
product hydrolysed (Griner, Comp.

Rend. 116, 723 ; Bull. Soc. [3] 9,
218). When the unstable dibromide
is heated to 100° there is formed, with
the stable dibromide above referred to,
another dibromide which, on oxidation
with permanganate, gives the dibrom-
hydrin of natural erythritol from which
the latter can be obtained through the
diacetin and hydrolysis, or by heating
the dibromhydrin with potassium hy-
droxide and then hydrating the di-
hydroxybutane thus obtained by heating
with water (Griner, Comp. Rend. 117,
^^T, ; Bull. Soc. [3] 9, 218 ; also Thiele,
Ann. 308, ^^^ ; Maquenne and Ber-
trand, Comp. Rend. 132, 1565).

Or the acetylene and ethylene could
be indirectly converted into erythrene
through pyrrole as under C, this last
compound being formed among other
products when a mixture of acetylene,
ethylene, and ammonia are passed
through a hot tube (Dewar, Proc. Roy.
Soc. 26, 6^).

[B.j From a7ni/l alcohol [22]. Ery-
threne is said to be among the products
formed by passing the vapour through
a hot tube (Caventou, Ann. 127, 93),
or by pyrogenic decomposition by pass-
ing the vapour over heated iron (Ipatieff,
Ber. 35, 1053).

[C] From succinic acid [Vol. II] and
methyl alcohol [13] through succinimide
(D^Arcet, Ann. Chim. [2] 58, 294;
Fehling, Ann. 49, 198; Laurent and
Gerhardt, Comp. Rend. d. Travaux de
Chim. 1849, 108; Menschutkin, Ann.
162, 165; 187; 182,93; Bogert and
Eccles, Journ. Am. Ch. Soc. 24, 20),
pyrrole [Vol. II] by distilling succinim-
ide with zinc dust (Bell, Ber. 13, 877).
N-methylpyrrole (C4H4 . N . CH3) by
the action of methyl iodide on potassium
pyrtole (Ciamician and Dennstedt, Ber.
17, 2951), dihydromethylpyrrole (me-
thylpyrroline) by reduction with zinc
dust and acetic acid (Ciamician and
Magnaghi, Ber. 18, 725 : see also
Knorr and Rabe, Ber. 34, 3491 ; Cia-
mician, Ibid. 3952), tetrahydromethyl-
pyrrole (N-methylpyrrolidine) by
further reduction with hydriodic acid
and phosphorus (C. and M. Ibid. 2080),
the methiodide by addition of methyl
iodide, dimethylpyrrolidine (C^H^ .

60 C-E]

ERYTHRITOL

101

N[CH3]2) by distilling the methiodide
with potassium hydroxide, and dimethyl-
pyrrolidine-methiodide (trimethylpyrro-
lidine iodide; C^H^. N[CH3]3l) by
addition of methyl iodide. The latter
compound on distillation with caustic
alkali gives (among other products)
pyrrolylene or erythrene, which can be
treated as under A (Ciamician and
Magnaghi, Ber. 18, 2o8i ; 19, 569;
Gazz. 15, 504).

Or the siaccinimide can be converted
into dichlormaleinimide by the action
of chlorine at 160° (Ciamician and
Silber, Ber. 16, 2393), perch lorpyrrole
chloride by the action of phosphorus
pentachloride, reduction to tetrachlor-
pyrrole with zinc dust and acetic acid,
conversion into tetraiodopyrrole by heat-
ing with potassium iodide solution, and
reduction to pyrrole with zinc dust in
alkaline solution [Ibid. 17, 554 ; 19,
3027), and then through N-methyl-
pyrrole, &c., as above.

Also from succinic acid through
methylsuccinimide by distilling the
wethylamine [Vol. II] salt (Menschut-
kin, Ann. 182, 92), conversion into
N-methylpyrrole by distilling with zinc
dust, and then as above.

Or indirectly from succinic acid
through Isevulic acid by heating with
acetic anhydride (Fittig, Ber. 30,
3148). From Isevulic acid through
N-methylpyrrole, &c., as below under D.

Or succinic acid is converted into the
anhydride by heating with acetyl
chloride, the anhydride into mono-
p( dium ethyl ester by treatment with
soflimn ethoxide in alcoholic solution,
and the ester into succinoyl-ester
chloride (carbethoxypropionyl chloride)
by the action of phosphorus trichloride.
The chloride on treatment with zinc
methyl in benzene solution and decom-
position of the product with water
gives ethyl Isevulate, from which the
acid can be obtained by hydrolysis
(Blaise, Bull. Soc. [3] 21, 641 ; 647).
From Isevulic acid as below under D.

Succinic ester and methylethyl ketone
(from acetic and propionic acids) con-
dense under the influence of sodium
ethoxide to form y-ethylidene-y-methyl-
pyrotartaric acid (CH3 . CH : C[CH3] .

CH[COOH] . CH2 . COOH), which
gives Isevulic acid on oxidation with
potassium permanganate (Stobbe, Stri-
gel, and Meyer, Ann. 321, 105).

[D.] PVom ethyl alcohol [l4] and
acetic acid [Vol. II] by converting the
latter into chloracetic ethyl ester
(Willm, Ann. Chim. [3] 49, 97 ; Ann.
102, IC9; Conrad, Ann. 188, 3i8),
and then into acetylsuccinic ester by
the interaction of chloracetic ester and
sodio-acetoacetic ester (Conrad, loc. cit.;
Rach, Ann. 234, 0^6). Acetylsuccinic
ester on boiling with dilute hydro-
chloric acid is converted into /3-acetyl-
propionic or Isevulic (4-pentanonic) acid
(Conrad, Ann. 188, 222; Ber. 11, 2177),
the oxime of which (y-isonitrosovaleric
acid) is formed by the action of hydr-
oxylamine on the ketonic acid (Miiller,
Ber. 16, 161 8; Rischbieth, Ber. 20,
2670). The oxime on heating with
sulphuric acid forms methylsuccinamie
acid (Bredt and Boddinghaus, Ann.
251, 319), and the latter on heating
gives methylsuccinimide {Ibid. 320),
from which N-methylpyrrole can be
obtained by heating with zinc dust as
under C.

Or sodio-acetoacetic ester and ethyl-
ene bromide interact to form brom-
ethylacetoacetic ester, which on heating
with dilute hydrochloric acid gives
acetylpropyl alcohol. The latter gives
Isevulic acid on oxidation with chromic
acid mixture (Lipp, Ber. 22, 1197).

Divinyl is among the products
formed by passing the vapour of ethyl
alcohol over aluminium powder heated
to 580-680° (Ipatieff, Journ. pr. Ch. [2]
67, 420).

[E.] From isohexoic acid [Vol. II] by
long boiling with dilute nitric acid,
which gives the anhydride. of a-methyl-
hydroxyglutaric acid = 2 : 2-methylpen-
tanoldiacid (Bredt, Ber. 14, J 781).
This anhydride on heating with sul-
phuric acid gives Isevulic acid (Tollens
and Block, Ber. 19, 707), which can be
treated as under D.

The anhydride can also be obtained
from isohexoic [isobutylacetic) acid
through the anhydride of y-hydroxyiso-
hexoic acid by oxidising the former acid
with potassium permanganate (Bredt,

102

POLYHYDRIC ALCOHOLS

[50 E-G.

Ann. 208,59) and boilingtlie y-hydroxy-
isohexoic anhydride with dilute nitric
acid {Ibid. 62).

[P.] From walonic acid [Vol. II] and
glycerol [48] through allylmalonic acid
by the action of allyl iodide on sodio-
malonic ester and hydrolysis (Conrad
and Bischoff, Ann. 204, 168), allylacetic
acid by heating allylmalonic acid (Ihid.
1 70), and yS-dibromvaleric acid by the
addition of broinine (Messerschmidt,
Ann. 208, loo). The dibromo-acid on
boiling with water gives (with much
dihydroxyvaleric acid) Isevulic acid
(Fittig and Urban, Ann. 268, 64),
which can be treated as under D.

Or from malonic acid, glycerol, and
methylamine [Vol. II] (with ethyl al-
cohol as accessory) through ethyl brom-
propyl malonate by the action of trime-
thylene bromide (see under propylene
glycol [46 ; A]) on sodio-malonic ester.
Ethylbrompropyl malonate on bromina-
tion gives ethyl- aS-dibrompropyl ma-
lonate, and this on treatment with
methylamine yields-amethylamide which
on hydrolysis gives among other pro-
ducts N-methylpyrollidine-2-carboxylic
= hygric acid (Willstatter, Ber. 33,
1 1 60; W. and Ettlinger, Ber. 35, 620).
The latter on dry distillation yields N-
methylpyrollidine (Liebermann and Cy-
bulski, Ber. 28, 582), which can be
treated as above under C.

Malonic acid and acrolein [lOl] from
glycerol condense in presence of pyridine
to form /3-vinylacrylic acid, and this is
reduced by sodium amalgam to allyl-
acetic acid (Doebner, Ber. 35, 1136:
according to Thiele and Jehl, Ber. 35,
2320, the acid thus formed is /3y-pen-
tenoic acid).

[G.] From acetic acid [Vol. II], gly-
cerol [48], and ethyl alcohol [14] through
allylacetoacetic ester by tne action of
allyl iodide on sodio-acetoacetic ester
(Zeidler, Ann. 187, 33), allylacetic ester
by the action of sodium ethoxide [Ibid.
39), allylacetic acid by hydrolysis, and
then as under P.

Or allylacetoacetic ester can be hydro-
lysed to allylacetone (Zeidler, Ann.
187,35; Conrad, Ann. 192, 153; Mer-
ling, Ann. 264, 323), which gives lae-
vulic acid on oxidation with potassium

permanganate (v. Braun and Stechele,
Ber. 33, 1472).

Or glycerol can be converted into
trimethylene bromide (see under propyl-
ene glycol [46 ; A]) and the latter con-
densed with sodio-acetoacetic ester to
form brombutyl methyl ketone (Lipp,
Ber. 18, 3278). The latter on decom-
position by alkali gives allylacetone (v.
Braun and Stechele, /oc. cit. 1473), which
can be oxidised to Isevulic acid as
above.

Or from acetic acid or ethyl acetate
and acetone [IO6] through acetylacetone
(see under n-primary amyl alcohol [20 ;
B ; C]). The latter by the action of
ethyl chloracetate on the sodium deri-
vative gives ^y3-diacetylpropionic ethyl
ester (March, Comp. Rend. 130, 1192),
and this on treatment with strong caus-
tic soda solution yields Isevulic acid {Ibid.
132, 697).^

Or sodio-acetylacetone and ethyl-a-
brompropionate (see under aldehyde [92;
E]) interact to form /3/3-diacetyl-a-me-
thylpropionic ethyl ester, which is de-
composed by alkali as above into Ise-
vulic acid and ester (March, loc. cit.
134, 179 : see also Ann. Chim. [7] 26,

395).

Also from glycerol through allylamine
by the interaction of allyl iodide and
silver cyanate, and decomposition of the
allyl cyanate with alkali (Cahours and
Hofmann, Phil. Trans. 1857, $^^ ; Ann.
102, 301). Allylamine by the action
of ethyl iodide gives ethylallylamine
(Rinne, Ann. 168, 261), and the vapour
of the latter yields (among other pro-
ducts), when passed over heated lead
oxide, pyrrole (Konigs, Ber. 12, 2344),
which can be treated as under C.

Or from glycerol through allyl al-
cohol, allyl chloride (Tollens, Ann. 156,
154; Eltekoff, Journ. Russ. Soc. 14,
394), and trimethylene-chlorobromide=
I : 3-chlorbrompropane (Reboul, Ann.
Chim. [5] 14, 487). The latter by
the action of potassium cyanide gives
y-chlorbutyronitrile (Henry, Bull. Soc.
[2] 45, 341; Gabriel, Ber. 23, 1771),
and the chlornitrile by interaction with
sodium phenolate yields y-phenoxy-
butyronitrile (Gabriel, Ber. 24, 3231),
which by reduction with sodium in

50 G-V.]

ERYTHRITOL

103

alcohol gives 8-phenoxybutylamine, and
the latter on heating" with strong hydro-
chloric acid at 180-185° 8-chlorbutyl-
amine {Ibid. 3232). On distilling the
amine with potash solution pyrrolidine
is formed {Ibid. 3234 ; Schlinck, Ber. 32,
1025) and the latter might be methy-
lated and treated as above under C.

Or from glycerol through allyl alcohol
(see under ethyl alcohol [l4 ; G-]), which
probably gives divinyl among the pro-
ducts of pyrogenic contact decomposition
(Ipatieff, Ber. 35, 1054).

[H.] From lavtdose [155] through
Isevulic acid by boiling with dilute
sulphuric acid (Grote and Tollens, Ann.
175, 181) and subsequent treatment as
under D,

[I.] Mannose [l56] gives Isevulic
acid when its phenylhydrazone is heated
with hydrochloric acid (Fischer and
Hirschberger, Ber. 22, 370).

[J.] From dextrose [154] through
saccharic acid by oxidation with nitric
acid or bromine (Trommsdorff, Ann,
8, "^6 ; Guerin-Varry, Ann. Chim. [3]
49,280; 52,318; 65,332; Herzfeld,
Ann. 220, 352 ; Tollens, Ann. 249,
218). Ammonium saccharate gives
pyrrole on distillation (Bell and Lapper,
Ber. 10, 1962), and this can be con-
verted into dimethylpyrrolidine, &c., as
under C.

Or from dextrose through gluconic
acid [Vol. II], d-arabinose, and d-
erythrose (see under latter [152 ; D]).
The latter gives i-erythritol on reduc-
tion with sodium amalgam (RufP, Ber.
32, 3677).

[K.] From diethylamine [Vol. II].
Pyrrole is formed when the vapour is
passed through a hot tube (Bell, Ber.
10, 1868), and can be treated as under C.

[L.] From glutamic acid [Vol. II]
by converting the acid into pyroglu-
tamic acid by heating to 190°, the
latter on further heating giving pyrrole
(Haitinger, Monats. 3, 228).

[M.] From piperidine [Vol. II]
through dimethylpiperidine by heating
the hydrochloride with methyl alcohol
at 250° and decomposition of the
ammonium chloride derivative by
silver oxide, &c. (Ladenburg, Ber.
16, 2057; Ladenburg, Mugdan, and

Brzostovicz, Ann. 279, 344). Di-
methylpiperidine hydrochloride when
treated with hydrogen chloride at 220°
is converted into dimethylpyrrolidine
(Ladenburg, Mugdan, and Brzostovicz,
loc. cit. : also Merling, Ann. 264, 310),
which can be converted into erythrene
as under C, &c.

[N.] Bimetliynieptenol [35] gives Ise-
vulic acid among the products of its
oxidation by chromic acid mixture (Bar-
bier, Comp. Rend. 126, 1424).

[O.] From crotonic aldehyde [102] and
hydrogen cyanide [l72]. The cyanhydrin
of crotonic aldehyde hydrolyses to a-
hydroxypentenoic acid [CHg . CH : CH .
CH(OH) . COOH], and this on heating
with dilute hydrocnloric acid undergoes
(isomeric) transformation into Isevulic
acid (Fittig, Ber. 29, 2582 : see also
Lobry de Bruyn, Bull. Soc. [2] 42,
159; Fittig, Ann. 299, i).

[P.] From furfural [126] through
pyromucic acid by oxidation (Schwanert,
Ann. 114, 6^ ; 116, 257 ; Volhard, Ann.
261, 379). The acid on heating with
lime and ammonio-zinc chloride gives
pyrrole (Canzoneri and Oliveri, Gazz.
16, 487). From pyrrole to erythrene
as above under C.

[Q.] Methylheptenone [ill] on oxida-
tion with potassium permanganate gives
a ketone glycol which, on further oxida-
tion with chromic and sulphuric acid,
yields (with acetone) Isevulic acid (Tie-
mann and Semmler, Ber. 28, 2128).

[R.] From d-erythrose [l52] by re-
duction as above under J.

[S.] Azela'ic acid [Vol. II] gives ery-
threne among the products of its dis-
tillation with soda-lime (Miller and
Tschitschkin, Journ. Russ. Soc. 31, 414 ;
Ann. 307, 375).

[T.] From gluconic acid [Vol. II]
through d-arabinose and d-erythrose as
above under J.

[U.] From pyrrole [Vol. II] and
methyl alcohol [l3] as above under C.

[v.] Isopropyl alcohol [16] gives
divinyl (erythrene) among the products
of pyrogenic contact decomposition (Ipa-
tieff, Ber. 35, 1056).

Note : — The biochemical product, d-erythru-
lose [152], obtained from i-erythritol by the
action of the sorbose Bacterium, gives with the

104.

POLYHYDRIC ALCOHOLS

[50-51.

above i-erythritol, another modification, d-ery-
thritol :—

H OH
I I
HO . H,C . C . C . CH2 . OH

I I
H HO

on reduction (Bertrand, Comp. Rend. 130,
1472). A partial synthesis of l-erythritol start-
ing from 1-xylose has been effected by Maquenne
(Comp. Kend. 130, 1402).

51. Manuitol ;
1 :2:3:4:5:6- Eexauehexol.

H H HO HO

I I I I
HO. H^C-C— C— C-C— CHa. OH

I I I I
HOHO H H

(Dextro-modification).

Natural Soueces.

Mannitol is widely distributed through-
out the vegetable kingdom. Occurs in
' manna/ the thickened sap of the
manna ash, Fraxinus ornus = Ornus
europcea and 0. rotundifolia (Proust,
Ann. Chim. 57, 143 ; Tanret, Bull. Soc.
[3] 27, 947); in Australian manna from
iVlyoporum platycarpum (Fliickiger, Ch.
Zeit. 18, 185) ; in root of monkshood,
Aconitum napellus (Smith, Jahresber.
1850, ^'^^) ; in celery, Apium graveolens
(Payen, Ann. 12, 60 ; Monteverde, Ann.
Agronom. 19, 444), parsley (Monte-
verde, loc. cit.), and pomegranate root
(Boutron-Charlard and Guillemette,
Joum. Pharm. 21, 169) ; in leaves and
twigs of lilac, Syringa v^^lgaris (Roussin,
Jahresber. 1851, 550 ; Ludwig, Ibid.
1857, 503 : see also Monteverde, loc.
cit.) ; in bark of Canella alba (Meyer
and Reiche, Ann. 47, 234 ; Petroz and
Robiquet, Joum. Pharm. 8, 198), and
of ash, Fraxinus excelsior (Rochleder
and Schwarz, Ann. 87, 186).

Mannitol exists also in the sap of
Coniferse such as Pinus and Abies, &c.
(Kachler, Monats. 7, 410) ; in coffee
berries (Boussingault, Comp. Rend. 91,
639) and berries of Ephedra distachya
(Meunier, Ann. Chim. [6] 22, 412) ; in
fruit of cherry laurel,Prz/«?^* laurocerasus
(Vincent and Delachanal, Comp. Rend.
114, 486) ; in olives (De Luca, Jahres-
ber. 1861, 740 ; 1862, 505 ; Bull. Soc.

1863, 372) ; in pine-apple (Lindet, Ibid.
[2] 40, 6^), and in the fruit of Cactus
opuntia (Berthelot, Ann. Chim. [3]
46, 66). The 'manna'' of olives is an
exudation resulting from a bacterial
disease of the cambium layer and con-
tains 52 per cent, of mannitol (Trabut
and Schweinfurth, Comp. Rend. 132,
225 : see also Battandier, Journ. Pharm.
[6] 13, 177).

Mannitol occurs in the cambium layer
of larch, Larix europcea, and other Coni-
ferse ; in the water dropwort, (Enanthe
crocata ; in Meum athamaiiticum ; Foly-
podium vulgare ; Scorzonera hispjanica ;
Triticum, repens ; root-bark of Punica
granatum ; in leaves of privet, Ligustrum
vulgare ; in fruit of Laurus persea^ and
in leaves of the cocoanut palm, Cocos
nucifera (Watts^s Diet. Morley and Muir,
III, 189).

Mannitol occurs also in the tubercles
of Cyclamen europmim (De Luca, Comp.
Rend. 47, 295 ; 87, 297 ; Bull. Soc. [2]
32, 417). The mannitol complex ap-
pears to be contained in cyclamin, the
glucoside occurring in this and other
species of Cyclamen and in Primulacese.
Mannitol has been found in certain
Scrophulariacese (272 species) of the
genera Rhinanthus and Euphrasia and in
some Orobancheaceae, Oleacese, and Um-
belliferse (Monteverde, Ann. Agronom.
19, 444 ; Journ. Ch. Soc. 66, II, abst.
25) ; in leaves and bark of Genipa bra si-
nensis (Kwasnik, Ch. Zeit. 16, 109) ;
in leaves and bark of Basanacaritha
spinosa,y2kr.ferox (Griitzner and Pecholt,
Arch. Pharm. 233, i) ; in leaves of
Catha edulis (Beitler, Ibid. 239, 17); in
sap of the sea buckthorn, Hippophae
rhamnoides (Erdmann, Ber. 32, ^^S"^-

A true manna found on Andropogon
annulatus contains 58 per cent, manni-
tol (Baker and Smith, Journ. and Proe.
Roy. Soc. N. S. Wales, 30, 291). The
lichens Physcia [Xanthoria) parietina and
Callopisma vitellinum contain mannitol
(Zopf, Ann. 300, 354 ; for the former
Zopf quotes Lilienthal).

Mannitol occurs in algae and fungi: —
Lami7iaria saccharina (Stenhouse, Ann.
51, 349 ; Pussula Integra ( = Agaricus
integer) to the extent of 20 per cent.
(Thorner, Ber. 12, 1635) ; Lactariiis

61-A.]

MANNITOL

105

pallidus, L. pyrogallus, L. vellevreus, L.
iurjjis, L. piperatus, L. controversus, &e.
(Bourquelot, Comp. Rend. 108, 568) ;
Boletus and Amanita sp., Pholiota radi-
cosa, Hj/pholoma fascicular e [Ibid. Ill,
^"jS); Blaphomi/ces granulatus (Bissinger,
Arch. Pharm. [3] 21, 321); also in
erg-otised rye (Pelouze and Liebig",
Comp. Rend. 3, 418; Ann. Chim. [3]
63, 113: for occurrence of mannitol in
algEB, fungij &c., see also Braconnot,
Ann. Chim. [i] 79,265; 80,272; 87,
237 ; Vauquelin, Ibid. 85, 5 ; Knop and
Schnedermann, Ann. 49, 293 ; Journ.
pr. Ch. 32, 411 ; Dopping and Schloss-
berger, Ann. 52, 117; Miintz, Comp.
Rend. 76, 649; 79, 11 82; 82, 210;
Ann. Chim. [5] 8, ^6 ; Ferry, Ch.
Centr. 1889, 1, 541 ; 1891, 1, 220).

The alcoholic extract of Agaricus
campestris contains mannitol (Zega,
Ch. Zeit. 24, 285).

The mould Penicillium glaucum can
under certain conditions produce man-
nitol as a product of metabolism (Miintz ;
see Klocker's ' Garungsorganismen, &c.''
p. 229). _ ^

Mannitol is formed during the lactic
fermentation of sugar (Liebig, Jahres-
ber. 1847-48, 466 ; Strecker, Ann. 92,
80 ; Pasteur, Jahresber. 1857, 5 1 1 ;
DragendorfF, Ibid. 1879, 854 ; Arch.
Pharm. [3] 15, 47), and also during
the viscous or mucous fermentation of
sugar (Pasteur, Jahresber. 1861, 728;
Bull. Soc. 1861, 30; Journ. Pharm. [3]
39, 433). The sugar in wine is con-
verted into mannitol during the de-
generation known as ' bittering '
(Basile, Staz. Sper. Agrar. 26, 451 ;
Gayon and Dubourg, Ann. Inst. Past.
8, 1894; Laborde, Comp. Rend. 126,
1223). This mannitol fermentation is
an anaerobic process (Peglion, Centr.
Bakter. II, 4, 73) and the ferment
can produce mannitol from Isevulose
only (Gayon and Dubourg, loc. cit. 15,

527)-

Reducing micro-organisms generally
may give rise to mannitol during the
fermentation of sugars, especially under
anaerobic conditions. Thus, many fer-
mented liquors from various fruits, &c.,
may contain mannitol (Vauquelin and
Fourcroy, Ann. Chim. [i] 65, 161 ;

Pelouze, Ibid. [%] 47, 409 ; Berthelot,
Comp. Rend. 41, 392 ; Ann. Chim. [3]
46, 66; Scheibler, Ber. 6, 612; Gui-
bourt, Ann. Chim. [2] 16, 371 ; Mar-
cano, Comp. Rend. 108, 955 ; Carles,
Ibid. 112, 811 ; Blarez, Journ. Pharm.
[5] 27, 260; Roos, Ch. Centr. 1893,
1, 1098 ; Malbot, Bull. Soc. [3] 11, 87 ;
176; 413; Jandrier, Comp. Rend. 117,
498).

Mannitol has been found in beet-
sugar molasses (Margueritte ; quoted by
Maquenne, ^Les Sucres, &c.' p. 131 : also
Scheibler, Ibid.; and v. Lippmann, Ber.
25, 3216). The mannitol is produced
in this case from sugar by Leticonostoc
wesenterioides (Greig-Smith and Steel,
Journ. Soc. Ch. Ind. 21, 1386). JBa~
ci llus gummosKs Tproduces mannitol from
sugar (Happ ; quoted by Emmerling,
'Die Zersetzung, &e.^ p. 91).

Mannitol has been found in the urine
of dogs after giving morphia or after
feeding with rye bread (JafPe, Zeit.
physiol. Ch. 7, 297). The mannitol in
the last case may have been derived
directly from the bread.

Synthetical Pkocesses.

[A.] Formic aldehyde [9l] in contact
with lime water or a mixture of mag-
nesia, magnesium sulphate, and lead
gives a syrupy mixture containing a-
acrose = i-fructose (Loew, Journ. pr.
Ch. [2] 33, 321, 34, 51; Fischer, Ber.

21, 989; Fischer and Passmore, Ber.

22, 359 ; Loew, ibid. 475 : see also
ButlerofP, Ann. 120, 295 ; Tollens, Ber.
15, 1629; 16, 1917; Wehmer and
Tollens, Ber. 19, 707 and 2135). On
treatment with phenylhydrazine the
a-acrosazone is obtained (Fischer), and
this by the action of strong hydrochloric
acid furnishes the corresponding a-acros-
one (Fischer and Tafel, Ber. 22, 98).
The latter by reduction with zinc dust
and acetic acid gives i-fructose which,
by reduction with sodium amalgam, is
converted into i-mannitol = a-acritol
(Fischer and Tafel, Ber. 22, 100) ; the
i-mannitol by oxidation with dilute
nitric acid gives i-mannose (Fischer,
Ber. 23, 390), and by further oxidation
with bromine i-mannonic acid. The

106

POLYHYDRIC ALCOHOLS

[51 A-52.

latter by fractional crystallisation of
the morphine or strychnine salt is re-
solved into d- and 1-mannonic acids.
The d-acid on reduction with sodium
amalgam in acid solution gives (l-ma7i-
nose [156], and by further reduction of
the latter with sodium amalgam in
alkaline solution d-mannitol (Fischer
and Hirschberger, Ber. 21, 1 8o8 : see
also Ber. 23, 2133).

[B.] Glycerol [48] when heated with
dehydrating agents, such as acid potas-
sium sulphate, yields acrolein [lOl]
(Redtenbacher, Ann.47, I20j Aronstein,
Ann. Supp. 3, 1 80 ; Van Romburgh, Bull.
Soc. [a] 36, 550 ; Griner, Ann. Chim.
[6] 26, 367 ; Wohl and Neuberg, Ber.
32, 1352), which combines with bromine
to form acrolein bromide = 2 : 3-di-
brompropionic aldehyde (Aronstein, loc.
cit. 185; Henry, Ber. 7, iii2; Linne-
mann and Penl, Ber. 8, 1097). The
latter on treatment with baryta water
gives a product from which the osazone
of a-acrose can be isolated (Fischer and
Tafel, Ber. 20, 109a; 3566) and con-
verted into mannitol as under A.

Glycerol can also be directly oxidised
by means of bromine in presence of
sodium carbonate solution (Fischer and
Tafel, Ber. 20, 3385), the 'glycerose'
thus obtained giving rise by the action
of alkali to a mixture of sugars from
which a-acrose can be isolated and
treated as above.

Note : — According to Neuberg (Ber. 35, 2632)
acrose partly consists of d-fructose. Glycerose
is a mixture of dihydroxyacetone and glyceric
aldehyde, the former predominating (see under
dihydroxyacetone [151 ; D]).

[C] Acetone [IO6] gives a dibromide
(CgHgO . Brg) by the action of bromine,
this compound on distillation giving
acrolein (Linnemann, Ann. 125, 310),
which can be converted into a-acrose,
&c., as under B.

[D.] From dextrose [l54] by reduc-
tion with sodium amalgam (Dewar,
Phil. Mag. 4, 39 ; Adrian Brown,
Trans. Ch. Soc. 51, 642; Bouchardat,
Bull. Soc. [2] 16, 38). The yield is
small.

[E.] From IfBvulose [155] by reduc-
tion with sodium amalgam (Krusemann,
Ber. 9, 1465 ; Fischer, Ber. 23, 3684).

The yield is 30-40 per cent, of the
Isevulose, about 50 per cent, of sorbitol
being formed simultaneously.

[F.] From mannose [l56] through
Isevulose (see under sorbitol [52; C]),
and then as above under E.

[G.] From tartaric acid [Vol. II]
through dihydroxymaleic acid by oxida-
tion with hydrogen peroxide in presence
of ferrous salts. The acid referred to
decomposes in aqueous solution with
the formation of glycollic aldehyde, and
the latter, on heating in vacuo at 100°,
polymerises to a mixture of a- and j8-
acrose (Fenton, Trans. Ch. Soc. 65,
899; 67,48; 774; 69,546; 71,375;
Jackson, Knd. 77, 129). The polymeri-
sation of the aldehyde takes place in
presence of dilute caustic soda at 0°
(Jackson, loc. cit.).

[H.] From acefal [93] through gly-
collic aldehyde (see under furfural [126 ;
P]), and then as above.

[I.] From etki/l alcohol [14] through
glycollic aldehyde . (see under furfural
[126 ; G]), and then as above.

[J.] From choline [Vol. II] through
glycollic aldehyde (see under furfural
[126 ; H]), and then as above.

[K.] Gluconic acid [Vol. II] has been
said to give mannitol on reduction with
sodium amalgam in acid solution (v.
Wachtel ; Tollens, ' Kohlenhydrate,' II,
282; Fischer, Ber. 23, 930 : see also
Herzfeld, Ann. 220, '^'^S).

52. Sorbitol ; Hexauehexol.

HOH HO HO

I I I I
HO . H.C-C-C-C-C-CH^ . OH

I I I I
H HOH H

(Dextro-modifieation).

Natural Sources.

In berries of mountain-ash (Boussin-
gault, Ann. Chim. [4] 26, 376 ; Hitze-
mann and Tollens, Ber. 22, 1048) ; in
apples, pears, medlars, plums, and
cherries (Vincent and Delachanal,
Comp. Rend. 108, 354; 109, 676;
114, 486 ; Bull. Soc. [2] 34, 218), and
in beet-sugar molasses (v. Lippmann,
Ber. 25, 3216).

52-54.] SORBITOL

Sorbitol is converted into sorbose,
the hexose (ketose) from mountain- ash
berries, by the action of a Bacferinm
(Bertrand, Comp. Rend. 122, 900;
126, 653). The sorbose Bacterium of
Bertrand is, as suspected by this author,
J3. xylinum of A. J. Brown (Emmerling,
Ber. 32, 541).

Synthetical Processes.

[A.] From dextrose [154] by reduction
with sodium amalgam (Meunier, Comp.
Rend. Ill, 49). Mannitol is formed to
some extent [51 ; D].

[B.] From lavulose [155] by reduc-
tion with sodium amalgam (Fischer,
Ber. 23, 3684 : see also under manni-
tol [51; E]).

[C] Mannose [l56] with phenyl-
hydrazine in excess gives glucosazone
(Fischer, Ber, 20, 831; Fischer and
Hirschberger, Ber. 21, 1805; 22, 365;
1 155; Reiss, Uid. 609), and this on
heating with fuming hydrochloric acid
yields the osone (Fischer, Ber, 21, 3631 ;
22, 88 j 23, 2120). The latter on
reduction with zinc and acetic acid
gives IfBvnIose [l55] (Fischer, Ber. 23,
2121), which can be reduced to sorbitol
as above under B.

lor

53. Mannoheptol ; Ferse'itol ;
Heptaneheptol.

H H HO HO

I I I I
HO . H,C . CH(OH)-C— C-C-C— CHa . OH

I I I I
HOHOH H
or

H H HO HO

I I I I
HO . HjC . C-C— C-C— CH(OH) . CH, . OH

I I I I
HOHOH H

(Dextro-modification).

Natural Source.

In fruit, seeds, and leaves of Laurus
persea (Avequin, 1831 ; Melsens, Ann.
Chim. [2] 72, 109 ; Miintz and Mar-
cano, Comp. Rend. 99, 38 ; Ann. Chim.
[6] 3, 279; Maquenne, Comp. Rend.
107, 583 ; Ann. Chim. [6] 19, 5).

Synthetical Process.

[A.] From formic aldehyde [9l] or
glycerol [48] through d-mannose as
under mannitol [51 ; A]. The d-man-
nose forms a cyanhydrin by the action
of hydrogen cyanide [172], which hydro-
lyses to d-mannoheptonic acid (Fischer
and Hirschberger, Ber. 22, 370; Fischer
and Passmore, I3er. 23, 2226). The
anhydride (lactone) of this acid reduces
to d -mannoheptol by the action of
sodium amalgam (Fischer, Ber. 23,
936 J Fischer and Passmore, ibid. 2231).

AROJMATIC ALCOHOLS AND PHENOLS.

54. Benzyl Alcohol ;
Fhenylcarbinol ; Fhenemethylol.

CH2 . OH

Natural Sources.

Occurs as benzoate in Peru balsam
from ]\1yroxylo7i {Tohifera) pereiree, San
Salvador ; as cinnamic ester in this
balsam and in liquid storax from
Liquidambar orientalis. As benzoate

and cinnamate in tolu balsam from
Myroxylon toluiferxim, New Granada,
Venezuela, Brazil, and Ecuador (Schar-
ling, Ann. 97, 168 ; Kraut, Ann. 107,
208; 109, 255; 152, 129; Strecker,
Jahresber. 1868, 566 ; Laubenheimer,
Ann. 164, 289 ; Busse, Ber. 9, 830 ;
Erdmann, Pharm. Journ. 65, 387 ;
Journ. Soc. Ch. Ind. 19, 1140).

The alcohol is said to occur in small
quantity in the free state in Peru bal-
sam (Kraut, Ann. 152, 129: compare
Thorns, Arch. Pharm. 237, 271). Ben-
zyl alcohol has been found in the
volatile oil of the cherry laurel, Prunvs

103

AROMATIC ALCOHOLS AND PHENOLS

[54 B.

laurocerasus (Tilden, Pharm. Journ. [3]
5, 761).

Benzyl acetate is the chief constituent
of the ethereal oil of jasmine from
Jasminnm grandijiorum (Hesse and
Miiller, Ber. 32, 565 ; 765 ; Hesse,
Ibid. 1611; 33,1585; 34,291; 2916:
see also E. Erdmann, Ber. 34, 2281).
The free alcohol occurs also in this oil
(Hesse and Miiller, loc. cit., ']6$ ; Hesse,
Ibid. 2619; Ch. Ind. 25, i).

The lower boiling fraction of the oil
of cassia flowers from Acacia farnesiana
probably contains benzyl alcohol (Schim-
meFs Ber. April, 1901). The alcohol
lias been found in considerable quantity
in the distillation water from ylang-
yla.ng essence (v. Soden and Rojahn,
Ber. 34, 2809). It is contained in this
last oil probably as benzyl salicylate and
benzoate (Schimmel^s Ber. Oct. 1901).
The chief constituent of the oil of
Gardenia is benzyl acetate (Parone,
Boll. Chim. Farm. 41, 489; Ch. Centr.
1902, 2, 703).

Synthetical Processes.

[A.] From acetylene through benzene
(see under cymene [6; A]). Benzene
can be converted into toluene by treat-
ing brombenzene and methyl iodide with
sodium (Fittig and Tollens, Ann. 131,
303), or by passing methyl chloride
into benzene containing aluminium
chloride (Friedel and Crafts, Ann.
Chim. [6] 1, 460 ; 11, 264). Toluene
gives benzyl alcohol among the pro-
ducts of its oxidation by manganese
dioxide and sulphuric acid (Weiler, Ber.
33, 464), and benzyl acetate by oxida-
tion with chromic acid or potassium
permanganate in acetic acid solution
(Boedtker, Bull. Soc. [3] 25, 843).

Toluene is converted into benzyl
chloride by passing chlorine into the
boiling liquid (Cannizzaro, Ann. Chim.
[3] 45, 468 ; Beilstein and Geitner,
Ann. 139, 337 : see also Lauth and
Grimaux, Bull. Soc. [2] 7, 105), or at
ordinary temperatures by chlorinating
in sunlight (Schramm, Ber. 18, 608).
Benzyl chloride can be converted into
benzyl alcohol by treatment with
potassium acetate and subsequent hydro-

lysis (Cannizzaro, Ann. 96, 246 ; Seelig,
tfourn. pr. Ch. [2] 39, 167), by heating
with a solution of potassium carbonate
(Meunier, Bull. Soc. [2] 38, 159), with
water and lead hydroxide (Lauth and
Grimaux, Ann. 143, 81), or with water
only (Niederist, Ann. 196, '^f^'^- Ben-
zyl acetate is formed by the interaction
of benzyl chloride and lead acetate
(Bodroux, Bull. Soc. [3] 21, 288).

Also from acetylene through ethylene
(see under ethyl alcohol [14; A]), ethy-
lene chloride, vinyl chloride by alcoholic
potash (Regnault, Ann. 14, 28), and
chloracetaldehyde by the action of
mercuric oxide on vinyl chloride (Glin-
sky, Zeit. [2] 3, 678 ; 4, 617 ; 6, 647).
The aldehyde by treatment with hydro-
gen cyanide [l72] and hydrochloric acid
gives ^-chlorlactic acid {Ibid. [2] 6,
515; Frank, Ann. 206, 344), which is
converted by silver oxide into glyceric
acid (Frank, loc. cit. 348). The latter
gives pyrotartaric acid as under F,
citrabrompyrotartaric acid and allylene
as under W, mesitylene, uvitic acid, and
toluene as under D.

Note : — All generators of ethylene thus be-
come generators of toluene and of benzyl
alcohol.

[B.] Benzoic aldehyde [114] on treat-
ment with caustic alkali gives benzyl
alcohol and benzoic acid (Cannizzaro,
Ann. 88, 129; Meyer, Ber. 14, 2394;
Kohn and Trantom, Trans. Ch. Soc.
75, 1155; Raikoff and Raschtanoff,
Ch. Centr. 1902, 1, 1212), or benzyl
alcohol by reduction with sodium amal-
gam (Friedel, Jahresber. 1862, 263;
Bull. Soc. 1862, 18). Also from benzoic
aldehyde through toluene by heating
with hydriodic acid (Berthelot, Jahres-
ber. 1867, 346), and then as under A.

Or benzaldoxime or hydrazone gives
benzylamine on reduction with sodium
amalgam and acetic acid, or by electro-
lysis (Goldschmidt, Ber. 19, 3232;
Tafel, Ibid. 1928; Tafel and Pfeffer-
mann, Ber. 35, 15 10). Benzylamine
may be converted into benzyl alcohol
by the action of nitrous acid (see Curtius,
Ber. 17, 958).

Note: — For generators of benzylamine see
also under benzyl mustard oil [169].

54 C-F.J

BENZYL ALCOHOL

109

[C] Benzoic acid [Vol. II] g-ives
benzyl alcohol on reduction with sodium
amalgam (Herrmann^ Ann. 132^ 76 ;
133,335).

Benzoyl chloride by reduction with
sodium amalg-am in presence of hydro-
gen chloride, or by reduction with
sodium amalgam alone in moist ethereal
solution, gives benzyl alcohol (Lipp-
mann, Zeit. [2] 1, 700; Bull. Soc. [2]
4, 249 ; W. H. Perkin, junr., and Sud-
borough, Proc. Ch. Soc. 10, 216).

The following synthetical products
are generators of toluene, and therefore
of benzyl alcohol under A : —

Generators of Toluene through Mesitylene
and Uvitic Acid.

[D.] Acetone [l03] on treatment with
sulphuric acid condenses to mesitylene
(Kane, Phil. Trans. 44, 474 ; Hofmann,
Journ. Ch. Soc. 2, 104; Cahours, Comp.
Eend. 24, 255 ; Varenne, Bull. Soc. [2]
40, 266 ; Fittig and Briickner, Ann.
147, 42 ; Orndorff and Young, Am. Ch,
Journ. 15, 249 ; Meyer and Molz, Be?.
29, 2831 ; Lucas, ibid. 2884; Kiister
and Stallberg, Ann. 278, 210 ; Noyes,
Am. Ch. Journ. 20, 807). Mesitylene
on oxidation with nitric acid gives uvitic
acid (Fittig and V. Furtenbach, Zeit. [2]
4, I ; Ann. 147, 295), and the latter on
distillation with soda-lime yields toluene
(Baeyer, Zeit. [2] 4, 119).

[E.] Normal and isopropyl alcohols
[15 ; 16] through propylene (see under
glycerol [48 ; A]), propylene bromide,
allylene by the action of alcoholic potash
on the latter (Markownikoff, Ann. 118,
332 : see also Valentin, Ber. 28, 2664),
mesitylene by the action of sulphuric
acid on allylene (Schrohe, Ber. 8, 1 7 ;
Michael, Journ. pr. Ch. [2] 60, 441),
and then as under D.

Or indirectly through propylene brom-
ide and cyanide, pyro tartaric acid by
hydrolysis of the latter (Simpson, Ann.
121, 161), and then through citrabrom-
pyrotartaric acid as under N and ally-
lene as under M.

Propylene also forms a compound
with mercuric sulphate in acid solution
which readily decomposes with the for-
mation oi acrolein [lOl] (Deniges,Comp.

Kend. 126, 1145). The latter oxidises
readily to acrylic acid, which can be
converted into a-chlorlactic acid, glyceric
acid, pyrotartaric or pyroraeemic acid,
allylene, &c. (see under P, I, M).

Note : — All the generators of propylene re-
ferred to under glycerol [48 ; B ; C ; D ; E ;
F ; G, &c.] can be regarded as sources of allyl-
ene as above.

[P.] Glycerol [48] gives rise to allyl
alcohol or iodide (see under ethyl alco-
hol [14 ; G] and under isobutyl alcohol
[18 ; Dl), either of which can be con-
verted mto allyl chloride (Oppenheira,
Ann. 140, 205 ; Tollens, Ann. 156,
154; EltekofP, Journ. Buss. Soc. 14,
394). The latter on heating with strong
aqueous hydrochloric acid at 100° gives
propylene chloride (Reboul, Ann. Chim.
[5] 14, A^"^} which by the action of
alcoholic potash yields a mixture of a-
and ^chlorpropylene {Iljid., loc. cit.
460^ the latter on further treatment
>mh alcoholic potash giving allylene
/ (Friedel, Ann. 134, 262), which can be
converted into mesitylene and toluene
as under E and D.

Or the allyl iodide can be converted
into allyl cyanide by the action of
potassium, cyanide [l72] (Claus, Ann.
131, 58 ; Rinne and Tollens, Ann. 159,
106), and then into a-crotonic acid by
heating with potash solution (Will and
Korner, Ann. 125, 273). The crotonic
acid can be converted into allylene as
under G.

Or the allyl iodide can be converted
into pyrotartaric (methylsuccinic) acid
by heating with alcoholic potassium
cyanide and decomposition of the product
with potash (Claus, Ann. 191, "i^"] ; Ber.
5, 612; Euler, Ber. 28, 2952). The
pyrotartaric acid can be converted into
citrabrompyrotartaric acid and then into
allylene as under N.

Glycerol on oxidation with nitric acid
(Debus, Phil. Mag. [4] 15, 195 ; Ann.
106, 79 ; Sokoloff, Ibid. 95 ; Mulder,
Ber. 9, 1902; Beilstein, Ann. 120,
226), with bromine and water (Barth,
Ann. 124, 341) or mercuric oxide in
presence of barium hydroxide (Born-
stein, Ber. 18, 3357) gives glyceric acid
which on dry distillation yields, among
other products, pyrotartaric acid (Mol-

110

AROMATIC ALCOHOLS AND PHENOLS [54 F-H.

denhauer, Ann. 131, 337 ; 339 ; Bot-
tinger, Ann. 196, 92), which can be
treated as above. Glyceric acid also
gives among the products of its dis-
tillation (with acid potassium sul-
phate) pyroracemic acid (Moldenhauer,
Ann. 131, ^^^y; Bottinger, Ann.196, 93),
which can be converted into uvitic acid,
&c., as under I. (For preparation of
glyceric acid from glycerol by oxidising
with nitric acid in presence of red lead
see Zinno, Ch. Centr. 1898, 1, 26 ; also
Wohlk, Journ. pr. Ch. [2] 61, 200 : by
alkaline silver chloride, Cazeneuve, Bull.
Soc. [3] 15, 763.)

Or from glycerol through epichlor-
hydrin by the action of hydrochloric
acid (Berthelot, Ann. 92, 302 ; Ann.
Chim. [3] 41, 299 ; Hiibner and Miiller,
Zeit. [2] 6, 344 ; Watt, Ber. 5, 257 ;
Beboul, Ann. SuppL 1, 221 j Tollens
and Miinder, Zeit. [2] 7, 252 ; Prevost,
Journ. pr. Ch, [2] 12, 160 ; Claus, Ber.
10, 557 ; Cloez, Ann. Chim. [6] 9, T45).
Epichlorhydrin condenses with hydrogen
cyanide [172] to form a nitrile which
gives crotonic acid on reduction with
hydriodic acid (Lespieau, Comp. Bend.
127, 965 ; 129, 224).

Or from glycerol through acrolein
[101] (see under mannitol [51 ; B]),
acrylic acid (Wohlk, Journ, pr. Ch. [2]
61, 200), a-chlorlactic, glyceric, pyro-
tartaric acids, and allylene as above under
^ E. Or from acrolein through ^-chlor-
propionic aldehyde and acid and acrylic
acid (Geuther and Cartmell, Ann. 112,
3; Krestownikoff, Jahresber. 1880,696;
Wohlk, loc. cit.).

Or from glycerol through allyl alco-
hol (see under ethyl alcohol [l4 ; G]),
o/3-dibrompropyl alcohol, a^-dibrom-
propionic acid and acrylic acid (Biil-
mann and Wohlk, Journ. pr. Ch. [2]
61, 199 ; 215), and then as above. Or
from fi/3-dibrompropionic acid to gly-
ceric acid as under O below. Or from
allyl alcohol through glyoxal (172 ;
BB), and, by means of hydrogen cyanide
[172], the nitrile of pyroracemic acid as
below under H.

[G-.] Malonic acid [Vol. II], paralde-
hyde (by polymerisation of acetaldehyde
[92]), and glacial acetic acid [Vol. II]
when heated to 100° give a-crotonic

(2-butenoic) acid (Komnenos, Ann, 218,
149). The latter combines with hypo-
chlorous acid to form a-chlor-/3-hydroxy-
butyric acid (Erlenmeyer and Miiller,
Ber. 15, 49; Melikoff, Ann. 234, 198).
This acid on heating with strong aqueous
hydrochloric acid at 100° gives a/3-di-
chlorbutyric acid (Melikoff, loc. cit.
201), which, by heating with excess of
aqueous alkali, yields a-chlorisopropyl-
ene (Wislicenus, Ann. 248, 297). The
latter on heating with alcoholic potash
gives allylene which can be treated as
above.

Or crotonic acid (ester) is condensed
by sodium ethoxide to form dicrotonic
ester from which the acid can be ob-
tained by hydrolysis. Dicrotonic acid
gives on oxidation with alkaline per-
manganate methylsuccinic = pyrotar-
taric acid (v. Pechmann, Ber. 33, 3323),
which can be converted into allylene,
&c., as under N below.

Or malonic acid (ester) can be con-
verted into methylmalonic ester by
sodium and methyl iodide. The sodium
derivative of methylmalonic ester inter-
acts with ethyl chloracetate to form
a propanetricarboxylic ester, the acid
( = a-methylethenyltricarboxylic acid)
from which gives pyrotartaric acid on
hydrolysis (Bischoff and Kuhlberg, Ber.
23, 635).

Or from diethyl malonate, aldehyde,
and acetic anhydride through ethyli-
denemalonic ester, /3-cyanobutyric acid,
and pyrotartaric acid (see under n-propyl
alcohol [15 ; T]).

[H.] Acetic aldehyde [92] by the action
of chlorine gives butyrochloral = 2:2:
3-trichlorbutanal (Kramer and Pinner,
Ber. 3, 383 ; Pinner, Ann, 179, 26),
which, by oxidation with nitric acid,
yields ao/3-trichlorbutyric acid (Kramer
and Pinner, loc. cit. 389 ; Judson, Ber.
3,785; Garzarolli,Ann,182,i8j), The
latter on reduction with zinc and water
(Sarnoff, Ann. 164, 93) gives a-chlor-
crotonic acid, which, by heating with
aqueous hydrochloric acid, yields a/3-
dichlorbutyric acid (Merlikoff, Ann.
234, 201). The latter can be converted
into allylene, &c., as under G.

aa/3-Trichlorbutyric acid also decom-
poses on heating the aqueous solution

54 H-I.J

BENZYL ALCOHOL

111

of the sodium salt with the formation
of aa-dichlorpropylene ; the latter on
heating- with alcoholic potash at 150°
gives allylene (Valentin, Ber. 28, 2661).
Butyrochloral also on treatment with
caustic alkali gives an allylene dichloride
which yields allylene by the action of
sodium (Kramer and Pinner, Ann. 158,
47 ; Pinner, Ann. 179, 44 ; Ber. 8, 898 ;
14, 108 1). The aa^iS-trichlorbutyric acid
also gives the same allylene dichloride
when the silver salt is boiled with water
^bid.).

Or aa/3-trichlorbutyric acid by the
action of caustic potash gives ay3-dichlor-
crotonic acid (Garzarolli, Ber. 9, 1209)
which, on heating with zinc and water,
yields tetrolic acid (SzenicandTaggesell,
Ber. 28, 167 1). The latter decomposes
at 210° with the formation of allylene
(see below under I).

Or the acetic aldehyde can be con-
verted into crotouic aldehyde [l02] (see
under normal butyl alcohol [17; G])
and the latter oxidised to a-crotonic acid
(Kekule, Ber. 3, 604; Zeit. [2] 6, 705),
which can be converted into allylene, &c.,
as under G.

Note : — Other generators of crotonic aldehijde
[102] are given under that compound, viz.
malic acid, acetylene, formic and acetic esters.

Or acetic aldehyde and hydrogen
cyanide [172] give a cyanhydrin which by
the action of phosphorus pentachloride
yields a chlorcyanhydrin, and this by
hydrolysis a-chlorpropionic acid (Michael
and Garner, Ber. 34, 4049). The latter
on heating with barium hydroxide gives
acrylic acid {Ibid. 4050). From the latter
through a-chlorlactic acid, glyceric acid,
&c., as above under E, F, &c.

Or from the aldehyde through glyoxal
(see under hydrogen cyanide [172 ; O]) :
the latter combines with hydrogen
cyanide to form pyroracemic nitrile,
from which the acid can be obtained
and treated as under I below.

[I.] From ethyl alcohol [l4] and acetic
acid through acetoacetic ester [Vol. II],
which gives a-crotonic acid by reduction
with sodium amalgam (Beilstein and
Wiegand, Ber. 18, 482). The acid can
be converted into allylene as under G-.

Ethyl alcohol on treatment with iodine

in the presence of alkali gives iodoform,
which by the action of sodium ethylate
yields acrylic acid (Butleroff, Ann. 114,
204). The latter combines with hypo-
chlorous acid to form a-chlorlactic acid
(Melikoff, Ber. 12, 2227), which by treat-
ment with silver oxide gives glyceric
acid [Ibid. 13, 272) : from the latter
pyrotartaric acid, citrabrompyrotartaric
acid, allylene, &c., can be obtained as
under P and M.

Ethyl ether (from ethyl alcohol) on
chlorination gives dichlorether (D^Areet,
Ann. 28, 82 ; Malaguti, Ann. Chim.
[2] 70, 338; [3] 10. 5; 19; Regnault,
Ibid. [2] 71, 392; Lieben, Ann. Ill, 121 ;
123, 130; 133, 287; 141, 236; 146,
180; 150, 87 ; Abeljanz, Ann. 164,
197), which by the action of strong sul-
phuric acid yields chloracetaldehyde
(Jacobsen, Ber. 4, 216). The latter
can be converted into ^Q-chlorlactic acid,
glyceric acid, &c., as under A.

Or ethyl alcohol can be converted
into chloracetal by chlorination (Lieben,
Ann. 104, 114), and the latter into
chloracetaldehyde by heating with acetic
acid, dilute sulphuric, or dry oxalic acid
(Natterer, Monats. 3, 446). The
chloracetaldehyde is treated as above.

Or ethyl alcohol can be converted
into chloral by chlorination, into chloral
cyanhydrin (Hagemann, Ber. 5, 151 ;
Pinner and Bischoff, Ann. 179, 77;
Pinner, Ber. 17, 1997), trichlorlactic
acid by hydrolysis (Pinner and Bischoff,
loc. cit. I'jg ; Pinner, /oc. cit.), dichlor-
acetaldehyde by heating the sodium salt
with water (Reisse, Ann. 257, 331),
dichlorlactic acid by forming the cyan-
hydrin of dichloracetaldehyde andhydro-
lysing (Grimaux and Adam, Ber. 10,
903; Bull.Soc. [2]34, 29), chloracetalde-
hyde by heating sodium dichlorlactate
with water (Reisse, Ann. 257, '^^S)> ^^^
then as above.

Or ethyl alcohol can be converted
into ethyl cyanide (propionitrile : see
under normal propyl alcohol [15 ; A]),
aa-dichlorpropionic acid by chlorination
of the nitrile and hydrolysis (Otto, Ann.
132, 181 ; Beckurts and Otto, Ber.
9, 1877), pyroracemic (propanonic) acid
by heating dichlorpropionic ester with
water or the acid with water and silver

112

AROMATIC ALCOHOLS AND PHENOLS

[54 I-K.

oxide (B. and O.^ Ber. 10, 264; 18,
228). Pyroracemic acid gives pyro-
tartaric acid among other products by
heating to 100° with hydrochloric acid
or to 170° per se (De Clermont, Ber.
e, 72; Bottinger, Ber. 9, 837; 1823;
Ann. 188, 308 ; De Jong, Bee. Tr. Ch.
20, 81 ; 21, 191 : see also Wolff, Ann.
317, 22). Pyrotartaric acid can be con-
verted into allylene, mesitylene, &c., as
above.

Or (more directly) pyroracemic acid
gives uvitic acid, among other products,
on boiling with baryta water (Finckh,
Ann. 122, 184; Bottinger, Ann. 172,
241; 253; 188,313; 208, 129; Wolff
and Heipp, Ann. 305, 125 ; 152), which
acid can be converted into toluene, &c.,
as under D.

Or uvitic acid may be synthesised by
heating a mixture of pyroracemic acid
and acetic aldehyde [92] with baryta
water (Doebner, Ber. 23, 2377).

Acetic and pyroracemic acids are also
generators of toluene through phthalide-
dicarboxylic acid (see under cymene [6 ;

Acetic acid can be converted into
acetyl cyanide by the interaction of
acetyl chloride and silver cyanide (Hiib-
ner, Ann. 120, 334; 124, 315); the
cyanide on hydrolysis gives pyroracemic
acid (Claisen and Shadwell, Ber. 11,
620 ; 1563), which yields uvitic acid,
&c., as above.

Acetoacetic ester by the action of
nitrous acid gives isonitrosoacetone
(Meyer and Ziiblin, Ber. 11, 695 ;
Ceresole, Ber. 15, 1328), which, by the
action of acetyl chloride, yields acetyl
cyanide (Claisen and Manasse, Ber. 20,
2196). The latter can be converted into
pyroracemic acid as above.

Acetoacetic ester by the interaction
of the sodium derivative and a-Lrom-
propionw ester (Friedel and Machuea,
Ann. 120, 286 j Comp. Rend. 53, 408 ;
Bischoff, Ann. 206, 319 ; Zelinsky,
Ber. 20, 2026) gives /3-methylaceto-
succinic ester (Conrad, Ann. 188, 226 ;
Bischoff, loc. cit. 320) : the latter on
treatment with alcoholic potash yields
pyrotartaric acid (Conrad, loc. cit. 227).

Or by the interaction of chloracetic
ester and sodio-acetoacetic ester aceto-

succinic ester is formed (Conrad, loc. cit.
218; Rach, Ann. 234, 36), which by
the action of sodium and methyl iodide
gives a-methylacetosuccinic ester (Kress-
ner, Ann. 192, 135) : the latter on treat-
ment with alcoholic potash also yields
pyrotartaric acid [Ibid. 138).

Or the a- and /3-methylacetosuccinic
esters on heating with hydrochloric acid
give /3-acetyl butyric and ^-acetylisobu-
tyric acids respectively (Bischoff, Ann.
206, 319 and 331). Both these acids
on oxidation with dilute nitric acid yield
pyrotartaric acid {Ibid. 337) with other
products.

Acetoacetic ester also by the action
of methyl iodide on its sodium deriva-
tive gives methylacetoacetic ester, which
by the successive action of bromine and
alcoholic potash yields mesaconic acid
(Demar^ay, Ann. Chim. [5] 20, 473 ;
Gorboff, Journ. Russ. Soc. 19, 605 ;
Cloez, Bull. Soc. [2] 3, 598 and 602;
Wolf, Ann. 260, 89 ; Ssemenoff, Journ.
Russ. Soc. 23, 430 ; 30, TOC9 ; Conrad,
Ber. 32, 1005). Potassium mesaconate
solution gives allylene on electrolysis
(Aarland, Journ. pr. Ch. [2] 7, 142).

Acetoacetic ester by the action of
phosphorus pentachloride gives a mix-
ture of /3-chlor-a- and /3-crotonic acids
(Frolich, Zeit. [2] 5, 270 ; Geuther,
ibid. [2], 7, 237 j Autenrieth, Ann. 259,
359; Fittig, Ann. 268, 13). Both
these acids by the action of potassium
hydroxide give tetrolic (2-butinic) acid
(Geuther, loc. cit. 245 ; Friedrich, Ann.
219, 319, 342; Kahlbaum, Ber. 12,
2338; Fittig and Clutterbuck, Ann.
268, 96 : see also Desgrez, Bull. Soc.
[3] 11, 391). Tetrolic acid is decom-
posed at 210° into carbon dioxide and
allylene.

[J.] Allyl isothiocyanate [166] by the
action of zinc dust is converted into
allyl cyanide (Schwarz, Ber. 15, 2508),
which can be converted into a-crotonic
acid, allylene, &c., as under P. Water
also in contact with allyl isothiocyanate
gives allyl cyanide (Will and Korner,
Ann. 125, 272).

[K.] From normal butyric acid [Vol.
II] through the a-bromo-acid (see under
n- propyl alcohol [l5 ; P]), which gives
crotonic acid when the ethyl ester is

54 K-M.]

BENZYL ALCOHOL

113

treated with alcoholic potash or barium
hydroxide solution (Hell and Lauber,
Ber. 1, 560 ; Michael and Graves, Ber.
34j 4041 : compare also Duvillier,
Ann. Chim. [5] 17, ^3"^ ; Michael,
Journ. pr. Ch. [2] 35, 92; 38, 12;
Erlenmeyer and Marx as quoted by
Michael and Graves, loc. cit. 4040).
The sodium salt of a-brombutyric acid
also gives crotonic acid on distillation
(Bischoff and Walden, Ann. 279, loi).

Butyryl chloride on chlorination also
gives a- (with /3 and y) chlorbutyryl
chloride. The corresponding a-chloro-
acid gives crotonic acid (with a-hydroxy-
butyric acid) on treatment with barium
hydroxide solution (Michael and Garner,
Ber. 34, 4051).

[L.] ^-Hi/droxyhutyric acid [Vol. II]
gives crotonic acid on distillation (Wis-
licenus, Zeit. [2] 5, 325; Avaki, Zeit.
physik. Ch. 18, i). Or the acid (sodium
salt) gives crotonic aldehyde [102] on
electrolysis (v. Miller and Hofer, Ber.
27, 468). From the aldehyde through
crotonic acid, &c., as under H.

[M.] Cilric acid [Vol. II] gives
citraeonic anhydride on distillation
(Lassaigne, Ann. Chim. [2] 21, 100 ;
Bobiquet, Ihid. 75, 78 ; Liebig, Ann.
26, 119 ; 152 ; Gottlieb, Ann. 77, 365 ;
Baup, Ann. Chim. [3] 33, 192; Wilm,
Ann. 141, 28 ; Kammerer, Ann. 170,
191), which combines readily with
water to form citraeonic acid. The
latter is also obtained by heating citric
acid with hydriodic acid (Kammerer,
Ann. 139, 269). Potassium citraconate
gives on electrolysis in aqueous solution
allylene (Aarland, Journ. pr. Ch. [2] 7,
142) among other products, and this can
be converted into mesitylene, &c., as
under E.

Or the citraeonic anhydride can be
converted into citrabrompyrotartaric
acid by the action of hydrogen bromide
(Fittig, Ann. 188, 77), the silver salt of
the acid giving allylene on heating with
water at 130° (Bourgoin, Bull. Soc. [2]

28,459)-

Mesaconic acid, the isomeride of citra-
eonic acid produced from the latter by
heating with aqueous acids or alkalis or
by the action of bromine (Gottlieb, Ann.
77, 268 ; Kekule, Ann. Suppl. 2, 94 ;

Fittig, Ann. 188, 77 ; 80 ; Delisle, Ann.
269, 82 ; Swarts, Jahresber. 1873, 579 ;
Fittig and Langworthy, Ann. 304^ 145),
also gives allylene on electrolysis of a
solution of the potassium salt (Aarland,
Journ. pr. Ch. [2] 7, 142).

Citraeonic acid also by boiling with
alkali gives (with mesaconic acid) ita-
conic acid. The three isomerides, citra-
eonic, mesaconic, and itaconic acids, all
give pyrotartaric acid on reduction by
sodium amalgam, preferably in acid
solution (Kekule, Ann. Suppl. 1, 338 ;
Suppl. 2, 95 : also Fittig and Lang-
worthy, loc. cit.). The latter can be
treated as underN. Citraeonic and mesa-
conic acids give pyroracemic (pyruvic)
acid on oxidation (Fittig and Kohl, Ann.
305, 41). The latter can be converted
into uvitic acid, &c., as under I above.
Conversely pyroracemic and malonic
acid combine when heated in acetic
acid solution to form itaconic acid and
some citraeonic acid (GarzaroUi-Thurn-
lach, Monats. 20, 467).

Note : — Other synthetical products which
are generators of citraeonic acid are : — Lactic
acid [Vol. II] by distillation (Engelhardt, Ann.
70, 243 ; 246).

Acetic acid [Vol. II], alcohol [14], and hydrogen
cyanide [172], by the action of the latter on aceto-
acetic ester (Morris, Journ. Ch. Soc. 37, 7 ; De-
mar9ay, Bull. Soc. [2] 27, 120), hydroxypyro-
tartaric acid by boiling the product with dilute
hydrochloric acid and dry distillation of the
former, which thus gives citraeonic anhydride
(Demarfay, Comp. Rend. 82, 1337 ; Ber. 9,962).

Isovaleric acid [Vol. II], which by oxidation
with nitric acid gives hydroxy pyrotartaric acid
(Bredt, Ber. 14, 1782 ; 15, 2318) and citraeonic
anhydride as before. [The hydroxypyrotar-
taric acid formed is the ;8-acid = citramalic =
2-methyl-2-butanoldiacid ; for preparation from
acetoacetic ester and potassium cyanide see also
Michael, Journ. pr. Ch. [2] 46, 287.]

Propionic and malonic acids [Vol. II] by the
action of a-brompropionic ester (Friedel and
Machuea, Ann. 120, 286) on sodio-malonic
ester, which gives propanetricarboxylic tri-
ethyl (/3-methylethenyltricarboxylic) ester (Bi-
schoff, Ann. 214, 53), the chloro-derivative of
the latter {Ibid. Ber. 23, 1934) giving citra-
eonic (and mesaconic) acid on heating with
hydrochloric acid {Ibid.). [This propanetricar-
boxylic acid obtained from the ester by hydro-
lysis gives pyrotartaric acid on heating with
hydrochloric acid or per se.]

Acetic and propionic acids [Vol. II], alcohol [14],
and potassium cyanide [172] through a-methyl-
/3-eyanosuecinic ester by the action of a-brom-
propionic ester on sodio-cyanacetie ester
(Bar the, Ann, Chim. [6] 27, 277), and decompo-
sition with alcoholic hydrogen chloride {Ibid.
281).

114

AROMATIC ALCOHOLS AND PHENOLS [54 M-B.

Oxalic and propionic acids [Vol. II] and alcohol
[14] through methyloxalacetic ester by the
action of sodium ethoxide followed by that of
ethyl propionate on oxalic diethyl ester (Ar-
nold, Ann. 246, 329). Methyloxalacetic ester
gives /3 - methylmalic (2-methyl-3-butanoldi-
carboxylic) acid on reduction with sodium amal-
gam (Wislicenus, Ber. 25, 199), and this acid
gives citraconic anhydride and mesaconic acid
on distillation.

[N.] Tartaric acid [Vol. II] throug-h
pyrotartaric (methylsuccinic) acid (see
under normal propyl alcohol [15 ; V]),
citrabrompyrotartaric acid by the action
of bromine and phosphorus (Auwers
and Imhauser, Ber. 24^ l^^fi), and then
through allylene, &c., as under M.

Itacemic acid also gives pyrotartaric
acid on distillation (references as under
normal propyl alcohol [15 ; V]).

Both tartaric and racemic acids give
pyroracemic acid among the products of
their distillation (Berzelius, Pogg- Ann.
36^ I ; Ann. 13, 61 ; Volckel, Ann.
89, 65; Wislicenus, Ann. 126, 225).
Tartaric acid gives pyroracemic acid by
heating to 180° with hydrochloric acid
(Geuther and Riemann, Zeit. [a] 5,
318), to 40° with strong sulphuric acid
(Bouchardat, Comp. Rend. 89, 99), or
by dry distillation per se, or mixed with
sand, pr with acid potassium sulphate
at 220° (Clewing, Journ. pr. Ch. [2] 17,
243 ; Erlenmeyer, Ber. 14, 320 ; Dobner,
Ann. 242, 269; Seissl, Ann. 249,
^97 ; Erdmann, Zeit. f. Naturwissen-
schaften, 71, 385). Pyroracemic acid
is produced in aqueous solutions of tar-
taric acid by photochemical action
(Otto, Ber. 27, 838 j 1264). Pyrorace-
mic acid can be converted into uvitic
acid, &c., as under I. (For conversion
of acetic and pyroracemic acids into
toluene via phthalidedicarboxylic acid
see under cymene [6 ; IX].)

[O.] Propionic acid [Vol. II] on bro-
mination gives aa-dibrompropionic acid
(Friedel and IVTachuca, Comp. Rend.
54, 220; Philippi and Tollens, Ann.
171, 315; Epstein, Comp. Rend. 124,
688), which on long heating with fum-
ing hydrobromio acid solution is con-
verted into the a^-acid (P. and T. loc.
cit. '^2)1)' ^^^ latter on heating with
water and silver oxide gives glyceric
acid (Beckurts and Otto, Ber. 18, 238),

which furnishes pyrotartaric acid, &c.,
as under F, M, and N.

Or the aa-dibrompropionic acid on
heating with silver carbonate and water
yields pyroracemic acid {Ibid. 235),
which gives uvitic acid, &c., as under
I and D.

Or the propionic acid can be con-
verted into propionamide and propioni-
trile (Dumas, Malaguti, and Leblanc,
Ann. 64, 334), and then into aa-dichlor-
propionic acid, pyroracemic acid, &c., as
before.

Or through propionyl chloride and
/3-chlorpropionic acid, which gives acrylic
acid on heating with barium hydroxide
solution (Michael and Garner, Ber. 34,
4047). From acrylic through a-chlor-
lactic to glyceric and pyrotartaric or
pyroracemic acid as before.

[P.] Lactic acid [Vol. II] gives
pyroracemic acid by oxidation of the
calcium salt with potassium perman-
ganate (Beilstein and Wiegand, Ber.
17, 840). Subsequent steps as above.

Or from lactic acid through a-chlor-
propionic acid (Wurtz, Ann. Chim. [3]
49, 58 ; Briihl, Ber. 9, '^^), which on
heating with barium hydroxide solution
gives acrylic acid (Michael and Garner,
Ber. 34, 4050). From the latter through
a-chlorlactic to glyceric and pyrotartaric
or pyroracemic acid as before.

[Q.] Isovaleric acid [Vol. II] gives
mesitylenic acid among other products
when the dry sodium salt mixed with
sodium ethoxide is heated in the pre-
sence of carbon monoxide at 160° (Loos,
Ann. 202, 321). Mesitylenic acid gives
uvitic acid on oxidation (Fittig and v.
Furtenbach, Zeit. [2] 4, i ; Ann. 147,
295), and the latter yields toluene as
under D.

Note : — Allylene is among the products formed
when the vapours of acetone [106], ethyl [14],
propyl [15], isobutyl [18], and amyl [22] alcohols
are passed over hot magnesium, and the product
decomposed by water (Reiser and Breed, Ch.
News, 71, 118 ; Reiser, Am. Ch. Journ. 18, 328).

Generators of Toluene through Toluic
Acid.

[R.] Naphthalene [12] and deriva-
tives by various processes of oxidation
give phthalic acid (Laurent, Ann. 19,
38 ; Ann. Chim. [2] 61, 1 13 ; Marignac,

64 B-Y.]

BENZYL ALCOHOL

115

Ann. 42_, 315 ; Haussermann, Jahresber.
1877, 763 ; 1 158 ; Fischer, Ber, 11, 738 ;
Depouilly, Ann, 137, c^y^ ; Beilstein
and Kurbatoff, Ann. 202, 215; Liid-
dens, Chem. Zeit. 15, 585 ; Fuchs, J bid.
735 ; Graebe, Ber. 29, 2806 ; Pro-
chazka, Ber, 30, 3108; Tcherniac, Ber.
31, 139 : for electrolytic oxidation see
Darmstadter, Germ. Pat. 1090 12 o£
1897; Ch. Centr, 1900, 2, 151 : for
technical process see Germ. Pat. 91202
of the Bad. An. Sod. Fab. and Brunek,
Ber. 33, Suppl. Ixxx : for production
by oxidation of the naphthols see Eng-.
Pat. 15527 of 1901, Basle Ch. Co.;
from a-nitronaphthalene via the 2- and
4-nitronaphthols, liid. Germ. Pat.
136410 of 1901 j Ch. Centr. 1902, 2,
137 1). Phthalic acid on distillation
with phosphorus pentachloride is con-
verted into phthaloyl chloride (Miiller,
Zeit. 1863, 257; Graebe, Ann. 238,
329 ; Auger, Ann. Chim. [6] 22, 295 ;
Claus and Hoch, Ber. 19, 11 87), which
by reduction with zinc and hydrochloric
acid or magnesium and acetic acid gives
phthalide (Kolbe and Wischin, Zeit.
[2] 2, 315; Journ. Ch. Soc. 19, 339;
Hessert, Ber. 10, 1445; Baeyer, Zeit.
[2] 6, 399 ; 10, 123; 1445; 11. 6s7).

Or phthalic acid can be converted
into phthalide through phthalimide by
beating the acid ammonium salt (Lau-
rent, Ann. 41, iio; Ann. Chim. [2]
61, 121; [3] 23, 119; Lansberg-, Ann.
215, 181 : also Matthews, Journ. Am.
Ch. Soc. 18, 679), reduction to phthal-
imidine by tin and hydrochloric acid
(Graebe, Ber. 17, 2598 ; Ann. 247,
291), formation of nitroso-derivative
by the action of sodium nitrite and acid
(Pnd. Ann. 247, 297), and action of
sodium hydroxide solution on the ni-
troso-derivative (Ibid. 292). By heating
phthalide with hydriodic acid solution
and phosphorus, orthotoluic acid is
formed (Hessert, Ber. 11, 238 ; Racine,
Ann. 239, 72), and this by distillation
with lime or soda-lime gives toluene.

Naphthalene also can be sulphonated
so as to give a mixture of disulphonic
acids, the product nitrated and reduced,
and the 1:3: 8-naphthylamine-disul-
phonic acid converted into i : 3-naph-
thylaminesulphonic acid by sodium

i2

amalgam, or by heating* with sulphuric
acid of y^ per cent. (Friedlander and
Lucht, Ber. 26, 3028 ; Kalle & Co.,
Germ. Pat. 64979 of 1892). The i : 3-
sulpho-acid is converted by potash fusion
into 1 : 3-aminonaphthol (Friedlander,
Ber. 28, 1952). The latter on sul-
phonation gives i : 3-aminonaphthol-4-
sulphonic acid, and this on heating with
water or dilute sulphuric acid at 120°
yields i : 3-dihydroxynaphthalene (Tdid.
29, 1609), which on heating with 60
per cent, sodium hydroxide solution at
180-190° breaks down into o-toluic and
acetic acids (Ibid. 161 1).

Other naphthalene derivatives such
as the I : 3-disulphonic acid, i : 3-naph-
thylamine-sulphonic acid, &c., give
o-toluic acid on heating with alkali
(Kalle & Co., Germ. Pat. 79028 of
1893; Ber. 28, Ref. 364).

[S.] Cymene [6] on oxidation with
dilute nitric acid gives paratoluic acid
(Noad, Phil. Mag. [3] 32, 19; Ann.
63, 289), which on distillation with
baryta g-ives toluene {Ibid. Ann. 63,
3'^h)'

Miscellaneous Generators of Toluene.

[T.] Heptane [2] gives toluene among
other products when the vapour is
heated to 900° (Worstall and Burwell,
Am. Ch. Journ. 19, 815).

[U.] Mannoheptol [53] on heating
with hydriodic acid gives among other
products a * heptine,' ^7^x2 (Maquenne,
Bull. Soc. [2] 50, 548). If, as is
probable, this hydrocarbon is tetra-
hydrotoluene, it can be converted (par-
tially) into toluene by the action of
strong sulphuric acid.

[v.] From the cresols [61 ; 62 ; 63]
through toluene (see under quinol
[71; G]).

[W.] From phenylacetic acid [Vol. II]
through toluene by the action of heat
on the acid (Engler and Low, Ber. 26,

^438).

[X.] From aconitic acid [Vol. II]
through itaconic acid (Pebal, Ann. 98,
94), and then as above under M, &c.

[Y.] From pulegone [128] through
methylcyclohexanone (see under phenol
[60; SJ). The latter gives an oxime

116

AROMATIC ALCOHOLS AND PHENOLS [54 Y-55.

which on heating with phosphorus
pentoxide yields toluene among other
products (Wallach, Ann. 309, 7).

Pulegone and menthone [l29] give
pyrotartaric acid among the products
of oxidation by potassium perman-
ganate (Markownikoff, Ber. 33, 1909).
Subsequent steps as above under M".

[Z.] From malic acid [Vol. II]
through coumalic acid and crotonic
aldehyde [l02], and then as above
under H.

Malic acid also gives oxalacetic acid
on oxidation with hydrogen dioxide in
presence of ferrous salts. If the tem-
perature is not kept low pyroracemic
acid is produced (Fenton and Jones,
Trans. Ch. Soc. 77, 77). From oxal-
acetic acid through pyrotartaric acid,
&c., as before (see under n-propyl alcohol
[15 J Z]).

[AA.] From mannltol [5l], which
gives acrolem [lOl] among the pro-
ducts of oxidation by sulphuric acid
and manganese dioxide (Backhaus,
Jahresber. 1860, 522). Subsequent
steps via acrylic acid as under I, &c.

[BB.] From alanine [Vol. II], which
gives acrylic acid on treatment with
metJiyl iodide in the presence of alkali
(Korner and Menozzi, Gazz. 11, 258 ;

549 ; 13, 350).

[CO.] From oxalic and acetic acids
[Vol. II] and alcohol [14] through
aiethyloxalacetate and pyrotartaric
acid (see under n-propyl alcohol [15;

[DD.] From succinic acid [Vol. II]
through the dibro mo-acid, ethoxyfuma-
rie acid, and oxalacetic acid (see under
n-propyl alcohol [15 ; Y]). From the
latter to pyrotartaric acid, &c., as under
n-propyl alcohol [l5; Z].

[EE.] From fumaric or malew acid
[Vol. II] through dibromsuccinie acid
(n-propyl alcohol [l5 ; EE]), and then
as above under DD.

[PP.] From hydracrylic acid [Vol. II]
through acrylic acid (n-propyl alcohol
[15 ; S]). From acrylic acid through
a-chlorlactic acid, glyceric acid, &c., as
above under I, &c.

[GG.] From isobutyl [is] or tertiary
butyl alcohol [19] through isobutylene
[I8 ; A j 19 ; B]. Toluene is among

the products formed by passing iso-
butylene through a hot tube (Noyes;
Beilstein, I, 115).

Note : — Genera tors of isobutylene thus become
generators of benzyl alcohol.

[HH.] From lysine [Vol. II] through
pyrotartaric acid (see under n-propyl
alcohol [15 ; II]).

[II.] From catechol [69] and hydrogen
cyanide [172] through dioxytartaric acid
and glyoxal (see under hydrogen cyanide
[172 ; P]), and the pyroracemic nitrile
and acid as above under H.

[JJ.] Yrom. protocateohuic acid [Vol.
II] through dioxytartaric acid and
glyoxal, &c., as under hydrogen cyanide
[172 ; Q], and as above under H.

55. Saligenin ;

Orthohydroxybenzyl Alcohol ;

Fhenol-2-Meth7lol.

CH2.OH
H

'^

Natural Sources.

Occurs as the glucoside (salicin [157])
in bark, twigs, and leaves of various
species of willow {Salix helix, S. pur-
purea, S. alba, S. lambertina, S. incana,
S. Jissa, S. has lata, S. polyandra, S.fra-
gilis, S. amygdalina, S. pentandra, S. pre-
cox, &c.), in poplar (Populus tremnla,
P. alba, P. balsamifera, and P. grceca),
and in flower buds of the meadowsweet
{Spircea ^dmaria).

Salicin is found also in the buds of
Populus pyramidalis, P. nigra, and P.
monilifera. (For liberation of saligenin
from salicin see Piria, Ann. 56, 37 : for
distribution of salicin in vegetable
kingdom, Leroux, Ann. Ch. [2] 43,
440 ; Tischhauser, Ann. 7, 280 ; Bra-
connot, Ann. Chim. [2] 44, 296 ;
Pelouze and Gay-Lussac, Ibid. 220;
48, III ; Piria, Ibid. 69, 281 ; [3] 14,
257; Grerhardt, Ibid. [3] 7, 215;
Bouchardat, Comp. Rend. 18, 299 ; 19,
602; 1 1 79; 20,610; 1635; vciSpiroia
flowers, Buchner, Ann. 88, 224 : see

55-56.]

SALIGENIN

117

also Van Rijn's 'Die Glycoside/ p. 143,
and Jowett and Potter, Pharm. Journ.

[4] 15, 157.)

Salicin liberates saligenin under the
influence of certain moulds, such as
Aspergillus niger (Puriewitsch, Ber.
deutsch. bot. Gesell. 16, 368) and
A. oryz(B (Brunstein, Abst. in Journ.
Fed. Inst. 7, 367 ; 8, 507). Poptilin
[158], which is benzoylsalicin, liberates
benzoylsaligenin under the influence of
an enzyme (? emulsin) contained in
Aspergillus niger.

Salicin is said to occur also in cas-
toreum from glands of the beaver
(Wohler, Ann. 67, 360).

Synthetical Processes.

[A.] From salicylic aldeTiyde [HV] by
reduction with sodium amalgam (Beil-
stein and Beineke, Ann. 128, 179).

[B.] From salicylic acid [Vol. II]
through the amide (Limpricht, Ann.
98, 258), and reduction of the latter
with sodium amalgam in acid solution
(Hutchinson, Ber. 24, 175).

[C] From toluene (see under benzyl
alcohol [54 J A, &c.]), o-nitrotoluene,
which is formed (with p-nitrotoluene)
by nitration, o-nitrobenzyl chloride by
chlorination at 1 20-130° in the presence
of sulphur (Haussermann and Beck,
Ber. 25, 2445), o-nitrobenzyl alcohol
by heating the chloride with potassium
carbonate solution or with chalk and
water (SoderbaumandWidman, Ber. 25,
3291 ; Haussermann and Beck, Journ.
pr. Ch. [2] 47, 400 : see also Paal and
Bodewig, Ber. 25, 2962 ; Fischer, Germ.
Pat. 48722 of 1888; Ber. 22, Bef. 788;
Kalle & Co., Germ. Pat. 10436 of
1897; C^- Centr. 1899, 2, 950; Ch.
Fab. Griesheim-Elektron, Germ. Pat.
128046 of 1900; Ch. Centr. 1902, 1,
445; Germ. Pat. 128998 of 1900; Ch.
Centr. 1902, 1, 686). From o-nitro- to
o-aminobenzyl alcohol by reduction
(Friedlander and Henriques, Ber. 15,
3109) and diazo-reaction with latter
(Paal and Senninger, Ber. 27, 1084).

Note : — For references to processes for oxi-
dising o-nitrotoluene to o-nitrobenzaldehyde,
■which gives the alcohol as below under D, see
under indigo [Vol. II]. Orthonitrotoluene also
gives o-nitrobenzaldoxime by interaction with
amyl nitrite and dry sodium ethoxide (Lap-

worth, Trans. Ch. Soc. 79, 1274). o-Nitrotol-
uene gives o-nitrobenzyl alcohol by electrolytic
oxidation (Pierron, Bull. Soc. [3] 25, 852).

[D.] From cinnamic acid [Vol. Ill
through the o-nitro-acid which is formed
(with the p-nitro-acid) by nitration
(Beilstein and Kuhlberg, Ann. 163,
126), o-nitrobenzaldehyde by oxidising
the acid with potassium permanganate
(Einhorn, Ber. 17, I3i), and o-nitro-
benzyl alcohol, which is formed (with
o-nitrobenzoic acid) by the action of
cold aqueous caustic alkali on the alde-
hyde (Friedlander and Henriques, Ber.
14, 2804). Subsequent steps as above.

Note : — One of the products of nitration of
<u-bromstyrene from cinnamic acid (see under p-
hydroxybenzaldehyde [119 ; B]), viz. a-o-nitro-
phenyl-/3-bromnitroethylene, gives o-nitrobenz-
aldehyde on boiling with water (Fliirscheim,
Journ. pr. Ch. [2] 66, 16).

[E.] From phenol [6O] by the action
of methylene chloride in the presence of
alkali (Greene, Am. Ch. Journ. 2, 19).
Methylene chloride can be prepared
from chloroform [l ; D, &c.] by reduc-
ing the alcoholic solution with zinc and
hydrochloric acid (Greene, Ibid. 1, 522 ;
Ch. News, 50, 75; Comp. Rend. 89,
1077).

Also from phenol and formic aldehyde
[91] by the action of caustic alkaline
solution on a mixture (Manasse, Ber.
27, 2411 ; Lederer, Journ. pr. Ch. [2]
50, 225 : see also Farbenfab. vorm.
F. Bayer & Co., Germ. Pat. 85588 of
1894). Parahydroxybenzyl alcohol is
formed simultaneously in this process.

56. Parahydroxybenzyl Alcohol ;
Fheiiol-4-Methylol.

CHo.OH

HO

Natural Source.

The p-hydroxybenzyl complex occurs
in sinalbin, a glucoside found in white
mustard seed (see under p-hydroxy-
benzyl mustard oil [l7l]).

118

Synthetical Processes.

AROMATIC ALCOHOLS AND PHENOLS [56 A-58 O.

gam (Radziszewski, Ber. 9, 373) or^
preferably^ with zinc and acetic acid
(v. Sod en and Rojalin, Ber. 33^ 1723).

The generators of a-toluic aldehyde
given under phenylethyl mustard oil
[170] thus become generators of this
alcohol : —

[B.] From benzene or toluene through
a-toluic aldehyde (phenylethyl mustard
oil [170 ; A]).

[C] From styrene [7] through a-
toluic aldehyde (170 ; B).

[D.] From benzoic aldehyde [114], al-
cohol [14]^ and acetic acid [Vol. II]
through a-toluic aldehyde (170 ; C).

[E.] From cinnamic acid [Vol. II]
through a-toluic aldehyde (l70 ; E).

[F.] From benzoic and acetic acids
[Vol. II] through a-toluic aldehyde
(170; P).

[G.] From tartaric or racemic acid
[Vol. II] and n-propyl alcohol [15]
through a-toluic aldehyde (170 ; D).

[H.] From cymene [6] through aceto-
phenone and a-toluic aldehyde (170 ; G).

[A.] From phenol [60] through p-
hydroxybenzaldehyde [II8] by the action
of chloroform in the presence of caustic
alkali, the o-hydroxy-aldehyde being
also formed (Reimer and Tiemann, Ber.

9, 824; Tiemann and Herzfeld, Ber.

10, 6^), and reduction of the aldehyde
with sodium amalgam and dilute sul-
phuric acid (Biedermann, Ber. 19, 2374).

Also from phenol, together with sali-
genin, by the action of formic aldehyde
in the presence of alkali (see under
saligenin [55; E]).

[B.] Parahydroxybenzoic acid [Vol.
II], by heating its ethyl ester with
aqueous ammonia, is converted into p-
hydroxybenzamide (Hartmann, Journ.
pr. Ch. [2] 16, 50), and the latter on
reduction with sodium amalgam in acid
solution gives p-hydroxybenzyl alcohol
(Hutchinson, Ber. 24, ] 75 ; Auwers
and Daecke, Ber. 32, 3373).

57. Phenylethyl Alcohol; Benzyl
Carbinol ; 1^-Fhenethylol.

CgHg . CH2 . CHg . OH

Natueal Sources.

In small quantity in the steam distil-
late from German oil of rose (v. Soden
and Rojahn,Ber. 33, 1730 ; 3063 ; Wal-
baum and Stephan, Ibid. 2305 ; v. S.
and R. Ber. 34, 2803). In dried and in
fresh rose petals (Walbaum, Ber. 33,
1904; 2299), and to a small extent in
Bulgarian oil of rose (v. Soden and
Rojahn, Ber. 33, 3065).

In the aqueous distillate from orange
flowers (Hesse and Zeitschel, Journ.
pr. Ch. [2] 64, 245). Esters of this
alcohol occur in French neroli oil
(SchimmeFs Ber. Oct. 1902; Ch.
Centr. 1902, 2, 1208).

Synthetical Processes.

[A.] From phenylacetic and formic
acids [Vol. II] by distilling a mixture
of the calcium salts (Cannizzaro, Ann.
119, 254) which gives a-toluic =:phenyl-
acetaldehyde. The latter yields the
alcohol on reduction with sodium amal-

58. Methylphenyl Carbinol;
1^-Phenethylol ; Styrolyl Alcohol.

C6H5.CH(OH).CH3

Natural Source.

Occurs as acetate in Gardenia oil
(Parone, Boll. Ch. Farm. 41, 489 ; Ch.
Centr. 1902, 2, 704).

Synthetical Processes.

[A.] From benzene [6] and ethyl al-
cohol [14] through ethylbenzene (see
under phlorol [64; A]). The latter on
bromination at its boiling-point or in
presence of strong light gives i^-brom-
ethylbenzene (see under styrene [7;
a]). The latter gives the alcohol ace-
tate by interaction with silver acetate
(Radziszewski, Ber. 7, 141 ; Berthelot,
Zeit. [2] 4, 589).

[B.] From styrene [7] through i^-
bromethylbenzene by combination with
hydrogen bromide (Schramm, Ber. 26,
1 7 10), and then as above.

[C] From benzoic and acetic acids
[Vol. II], or from benzene and acetyl

58 C-60.]

METHYLPHENYL CARBINOL

119

chloride through acetophenone. The
latter is reduced to the alcohol by so-
dium amalgam (Emmerling and Engler,
Ber. 6, I oo6 : see also under styrene
[7; A and D]), or by sodium and al-
cohol (Klages and Allendorf, Ber. 31,
1003).

[D.] From lenzoic aldehyde [114] and
methyl alcohol [13] by the interaction
of the aldehyde and magnesium meth-
iodide (Klages and Keil, Ber. 36, 1632).

59. Fhenylpropyl Alcohol ;
1 ^-Phenepropylol.

C6H5.CH2.CH2.CH2.OH

Natural Sources.

Phenylpropyl cinnamate occurs in
storax from Liquidambar orientalis and
from the American L. styraciflua (v.
Miller, Ann. 188, 184; Arch. Pharm.
220, 648; Tschirch and Van Itallie,
Ibid. 239,506; 532; Ch. Centr. 1901,
2,553; 856).

Synthetical Process.

[A.] From benzene, [6] trimethylene
glycol [46], and ethyl alcohol [l4]. The
monosodium glycol is converted into the
ethyl ether by means of ethyl iodide
and the hydroxyl-group replaced by
bromine by means of phosphorus tri-
bromide. A mixture of ethyl-y-brom-
propyl ether and monobrombenzene on
treatment with sodium in ethereal solu-
tion gives the ethyl ether of phenyl-
propyl alcohol = phenylpropyl-y-ethyl
ether (Noyes, Am. Ch. Journ. 19, 766,
&c.). The ether would yield the al-
cohol by de-ethylation.

60. Phenol ; Carbolic Acid.
HO

Natural Sources.

In normal and pathological urine of
man (Salkowski, Ber. 9, 138; 1595;

10, 842 ; Munk, Ber. 9, 1595 : see also
Lewin, Beit. ch. Physiol. Path. &c.,
1,472; Ch. Centr. 1902, 1, 487), and
in the urine of herbivorous animals
(Stadeler, Ann. 77, 18; Lieben, Ann.
Suppl. 7, 240 ; Hoppe-Seyler, Pfliiger's
Arch. 5, 470).

The phenol is said to exist in urine
as a salt of phenylsulphuric acid (Bau-
mann, Ber. 9,54; 1389; 1715; Brie-
ger, Zeit. physiol. Ch. 4, 204) or (in
normal urine) as glycuronate (Mayer
and Neuberg, Zeit. physiol. Ch. 29, 271).
Phenol (combined) has been found in
sweat of sheep (Buisine, Comp. Bend.
103, 66) and of man (Kast, Zeit. physiol.
Ch. 11, 501). Occurs also in minute
quantity in castoreum (Wohler, Ann.
67, 360). _

Phenol is among the products of the
putrefaction of many proteids (Bau-
mann, Ber. 10, 685; 12, 2166; Zeit.
physiol. Ch. 1, 60 ; 3, 250 ; Weyl, Ibid.
1, 339; Brieger, Ber. 10, 1028; Zeit.
physiol. Ch. 3, 134 ; Journ. pr. Ch. [2]
17, 134; Odermatt, Ibid. 18, 249; Sal-
kowski, Ber. 10, 842 ; Zeit. physiol. Ch.
12, 215).

Among the products of putrefaction
of tyrosin and of hydroparacoumaric
acid (Baumann, Ber. 13, Kef. 1881) and
among the products of anaerobic putre-
faction of milk by Bacillus putrijicus
and by the Bacilli of malignant oedema
and of symptomatic anthrax (Bienstock,
Ch. Centr. 1901, 1, 1209).

A product of putrefaction of wheat
gluten by Proteus vulgaris and of eg^
albumin by Staphylococcus pyogenes
aureus (Emmerling, Ber. 29, 2722 ;
2725). Occurs among the products of
fermentation of the aqueous extract
obtained by washing wool (A. and P.
Buisine, Comp. Rend. 125, 777).

Said to occur in the trunk, leaves,
and sap of Scotch fii-, Pinus sylvestris
(Griffiths, Ch. News, 49, 59).

The phenol complex may be con-
sidered to exist in certain natural pro-
ducts of the flavone group, such as api-
genin [l40], genistei'n, and kampherol
(see under phloroglucinol [86]).

120

AROMATIC ALCOHOLS AND PHENOLS [eo A-C.

Synthetical Peocesses.

[A.] From acetylene (see under me-
thane [l ; A])j the sulphonic acid formed
by absorbing the latter in fuming- sul-
phuric acid, and fusion of the sulphonic
acid salt with potash (Berthelot, Comp.
Rend. 68, 539 : could not be confirmed
by Schroeter, Ber. 31, 2189 ; Ann, 303,
132). According to later experiments
by Berthelot (Comp. Rend. 127, 908 ;
128, '^'^^i the 'potassium-acetylene
sulphonate^ is heated to 180-200° in
an atmosphere of hydrogen, and then
distilled with dilute sulphuric acid, when
phenol passes over. A further quantity
is obtained from the residue by fusion
with potash at 250° (see also Ann.
Chim. [4] 19, 432 and [7] 17, 289.)

Or from acetylene through benzene
(see under cymene \Q; A]), benzene-
sulphonic acid (Mitscherlich, Pogg. Ann.
31, 283; 634; Stenhouse, Proc. Roy.
Soc. 14, 351 ; Wurtz, Comp. Rend. 64,
749 ; Michael and Adair, Ber. 10, 585),
and fusion of the potassium salt with
excess of potash (Wurtz, Ann. 144, 121 ;
Bull, Soc. [2] 8, 197; Kekule, Lehrb.
d. org. Ch. 3, 13; Dusart, Zeit. [2] 3,
299). Benzene is said to be oxidised
by atmospheric air in the presence of
alkali with the formation of phenol
(Nencki, Ber. 14, 1144).

Also from benzene by passing air
through the boiling hydrocarbon in
presence of aluminium chloride (Friedel
and Crafts, Ann. Chim. [6] 14, 435 ;
Bull. Soc. [2] 31, 463); by the action
of palladium hydride, water, and air
(Hoppe-Seyler, Ber. 12, 1552); or by
oxidation with hydrogen peroxide or
nascent ozone (Leeds, Ber. 14, 976;
Cross, Bevan, and Heiberg, Trans. Ch.
Soc. 75, 751).

Also from benzene through nitro-
benzene, aniline, and action of nitrous
acid (diazo-reaction) on latter (Hofmann,
Ann. 75, '>,S^} Hunt, Silliman's Am.
Joum. [2] 8, 372; Jahvesber. 1849,
391 ; Griess, Ann. 137, 39 : for direct
production of aniline from benzene by
the action of hydroxylamine in presence
of aluminium chloride see Graebe, Ber.
84, 1778; Jaubert, Comp. Rend. 132,
841).

A synthesis of phenol from carbon
is possible through mellitic (benzene-
hexacarboxylic) acid, which is obtained
by oxidising charcoal with alkaline
permanganate (Schulze, Ber. 4, 802;
806), by the electrolysis of dilute acid
or alkali with retort carbon for the
positive electrode (Bartoli and Papa-
sogli, Gazz. 11, 468 ; Ch. Centr. 1881,
327), by the oxidation of animal char-
coal or lampblack with alkaline hypo-
chlorite {Ibid. Gazz. 15, 446), or by
heating wood charcoal with strong
sulphuric acid (Verneuil, Bull. Soc. [3]
11, 121).

Mellitic acid is converted by dry dis-
tillation into pyromellitic (i : 2 : 4 : 5-
benzenetetracarboxylic) acid (Erdmann,
Ann. 80, 281), which by reduction in
alkaline solution with sodium amalgam
is converted into hydropyromellitic acid
(Baeyer, Ann. Suppl. 7, 38 ; 166, '^'^'J ;
258, 205). The latter on heating with
strong sulphuric acid gives isophthalic
acid {Ibid. Ann. Suppl. 7, 4), which can
be converted into 5-sulpho- and 5-hy-
droxyisophthalic acid by sulphona-
tion and potash fusion (Heine, Ber.
13, 493). The latter acid gives phenol
on distillation with lime (see also
under L).

Mellitic acid can be obtained also by
the oxidation of charcoal with fuming
nitric acid (Dickson and Easterfield, Proc.
Ch. Soc. 14, 163).

Phenyl sulphuric acid (potassium salt)
is obtained by the action of potassium
pyrosulphate on phenol in potassium
hydroxide solution (Baumann, Ber. 9,
54 and 1715; 11, 1907; Brieger, Zeit.
physiol. Ch. 8, 311 ; Drechsel, Joum.
pr. Ch. [2] 29, 234). The acid is also
among the products of the electrolysis
of phenol by an alternating current in
the presence of magnesium sulphate and
acid magnesium carbonate (Drechsel,
loc. cit.).

[B.] Glycerol [48] is said to give
phenol when distilled with calcium
chloride (Linnemann and Zotta, Ann.
174, 87 ; Suppl. 8, 254).

[C] From salicylic acid [Vol. II] by
distillation with lime (Gerhardt, Rev.
Scien. 10, 210; Rosenthal, Zeit. [2]
6, 627) j also by heating per se, or with

60 C-H.]

PHENOL

121

water at 230-230°, or with strong hydro-
chloric or hydriodic acid, or with dilute
sulphuric acid at 140-150° (Graebe,
Ann. 139, 14.3).

Methyl salicylate g-ives phenol when
heated with dry aniline (Tingle, Am.
Ch. Journ. 24, 45).

[D.] ParaJiydroxyhenzoic acid [Vol. II]
gives phenol when distilled with lime ;
also when heated per se, or by heating
with sodium hydroxide, or by the dry
distillation of the sodium salt at 240-
250° (Gerhardt, Rev. Scien. 10, 210;
Rosenthal, Zeit. [2] 5, 627; Klepl,
Journ. pr. Ch. [2] 28, 194; Barth and
Schreder, Ber. 12, 1257; Kupferberg,
Journ. pr. Ch. [2] 16,425; Goldschmiedt
and Herzig, Monats. 3, 132). Also
by heating in sealed tube with dilute
sulphuric acid (Klepl, Journ. pr. Ch. [2]

25, 464).

p-Methoxyhenzolc = anisic acid [Vol. II]
gives phenol among the products of
the distillation of the calcium salt
(Goldschmiedt and Herzig, Monats.
3, 127).

[E.] From henzoic acid [Vol. II] by
fusion with caustic potash (Barth and
Schreder, Monats. 3, 802).

Also through metasulphobenzoic acid
by sulphonation (Mitscherlich, Pogg.
Ann. 31, 287; 32, 227; Offermann,
Ann. 280, 5; Barth, Ann. 148, 33),
and m-hydroxybenzoie acid by fusion
of the sulpho-acid with caustic potash
(Barth, loc. cit. ; Remsen, Zeit. [2]
7, 81 ; 199). Or from benzoic acid
through metachlorbenzoic acid by chlori-
nation (Scharling, Ann. 41, 49; 42,
268; Stenhouse, Phil. Mag. 27, 129;
Ann. 55, 10 ; Field, Ann. 65, $^;
Otto, Ann. 122, 157; Hiibner and
Weiss, Ber. 6, 175), and fusion of the
chloro-acid with caustic potash (Dembey,
Ann. 148, 222).

Or from benzoic acid through the
metanitro-acid by nitration (Mulder,
Ann. 34, 297; Gerland, Ann. 91, 186;
Hiibner, Ann. 222, 72; Holleman,
Zeit. physik. Ch. 31, 79), m-amino-acid
by reduction (Zinin, Berz. Jahresber.

26, 450; Journ. pr. Ch. 36, 103;
Gerland, Ann. 86, 143; 91, 188;
Schiff, Ann. 101, 94; Beilstein and
Wilbrand, Ann. 128, 265; Holleman,

Rec. Tr. Ch. 21, ^6), and m-hydroxy-
benzoic acid by the action of nitrous
acid (Gerland, Ann. 91, 189; Graebe
and Schultzen, Ann.' 142, 350).

In all these cases the metahydroxy-
benzoic acid can be best converted into
phenol by heating the barium salt with
excess of baryta at 350° (Klepl, Journ.
pr. Ch. [2] 27, 159).

[F.] Cinnamzc acid [Vol. II] on treat-
ment with bleaching powder is said to
give metachlorbenzoic acid (Stenhouse,
Ann. 55, i), which can be converted
into m-hydroxybenzoic acid and phenol
as under E.

Or cinnamic acid can be converted by
nitration into 0- (with p-) nitrociunamic
acid (Beilstein and Kuhlberg, Ann.
163, 126; Miiller, Ann. 212, 124), the
o-nitro-acid oxidised to o-nitrobenzoic
acid (B. and K. loc. cit. 134 ; Widn-
mann, Ber. 8, 393), reduced to anthra-
nilic acid [Vol. II], the latter converted
into salicylic acid [Vol. II] by the
diazo-method, and then into phenol as
under C.

Or cinnamic acid can be sulphonated,
the ortho- (? meta-) separated from the
parasulphonic acid, giving m-hydroxy-
benzoic acid on fusion with alkali (Rud-
neff, Ann. 173, 8).

[G.J From gallic acid [Vol. II] by
heating the acid or its ester with strong
sulphuric acid so as to form rufigallic
acid =1 : 2 : 3 : 5 : 6 : 7-hexahydroxy-
anthraquinone (Robiquet, Ann. 19,
204; Wagner, Jahresber. 1860, 288;
Ch. Centr. 1861, 47 ; Lowe, Journ. pr.
Ch. 107, 296; Zeit. [2] 6, 128; JafP^,
Ber. 3, 694; Widman, Ber. 9, 856;
Klobukowski and Noelting, Ber. 8,
819; 9, 1256; 10, 880). Rufigallic
acid on fusion with potash gives (with
m-hydroxybenzoic acid) 5-hydroxyiso-
phthalic acid (Schreder, Monats. 1,
437), and the latter on distillation
with lime gives phenol. Hydroxytere-
phthalic acid is also among the pro-
ducts of fused potash on rufigallic acid
{Ibid. 439), and this also gives phenol
on heating with sand.

[H.] From henzoic aldehyde [114]
through the m-nitro-derivative by
nitration (Bertagnini, Ann. 79, 259 ;
86, 190 ; Lij)pmann and Hawliczek,

122

AROMATIC ALCOHOLS AND PHENOLS [60 H- J.

Ber. 9, 146 ; Friedlander and Hen-
riques, Ber. 14, 2802 ; Ehrlich, Ber.
15, 3010), m-nitrobenzylidene chloride
(1^ : i^-dichlor-3-nitrotoluene) by the
action of phosphorus pentachloride
(Widman, Ber. 13, 676), m-toluidine
by reduction (Vienne and Steiner, Bulh
Soc. [2] 35, 428 ; Widman, loc.
cit. 6-]'] ; Bull. Soc. [2] 36, 2i6;
Ehrlich, Ber. 15, 201 1; Harz, Ber.
18, 3398), m-chlortoluene by the diazo-
reaction (Wroblewski, Ann. 168, 199),
m-chlorbenzoic acid by oxidation [Ibid.
200), m-hydroxybenzoic acid, &c., as
under E.

Or the m-nitrobenzoic aldehyde might
be directly oxidised to m-nitrobenzoic
acid, reduced to m-aminobenzoic acid,
and then converted into m-hydroxy-
benzoic acid and phenol as under E.
The aldehyde can also be converted
(partially) into m-chlorbenzaldehyde
by the action of iodine and antimony
pentachloride (Gnehm and Banziger,
Ber. 29, 875), and then oxidised to
m-chlorbenzoic acid and treated as
under E.

[I.] Metacresol [62] is said to give
m-hydroxybenzoic acid on fusion with
potash (Barth, Ann. 154, 361 ; Monats.
3, 802), and this can be converted into
phenol as under E.

[J.] Naphthalene [l2] when nitrated
gives a-nitronaphthalene (Laurent, Ann.
Chim. [2] 59, 378 ; Piria, Ann. 78, 32 j
Beilstein and Kuhlberg, Ann. 169, 83),
which on oxidation yields 3-nitrophthalic
acid (Guareschi, Ber. 10, 294 ; Beil-
stein and Kurbatoff, Ann. 202, 217).
The latter on reduction with tin and
hydrochloric acid gives m-aminobenzoic
acid (Faust, Ann. 160, 61 ; Miller,
Ann. 208, 245), which can be con-
verted into m-hydroxybenzoic acid and
phenol as under E.

Or the reduction can be regulated so
as to give 3-aminophthalic acid (Miller,
loc. cit.), from which, by the diazo-
method, 3-hydroxyphthalic acid can be
obtained (Bernthsen and Semper, Ber.
18, 167; 20, 937), and this gives phenol
on heating.

Or from naphthalene through phthal-
ic acid, phthalide, &c., to o-toluic acid
(see under benzyl alcohol [64; B,]), or

through 1:3: 8-naphthylaminedisul-
phonic acid, &c., to o-toluic acid {Ibid.).
The latter on sulphonation gives 6-
sulpho-o-toluic acid (Jacobsen and
Wierss, Ber. 16, 1959), from which, by
potash fusion, 6-hydroxy-o-toluic acid
can be obtained [Ibid. 1963).

Or o-toluic acid can be converted into
the 6-hydroxy-acid through the 6-
nitro- and 6-amino-acid and diazo-
method {Ibid. 17, 163). The 6-hydroxy-
o-toluic acid is converted into the
methoxy-o-toluic acid by methylation,
and the latter on oxidation with alka-
line permanganate gives 3-methoxy-
phthalic (3-methoxy-i : 2-dicarboxylic)
acid, which yields 3-hydroxyphthalic
acid on fusion with alkali (Jacobsen,
Ber. 16, 1965). The latter acid gives
phenol when heated.

Phthalie acid also may be nitrated,
and the 4-nitro- (separated from the
3-nitro-) acid (Miller, Ann. 208, 224)
converted into ester and reduced to
4-aminophthalic ester, which by the
diazo-method and hydrolysis gives 4-
hydroxyphthalic acid (Baeyer, Ber. 10,
1079; Miller, Ber. 11, 1191; Ann.
208, 237). The latter on heating with
hydrochloric acid yields m-hydroxyben-
zoic acid, from which phenol can be
obtained as under E.

Or phthalie acid may be sulphonated
by fuming sulphuric acid (Loew, Ann.
143, 257; Bee, Ann. 233, 219), the
4-sulphophthalic acid converted into
4-hydroxyphthalic acid by fusion with
alkali (Graebe, Ber. 18, 1130 ; Ree, loc.
cit.), and the latter converted into m-
hydroxybenzoic acid and phenol as
above.

Naphthalene may also be converted
into a-sulphonic acid and a-naphthol
(Eller, Ann. 152, 275), the latter into
acetate, and the acetate oxidised by
chromic acid into 3-hydroxyphthalic
acid (Miller, Ann. 208, 247), from
which phenol can be obtained as above.
[The acid thus obtained by Miller is
said to have been 2-hydroxyisophthalic
acid, but from its mode of formation
must be 3-hydroxyphthalic acid (Beil-
stein, II, 1936 and errata, 2209).]

Or naphthalene-a-sulphonic acid may
be converted into the sulphonamide.

60 J-P.]

PHENOL

123

the latter oxidised by permanganate to
3-sulphophthalic acid (Remsen and
Comstock, Am. Ch. Journ. 5, 107),
and the sulpho-acid converted into 3-
hydroxyphthalic acid by potash fusion
(Remsen and Stokes, Am. Ch. Journ.
6, 283), and then into phenol as before.

Or a-naphthol may be sulphonated
and nitrated so as to form dinitro-a-
naphtholsulphonic (2 : 4-dinitro-i-naph-
thol-7-sulphonic) acid (Caro, Ber. 14,
2029), which on oxidation with nitric
acid gives 4-sulphophthalic acid (Graebe,
Ber. 18, 1 1 27), from which 4-hydroxy-
phthalic acid, m-hydroxybenzoic acid,
and phenol can be obtained as above.

Naphthalene-/3-sulphonic acid, when
converted into its amide and the latter
oxidised with potassium permanganate,
also gives 4-sulphophthalic acid (Remsen
and Comstock, Am. Ch. Journ. 5, 110).

[K.] Indigo [Vol. II] on distillation
with potash gives aniline (Fritzsche,
Ann. 39, 76), which can be converted
into phenol as under A.

[L.] From acetone [IO6] through
mesitylene and uvitic or mesitylenic
acid (see under benzyl alcohol [54 ;
D]), m-toluic acid or m-xylene (see
under o-cresol [61 ; B]), and isophthalic
acid by oxidation of either the acid or
hydrocarbon (Weith and Landolt, Ber.
8, 721 ; Fittig and Velguth, Ann.
148, 11).

Isophthalic acid on nitration gives
a mixture of 4- and 5-nitro-acids
(Beyer, Journ. pr. Ch. [2] 22, '^S'^;
25, 470 ; Storrs and Fittig, Ann. 153,
285). The 5-nitro-acid on reduction
and application of the diazo-method
yields 5-hydroxyisophthalic acid (Beyer,
loc. cit. 25, 515), and this gives phenol
on heating with lime.

Or isophthalic acid can be sulpho-
nated (Heine, Ber. 13, 493), the 5-
Bulpho-acid converted into the 5-hy-
droxy-acid by potash fusion [Ibid.), and
then into phenol as above.

Or from acetone through phorone
and pseudocumene (see under o-cresol
[61 ; B]), methylterephthalic (a-xylidic)
acid by oxidising the latter with nitric
acid (Fittig and Laubinger, Ann. 151,
276), and isophthalic acid, which is
formed (with trimellitic acid) by further

oxidation with potassium permanganate
(Krinos, Ber. 10, 1494).

Or pseudocumene may be sulphonated,
the sulphonamide oxidised with alkaline
permanganate so as to form 4-sulph-
amide-a-xylic acid ( Jacobsen and Meyer,
Ber. 16, 190), which by further oxida-
tion with the same reagent gives 5-
sulphotrimellitic acid [Ibid. 192). The
latter on potash fusion yields 5-hydroxy-
trimellitic acid {Ibid.), and this gives
phenol on distillation with lime.

Or mesitylene maybe sulphonated, and
the sulphonamide oxidised with chromic
acid mixture or alkaline permanganate
so as to form o- and p-sulphamide-
mesitylenic acid (Hall and Remsen,
Ber. 10, 1040 ; Jacobsen, Ann. 206,
167). The latter acids on further
oxidation with potassium permanganate
give sulphamidetrimesic acid (Jacobsen,
loc. cit. 203), which by potash fusion
yields hydroxytrimesic acid [Ibid.), and
the latter gives phenol by heating with
lime.

Note : — Generators of mesitylene and uvitic
acid (see under benzyl alcohol [54 ; D to P])
thus become generators of phenol.

[M.] From cymene [6] through tere-
phthalic acid by oxidation (De la Rue
and Miiller, Ann. 121, 87 ; Schwanert,
Ann. 132, 257 ; Homeyer, Arch. Pharm.
[3] 5, 326; Beilstein, Ann.133,41). The
latter can be converted into nitro- and
aminoterephthalic acid by nitration and
reduction, and into hydroxyterephthalic
acid by the diazo-method (Burkhardt,
Ber. 10, 145), the latter giving phenol
on heating with sand.

Or terephthalic acid may be bromi-
nated, the bromo-acid fused with potash
(Fischli, Ber. 12, 621), and the hydroxy-
terephthalic acid thus formed converted
into phenol as above.

[N.] Carvacrol [66] when fused with
potash gives hydroxyterephthalic acid
(Jacobsen, Ber. 11, 570), and this can
be converted into phenol as above.

[O.] Thymol [67] also gives hydroxy-
terephthalic acid when fused with
potash (Jacobsen, loc. cit.).

[P.] Pheni/laceiic acid [Vol. II] on
nitration gives the 2 : 4-dinitro-acid,
which can be converted into o-nitro-

124

AROMATIC ALCOHOLS AND PHENOLS [60 P-61 A.

benzoic acid (as under quinol [71; l]),
into antliranilic acid, salicylic acid, and
phenol as under C.

[Q,] Hydro^nglone [90] gives phenol
among" the products of its fusion with
potash (Mylius, Ber. 18, 475).

[R.] Acetic aldehyde [92] gives phenol
in small quantity by the action of fuming
sulphuric acid and fusion of the product
with alkali (Berthelot, Comp. Rend.
128, 0,0^6).

[S.] Pulegone [l28] on heating with
formic acid or with water under pressure
gives (with acetone) methylcyclohexan-
one (Wallach, Ann. 289, 338; 340 ;
Klages, Ber. 32, 2567). The latter by
the action of phosphorus pentachloride
yields (as final product) tetrahydrochlor-
toiuene, and this by the action of
bromine gives m-chlortoluene (Klages,
Ber. 32, 3567). Subsequent steps as
under H and E.

Mineral acids (especially sulphuric)
may also be used for converting pule-
gone into the cycloketone (Zelinsky,
Ber. 30, 1532 ; Wallach, Ber. 32,

[T.] From o-coumaric acid [Vol. II],
which gives phenol on dry distillation.

[IT.] From malonic acid [Vol. II] and
elhyl alcohol [14] through dicarboxy-
glutaconic ester and glutaconic ester.
The sodium derivative of the latter on
heating with alcohol at 150° gives
hydroxyisophthalic acid (Lawrence and
W. H. Perkin, junr., Proc. Ch. Soc. 17,
47 : see also under cymene [6 ; XV]).
The latter gives phenol on distillation.

Note : — Generators of dicarboxyglutaconic
ester are given under cymene as above. Glu-
taconic acid is formed by the action of alcoholic
soda or hydrochloric acid on the dicarboxy-
glutaconic ester (Conrad and Gutzeit, Ann.
222, 253 ; Gutzeit and Bolam, Journ. pr. Ch.
[2] 54, 372).

Also from formic and acetic acids and alcohol
or from medic acid through coumalic acid =
formylglutaconic anhydride (see under n-butyl
alcohol [17 ; J ; O, &c.]). Coumalic acid gives
glutaconic acid on heating with barium hydr-
oxide solution (v. Pechmann, Ann. 264, 301).

Or citric acid can be converted into acetonedi-
carboxylic acid (see under n-seeondary amyl
alcohol [21 ; H]) and this, by reduction w^ith
sodium amalgam, gives )3-hydroxyglutaric acid
(v. Pechmann and Jenisch, Ber. 24, 3250) which,
on distillation in a vacuum or with sulphuric
acid, yields glutaconic acid {Ibid. 3256).

Or from acetic acid (ester) and acrylic acid
(ester) through pyrazolin-3:5-dicarbaxylic ester

by the interaction of diazoacetic and acrylic
esters (Buchner and Papendieck, Ann. 273,
232 : generators of acrylic acid are referred to
under benzyl alcohol [54 ; E], under resorcinol
[70; F], and under acetone [106 ; S]). Gluta-
conic ester is formed by the distillation of pyraz-
olindicarboxylic ester (Buchner, Ber. 23, 703).
a-Hydroxyglutaric acid [Vol. II] on dehydration
gives glutaconic acid among other products
(Paolini, Gazz. 32, 402).

61. Orthocresol; 2-Methylplienol.

HO

,CH3

Natural Soueces.

Occurs as a salt of o-cresylsulphuric
acid in urine of herbivorous animals and,
to a small extent, in human urine.
Found also among the products of
putrefaction of horse liver (Baumann,
Ber. 9, 1389 ; Zeit. physiol. Ch. 2, 335 ;
Preusse, Ibid. 355; Baumann and Brie-
ger, Ibid. 3, 149 ; 253 ; Brieger, Ibid. 4,
304 ; Baumann, Ibid. 304 ; Baumann
and Brieger, Ber. 12, 804; Baumann,
Zeit. physiol. Ch. 6, 183 ; Brieger, Ibid.
8, 311 : see also Salkowski, Ibid. 12,

215)-

The o-cresol complex exists possibly

in bebeerine, an alkaloid found in the
bark of Neclandra rodioei from British
Guiana, in the bark and leaves of Buxus
sempervirens, and in the root of Cissam-
pelos pareira (see Scholtz, Ber. 29, 2054,
and Arch. Pharm. 236, 530; Ch. Centr.
1898,2,983).

A cresol (? isomeride) has been found
in eascarilla oil from the bark of Croton
eluteria (Fendler, Arch. Pharm. 238,
671).

Synthetical Processes.

[A.] From toluene (see under benzyl
alcohol [54 ; A and D to T]). Toluene
on sulphonation gives (with para-) ortho-
sulphonic acid (Engelhardt and Lat-
schinoff, Zeit. [2] 5, 61 7 ; Wolkoff, Ibid.
6, 321 ; Claesson and Wallin, Ber. 12,
1848; Noyes, Am. Ch. Journ. 8, 176),
and this gives o-cresol by potash fusion
(Engelhardt and Latschinoff, loc. cit.
620).

61 A.]

ORTHOCRESOL

125

Toluene on nitration gives a mixture
of p- and o-nitrotoluenes (Glenard and
Boudault, Comp. Rend. 19, 505 ; Hof-
mann and Muspratt, Ann. 53, 221 ;
Kekule, Zeit. [2] 3^ 225 ; Rosenstiehl,
Ann. Chim. [4] 27, 433 ; Reverdin and
La Harpe^ Bull. Soe. 50, 44 : for direct
production of o- and p-toluidine from
toluene and hydroxylamine in presence
of aluminium chloride see Graebe, Ber.
34, 1778). The latter can be reduced
to o-toluidine, and this by the diazo-
reaction gives o-cresol (Kekul6, Ber. 7,
1006).

Or o-nitrotoluene gives o-cresol di-
rectly among the products of pyrogenic
(electric) decomposition when mixed with
steam and heated to 500-1000° (Lob,
Zeit. Elektroch. 8, yy^).

Or p-nitrotoluene can be reduced to
p-toluidine, the latter converted into
3 -brom -p-toluidine (Wroblewski, Ann.
168, 153), into 3-brom-p-toluic nitrile
by the diazo-method (Glaus and Kunath,
Journ. pr. Ch. [2] 39, 486), the acid by
hydrolysis, 3-brom-6-nitro-p-toluic acid
by nitration (Glaus and Herbabny, Ann.
265, 3*54), and then through 6-nitro-3-
amino-p-toluic acid, 6-nitro-m-toluidine,
o-nitrotoluene, and o-toluidine to o-cresol
as above and under C and P.

Toluene can be converted into para-
toluic acid by several processes: — By
heating p-bromtoluene with sodium in
an atmosphere of carbon dioxide (Kekule,
Ann. 137, 184), or by treatment with
sodium and ethyl chlorocarbonate and
hydrolysing the ester (Wurtz, Gomp.
Rend. 68, 1298; Ann. Supp. 7, 126).

By the action of aluminium chloride
on a solution of phosgene in toluene
and decomposition of the chloride with
water (Ador and Crafts, Ber. 10, 2 1 76).

By nitration, reduction of p-nitro-
toluene to p-toluidine, the formation of
the nitrile by the diazo- (Sandmeyer)
reaction and hydrolysis (Herb, Ann.
258, g; Glock, Ber. 21, 2650; Van
Scherpenzeel, Rec. Tr. Gh. 20, 149).

By the action of aluminium chloride
on a mixture of toluene and chlorocar-
bamide(urea chloride) dissolved in carbon
disulphide, and hydrolysis of the p-toluic
amide thus formed (Gattermann and
Schmidt, Ann. 244, 51).

By heating toluene with zinc chloride,
acetic acid, and phosphorus oxychloride,
and treating the product with dilute
sodium hydroxide solution (Frey and
Horowitz, Journ. pr. Gh. [2] 43, 116).

By the action of aluminium chloride
on a mixture of toluene and phthalic
anhydride (see under benzyl alcohol
[54 ; B,]), and potash fusion of the
p-toluyl-o-benzoic acid thus formed
(Friedel and Grafts, Ann. Ghini. [6] 14,
449 ; Bull. Soc. [2] 35, 50H).

By passing cyanic acid and hydrogen
chloride into toluene at 100° in presence
of aluminium chloride (Gattermann and
Rossolymo, Ber. 23, 1195).

By passing carbon monoxide and
hydrogen chloride through toluene in
the presence of aluminium and cuprous
chlorides and oxidising the p-toluic
aldehyde thus formed (Gattermann and
Koch, Ber. 30, 1622).

Paratoluic acid can be converted into
2-hydroxy-p-toluic acid (2-methylphenol-
4-carboxylic acid) by several processes : —

By sulphonation and potash fusion of
the 2-sulpho-acid (Weinreich, Ber. 20,
981).

By conversion into 2-brom-p-toluie
acid (Briickner, Ber. 9, 407) and potash
fusion of the latter (Vongerichten, Ber.
11,368).

By converting the acid (or nitrile)
into 3-nitro-p-toluic acid by nitration
(Fittig and Ramsay, Ann. 168, 251 ;
Banse, Ber. 27, 2162; Van Scherpen-
zeel, loc. cit.), reducing to amino-acid
and applying the diazo-reaction (Fittica,
Ber. 7, 927 ; Vongerichten and Rossler,
Ber. 11, 705).

The 2-hydroxy-p-toluic acid thus
formed gives o-cresol when distilled
with lime.

From Toluene through m-Xylene and
the Hydroxytoluic Acids.

Metaxylene is formed (among other
methylbenzenes) when methyl chloride
is passed into toluene in presence of
aluminium chloride (Friedel and Grafts,
Ann. Ghim. [6] 1, 461 ; Ador and Ril-
liet, Ber. 11, 1627), and this on sul-
phonation gives (chiefly) m -xylene- 4-
sulphonic acid (Jacobsen, Ann. 184,

126

AROMATIC ALCOHOLS AND PHENOLS

[61 A-B.

188; Ber. 11, 18), the amide of which
gives on oxidation with chromic acid or
potassium permanganate 6-sulphamide-
m-toluic acid (Remsen and lies, Am.
Ch. Journ. 1, 41 j Jacobsen, Ber. 11,
895 j Coale and Remsen, Am. Ch.
Journ. 3, 205). The latter on potash
fusion yields 6-hydroxy-m-toluic acid
(Jacobsen, loc. cit. 897; Remsen and
lies, loc. cit. 48 ; 114; Ber. 11, 462 ;
Mahon, Am. Ch. Journ. 4, 186), which
on heating with hydrochloric acid at
180-185° gives o-cresol.

Or m-xylene can be nitrated, the 6-
nitro-m-xylene oxidised to 6-nitro-m-
toluic acid by chromic acid (Beilstein
and Kreusler, Ann. 144, 168), reduced
to the amino-acid {Ibid. 177), the latter
converted into the 6-hydroxy-m-toluie
acid by the diazo-reaction (Remsen and
Kuhara, Am. Ch. Journ. 3, 428), and
the hydroxy-acid converted into o-cresol
as above.

Or m-xylene may be brominated, the
product oxidised to 6-brom-m-toluic acid
by chromic acid (Fittig, Ahrens, and
Mattheides, Ann. 147, 32 ; Jacobsen,
Ber. 14, 2352), the 6- hydroxy-acid
formed by potash fusion of the bromo-
acid (Jacobsen, loc. cit.), and then con-
verted into o-cresol as before.

When m-xylene is sulphonated the
2-sulphonic acid is produced as well as
the 4-sulphonic acid (Jacobsen, Ann.
184, 188; Ber. 10, 1015; 11, 19), and
the amide of the former on oxidation
with chromic acid gives 2-sulphamide-
m-toluic acid {Ibid. Ber. 11, 901), which
on fusion with potash yields 2-hydroxy-
m-toluic (/3-cresotic = o-homosalicylic)
acid. The latter on heating with strong
hydrochloric acid is converted into 0-
cresol.

Or m-xylene can be directly oxidised
to m-toluic acid by dilute nitric acid
(Tawildaroff, Zeit. [2] 6, 419; Ber. 4,
410 ; Briickner, Ber. 9, 406 ; Renter,
Ber. 17, 2028), m-Toluic acid on
nitration gives (with much 4-nitro-acid)
a small quantity of 2-nitro-m-toluic
acid (Jacobsen, Ber. 14, 2353 ; Van
Scherpenzeel, Rec. Tr. Ch. 20, 149),
and this on reduction to the amino-acid
and application of the diazo-reaction
yields 2-hydroxy-m-toluic acid (Jacobsen,

loc. cit.), which can be converted into
o-cresol as before.

Or m-toluic acid may be brominated
with the formation of 4-brom- and
6-brom-m-toluic acid (Jacobsen, loc.
cit.), the latter being convertible into
6-hydroxy-m-toluic acid by potash
fusion and then into o-cresol as above.

Note : — All the generators of toluene referred
to under benzyl alcohol (54 ; A and D to T,
&c.) by the foregoing methods become generators
of o-cresol.

[B.] From acetone [IO6] through
mesitylene (see under benzyl alcohol;
[54; D]), mesitylenic acid by oxida-
tion with dilute nitric acid (Fittig,
Ann. 141, 144; Fittig and Briickner,
Zeit. [2] 4, 493; Ann. 147, 45)^
m-xylene by distilling mesitylenic acid
with lime (Fittig and Velguth, Ann.
148, 10), and then as under the fore-
going methods. Or from acetone
through phorone (2 : 6-dimethyl-2 : 5-
heptadienone-4) by the action of lime
or acids (Fittig, Ann. 110, 32 ; Baeyer,
Ann. 140, 301), pseudocumene (i : 2 :4-
trimethylbenzene) by the action of phos-
phorus pentoxide or zinc chloride on
phorone (Jacobsen, Ber. 10, 855), xylic
acid (i : 3-dimethyl-4-benzoic acid) by
the oxidation of pseudocumene by dilute
nitric acid (Fittig and Laubinger, Ann.
151, 269), m-xylene by distilling xylic
acid with lime (Fittig and Bieber, Ann.
156, 236), and then as above. Or from
acetone through triacetonamine by the
action of ammonia (Heintz, Ann. 178,
305; 189, 214), nitrosotriacetonamine
by the action of nitrous acid {Ibid. 185,
I ; 187, 233), phorone by the action of
caustic alkali on the nitrosamine {Ibid.
187, 250), and then as above.

Note : — Mesitylenic acid is formed also in
small quantity by passing carbon monoxide over
a mixture of sodium ethylate and sodium acetate
heated to 205°, or by heating this same mixture
with zinc dust (Geuther and Frohlich, Ann.
202, 310). Also under similar conditions from
sodium isovalerate and ethylate at 160° (Loos, Ibid.
321).

Mesitylene also is converted by further
oxidation into uvitic acid (see under
benzyl alcohol [54; D]), and this on
heating the calcium salt with a small
quantity of lime gives m-toluic acid
(Bottinger and Ramsay, Ann. 168, 255)^

61 B-J.]

ORTHOCRESOL

127

which can be converted into a-hydroxy-
m-toluic acid and o-cresol as under A.

Note : — The generators of mesitylene and
uvitic acid referred to under benzyl alcohol
(54 ; D to Q,) thtis become generators of o-cresol.

[C] From cymene [6] through the
a-sulphonic acid (Claus and Cratz, Ber.
13^ 901 ; Spica, Ber. 14^ (>S'^', Claus,
Ihid. 2139), 2-sulpho-p-toluic acid by
oxidation of the sulphonic acid (Remsen
and Burney, Am. Ch. Journ. 2, 411;
Meyer and Baur, Ann. 220, 18), 1-
hydroxy-p-toluic acid by potash fusion,
&c., as under A.

Or from cymene through the 2-(a)-
sulphonic acid (see above), 3-brom-6-
sulphonic acid by bromination (Kelbe
and Koschnitzky, Ber. 19, 1730; Claus
and Christ, Ibid. 2165), 3-bromcymene
by heating the latter with sulphuric acid
{Ibid.), 3-brom-6-nitro-p-toluic acid by
the action of nitric acid on latter (Pileti
and Crosa, Gazz. 16, 297)^ 6-nitro-3-
amino-p-toluie acid by heating the brom-
nitro acid with alcoholic ammonia {Ibid.
18, 303), 6-nitro-m-toluidine by heating
the nitramino-p-toluic acid with hydro-
chloric acid at 150° {Ibid.), and then
through o-nitrotoluene and o-toluidine
to o-cresol as under F and A.

Or 3-bromcymene may be nitrated
(Mazzara, Gazz. 16, 193 ; Fileti and
Crosa, Ibid. 18, 289), the 3-brom-6-
nitrocymene oxidised to 3-brom-6-nitro-
p-toluic acid (F. and C. Ibid, 300), and
then treated as above.

[D.] From thymol [67] through 3-
amino-p-cymene (cymidine) by heating
with ammonium bromide and ammonio-
zinc bromide at 350-360° (Lloyd, Ber.
20, 1260), and then as under Q-.

Or thymol can be converted directly
into 3-bromcymene by phosphorus
pentabromide (Fileti and Crosa, Gazz.
16, 291), and then into o-cresol as
under O.

[E.] Carvacrol [66] on heating with
phosphorus pentoxide and hydrolysis of
the phosphate gives o-cresol (Kekule,
Ber. 7, 1006).

Or carvacrol by the action of phos-
phorus pentasulphide can be converted
into thiocarvacrol (Roderburg, Ber. 6,
669), which by oxidation with nitric

acid gives 2-sulpho-p-toluic acid (Flesch,
Ber. 6, 480 ; Bechler, Journ. pr. Ch.
[2] 8, 170). The latter can be con-
verted into the hydroxy-acid and o-
cresol as before.

[F.] Metacresol (see below) on heating
with ammonio-zinc chloride and am-
monium chloride at 330-340° is con-
verted into m-toluidine (Merz and
Miiller, Ber. 20, 548), the acetyl-de-
rivative giving on nitration 6-nitro-m-
toluidine (Beilstein and Kuhlberg, Ann.
158, 348 : see also Noelting and Stock-
lin, Ber. 24, 564), which by the diazo-
method gives o-nitrotoluene (B. and K.).
The latter can be reduced to o-toluidine
and converted into o-cresol as under A.

Or m-cresol may be ethylated, the
ether nitrated (Stadel, Ann. 217, 161),
the 6-nitro-m-cresol ether converted into
6-nitro-m-toluidine by heating with
strong ammonia (Stadel and Kolb, Ann.
259, 214), and the latter converted into
o-cresol as before.

[G.] From cumic aldehyde [II6]
through the 3-nitro-derivative by nitra-
tion, nitrocymylidene chloride by the
action of phosphorus pentachloride, 3-
amino-p-eymene (cymidine) by reduc-
tion, 3-amino-p-cymene-6-sulphonic acid
by sulphonation, 3-brom-p-cymene-6-
sulphonic acid by the diazo-method,
and then through 3-bromcymene, 3-
brom-6-nitro-p-toluic acid, 6-nitro-3-
amino-p-toluic acid, 6-nitro-m-toluidine,
and o-nitrotoluene to o-cresol as under C.

[H.] From phenylacetic acid [Vol. II]
through the 2 : 4-dinitro acid, 2 : 4-
dinitrotoluene and o-nitrotoluene (see
under quinol [71; l]), o-toluidine, &c.,
as under A.

[I.] Methylhepfenone [ill] by heating
with zinc chloride or with 75 per cent,
sulphuric acid gives dihydro-m-xylene
(Verley, Bull. Soc. [3] 17, 181). The
latter on nitration gives 6-nitro-m-
xylene (Wallach, Ann. 258, 330), and
this can be converted into 6-amino-
and 6 -hydroxy toluic acid and o-cresoI
as under A above.

[J.] Carvone [l27] through carvacrol
[66] gives o-cresol (see above under E).
Or from carvone through dihydrocarveol
by reduction and the ketone-alcohol
by oxidation. The latter by extreme

128

AROMATIC ALCOHOLS AND PHENOLS [eiJ-ea A.

oxidation gives hexahydro-m-liydroxy-
p-toluic acidj which is converted by
bromine into 3-hydroxy-p-toluic acid
(Tiemann and Semmler, Ber. 28_, 2141).
The latter gives o-cresol as above
under A.

[K.] From acetylene [l; A, &c.], the
copper compound o£ which gives a mix-
ture of cresols among the products of
distillation with zinc dust (Erdmann
and Kothner, Zeit. anorg. Ch. 18, 48).

Note : — Orthocresylsulphuricacid is obtained
from o-cresol by treating the potassium salt
■with potassium pyrosulphate (Baumann, Ber.
11, 1911).

62. Metacresol; 3-Methylphenol.
HO

CH,

Natueal Souece.

Possibly occurs (as salt of cresylsul-
phuric acid) in urine of horse (Preusse,
Zeit. physiol. Ch. 2, ^b^)-

Synthetical Peocesses.

[A.] From toluene (see under benzyl
alcohol [54; A]) by passing air through
the boilmg hydrocarbon in presence of
aluminium chloride (Friedel and Crafts,
Ann. Chim. [6] 14, 436).

Toluene on sulphonation (preferably
with chlorosulphonic acid) gives o-
(with p-) toluenesulphonic acid (Claesson
and Wallin, Ber. 12, 1848; Noyes,
Am. Ch. Journ. 8, 176 : see also under
61 ; A), which can be converted into
o-cyanotoluene (nitrile) by distilling the
potassium salt with potassium cyanide
[172] (Fittig and Ramsay, Zeit. [2] 7,
584; Ann. 168, 246) and into o-toluic
acid by hydrolysis (Cahn, Ann. 240,
280). The latter on bromination gives
3-brom- o-toluic acid (Jacobsen and
Wierss, Ber. 16, 1956; Racine, Ann.
239, 74), which by potash fusion yields
the corresponding hydroxytoluic acid
(Jacobsen, Ber. 16, 1963), and this on
heating with strong hydrochloric acid
at 200° gives m-cresol {Ibid,).

Or toluene can be nitrated, the 0-
nitrotoluene (separated from the para-)
reduced to o-toluidine, converted into
the nitrile by the diazo- (Sandmeyer)
method and the nitrile converted into
the acid (Cahn, loc. cit.), the bromo-acid,
&c., as before.

From Toluene through the Xylenes and
Hydroxytoluic Acids.

Toluene can be converted into o-xylene
by the action of sodium on a mixture of
o-bromtoluene and methyl iodide (Jan-
nasch and Hiibner, Ann. 170, 117;
Reymann, Bull. Soc. [2] 26, 532) or by
passing methyl chloride into warm tol-
uene in presence of aluminium chloride
(Jacobsen, Ber. 14, 2625). Ortho-
xylene gives o-toluic acid on oxidation
with dilute nitric acid (Fittig and Bieber,
Zeit. [2] 6, 496 ; Ann, 156, 242), and
this can be treated as above.

Orthoxylene also on sulphonation
(Jacobsen, Ber. 11, 22) and conversion
into the sulphonamide gives on oxida-
tion of the latter with alkaline perman-
ganate a mixture of 4- and 5-sulph-
amide-o-toluic acid {Ibid. Ber. 14, 39);
the latter on fusion with potash gives
5-hydroxy-o-toluic acid, which on heat-
ing with hydrochloric acid at 200° yields
m-cresol {1/jid.).

Or from o-xylene through 5-nitro-o-
xylene (Jacobsen, Ber. 17, 160), 5-nitro-
o-toluic acid by oxidising the latter with
dilute nitric acid {Ibid. 162), 5-amino-o-
toluic acid by reduction [Ibid. 164),
5-hydroxy-o-toluic acid by the diazo-
method (Ibid.), and then as above.

From toluene through m-xylene (see
under orthocresol [61 ; A]), ra-toluie
acid by oxidation with dilute nitric acid
(TawildarofP, Zeit. [2] 6, 419; Ber. 4,
410; Briickner, Ber. 9, 406; Renter,
Ber. 17, 2028), 5-sulpho-m-toluic acid
by sulphonation (Jacobsen, Ber. 14,
2355), 5-hydroxy-m-toluic acid by pot-
ash fusion {Ibid. 2357), and decompo-
sition of the latter by heating with
lime.

Or toluene can be nitrated, the p-
nitrotoluene reduced to p-toluidine, the
latter acetylated,* nitrated, and hydro-
lysed to 3-nitro-p-toluidine (Beilstein

62 A-C]

METACRESOL

129

and Kuhlberg", Ann. 155^ 23 ; Ehrlich,
Ber. 15, 2009; Gattermann, Ber. 18,
1483), the latter converted into ra-
nitrotoluene by the diazo-method [Ibid.
158, 346), reduced to m-toluidine, and
converted into m-cyanotoluene by the
diazo- (Sandmeyer) reaction (Buchka and
Schachtebeck, Ber. 22, 841), m-toluic
acid by hydrolysis, and then as above.
o-Nitrotoluene can be converted into
m-toluic acid by a similar series of pro-
cesses.

Or p-toluidine can be sulphonated
(v. Pechmann, Ann. 173, 19,5; Nevile
and Winther, Ber. 13, 1947), the p-
toluidine-3-sulphonic acid converted into
the nitrile by Sandmeyer^s process (Ran-
dall, Am. Ch. Journ. 13, 258), and the
latter hydrolysed to 3-sulpho-p-toluic
acid, which, by potash fusion, gives 3-
hydroxy-p-toluic = y-cresotic acid (We-
ber, Ber. 25, 1743). The latter on
heating with hydrochloric acid is con-
verted into m-cresol.

Or toluene can be converted into 3-
nitro-p-toluidine as above, the latter con-
verted into the nitrile (Leuckart,Ber.l9,
175 ; Niementowski and Rozanski, Ber.
21, 1993 '•> Noyes, Am. Ch. Journ. 10,
476), then into 3-nitro-p-toluic acid by
hydrolysis, into 3-amino-p-toluic =
homoanthranilic acid by reduction, and
then into 3-hydroxy-p-toluic = y-cresotic
acid by the diazo-method (N. and R.
loc. cit. 1998).

From toluene through p-xylene by
the action of sodium on p-bromtoluene
and methyl iodide (Fittig and Glinzer,
Ann. 136, 303 ; Jannasch, Ann. 171,
79), p-xylenesulphonic acid and 1:4:2-
xylenol ( Jacobsen, Ber. 11, 26 ; Wurtz,
Ann. 147, 373), 3-hydroxy-p-toluic acid
by potash fusion of latter (Jacobsen,
loc. cit. 570), and m-cresol as above.

Or p-xylene may be nitrated, reduced
to the corresponding xylidine, the latter
converted into p-xylenol by the diazo-
method (Noelting, Witt, and Forel, Ber.
18, 2665), and then as above.

Note: — All generators of toluene thus become
generators of m-cresol.

[B.] From acetone [IO6] through
mesitylene, mesitylenic acid (see under
o-cresol [61; B]), and m-xylene, and

then as under A. Or from mesitylene
through uvitic acid and m-toluic acid
and then as under A (see also under o-
cresol [61 ; B]).

Or from acetone through phorone,
pseudocumene, i : 3-dimethyl-4-benzoic
(xylic) acid, and m-xylene as under o-
cresol (61; B).

Note : — Generators of mesitylene and uvitic
acid (see under benzyl alcohol [54 ; D to Q,])
thus also become generators of m-ci-esol.

From acetone and ooralic acid [Vol. II]
and ethyl alcohol [14] through acetone-
oxalic ester by the action of sodium
ethylate on a mixture of acetone and
oxalic ester (Claisen and Stylos, Ber.
20, 2 1 88). This acetoneoxalic ester
( = acetyl pyroracemic ester) on heating
with baryta water is converted into
,5-hydroxy-m-toluic acid (Claisen, Ber.
22, 3271), from which m-cresol can be
obtained as under A.

[C] From acetic acid [Vol. II] and
ethi/l alcohol [14] through 5-methyl-
phenol-2 : 4-dicarboxylic acid (= m-
hydroxyuvitic acid) by the action of
chloroform, chloral, trichloracetic ester
or carbon tetrachloride on sodio-aceto-
acetic ester (Oppenheim and Pfaff, Ber.
7, 929 ; 8, 884; Oppenheim and Precht,
Ber. 9, 321 ; Conrad and Guthzeit,
Ann. 222, 249), and hydrolysis of the
ester thus formed. The acid on distil-
lation with baryta gives m-cresol (Op-
penheim and Pfalf, 13 er. 8, 886).

Or acetoacetic ester on treating the
sodium compound with methylene iodide
(Hagemann, Ber. 26, 876), or the ester
with formic aldehyde (Knoevenagel,
Ibid. 1090) and hydrolysis of the pro-
duct, gives 3-methyl-A2-keto-R-hexene
(i - methylcyclo - 3 - hexenone) (Hage-
mann, loc. cit. ; Knoevenagel, loc. cit.
1085; K. and Klages, Ann. 281,97). The
latter forms a dibromide (Hagemann,
loc. cit. 884 ; Knoevenagel, loc. cit.
1951), which readily decomposes into
hydrogen bromide and m-cresol (K.
Tbid.).

Acetoacetic ester through its methyl-
ene derivative can also be converted by
the action of ammonia under various
conditions into dihydrolutidine-dicarb-
oxylic ester (Knoevenagel and Klages,

130

AROMATIC ALCOHOLS AND PHENOLS [62 0-63.

Ann. 281j 96 ; Schiff and Prosio, Gazz.
25, 70 : see also Griess and Harrow, Ber.
21, 2740). The latter on heating with
alcoholic potash gives the above methyl-
cyelohexenone among other products
(S. and P. loc. c'lt. 76), and this can be
converted into m-cresol as before.

[D.] From napJithalene [12] through
o-toluie acid (see under benzyl alcohol
[54; B,]), and from the latter as under A.

Phthalic acid may also be converted
into phthalimidine {loc. c'lt.), the latter
nitrated (Honig, Ber. 18, 3447);. reduced
to 5-amino-o-toluic acid by heating with
hydriodic acid and phosphorus {Ibid.
3449), and the latter converted into
5-hydroxy-o-toluic acid and m-cresol as
under A.

Also from naphthalene through the
trisulphonic acids (heteronucleal) derived
from the m-disulphonie acid, which, on
fusion with alkali, give m-hydroxytoluic
acid and m-cresol (Kalle & Co., Germ.
Pat. 81484 of 1894; Ber. 28,Ref. 694;
also Ref. 364). The i : 6-dihydroxy-
naphthalene-3-sulphonic acid on fusion
with alkali gives the corresponding
trihydroxynaphthalene, which yields m-
cresol on further heating (Kalle & Co.,
Germ. Pat. 11 2176 of 1899 ; Ch. Centr.
1900, 2, 700 : see also Ber. 28, Ref.
671 and 693, relating to Germ. Pats.
8ia8i and 81333 of 1893 of Meister,
Lucius, and Briining, and also Ch. Centr.
1897,1, 1039). ^ ^ ^ .

[E.] Orf/iocresol [61] on heatmg with
ammonium chloride and ammonio-zinc
chloride at 330-340° gives o-toluidine
(Merz and Muller, Ber. 20, 547). The
latter can be converted into o-toluic
acid, and m-cresol as under A.

Or o-toluidine may be aeetylated,
nitrated, hydrolysed, and thus converted
into 5-nitro-o-toluidine (Beilstein and
Kuhlberg, Ann. 158, 345), from which,
by the diazo-method, m-nitrotoluene can
be obtained (Ibid.), and from this m-
toluidine. The latter might be directly-
converted into m-cresol by the diazo-
method, or indirectly through m-toluic
acid, &c., as under A.

[F.] Faracresol [63] on nitration
gives 3-nitro-p-cresol (Armstrong and
Thorpe, B. A. Rep. 1875, 112 ; Hof-
mann and Miller, Ber. 14, 573 ; Stadel,

Ann. 217, ^'^ ; Frische, Ann. 224, 138),
which, by heating with ammonia, gives
3-nitro-p-toluidine (Barr, Ber. 21, 1543).
The latter can be converted into m-
nitrotoluene, m-toluidine, and m-cresol
as under A.

[G.] From benzoic aldehyde [114]
through the m-nitro-derivative, m-tolui-
dine (see under phenol [60 ; H]), and
then as above.

[H.] From thijmol [67] by heating
with phosphorus pentoxide and decom-
position of the m-cresyl phosphate by
heating with alkali (Engelhardt and
Latschinoff, Zeit. [2] 5, 621; South-
worth, Ann. 168, 268 ; Stadel and Kolb,
Ann. 259, 209 ; Tiemann and Schotten,
Ber. 11, 769).

Or thymol can be converted into
thiothymol by the action of phosphorus
pentasulphide (Fittica, Ann. 172, 328),
3-sulpho-p-toluic acid by oxidation of
thiothymol with nitric acid [Ibid. 329),
and then through 3-hydroxy-p-toluic
acid and m-cresol as under A.

[I.] From ///^;i;!//c>;ze [129], which gives
tetrabrom-m-cresol among the products
of the action of bromine. The tetra-
brom-derivative gives m-cresol on reduc-
tion with sodium in alcoholic solution
(Baeyer and Seuffert, Ber. 34, 40).

[J.] From pidegone [128] through
meth} Icyclohexanone (see under phenol
[eO; S]). The latter gives m-cresol
on treatment with a chloroform solution
of bromine (Klages, Ber. 32, 2567 :
see also Wallach, Ibid, 3338).

63. Paracresol; 4-Metliylphenol.
HO

CH3

Natural Sources.

Occurs as a salt of cresylsulphuric
acid in urine of herbivorous animals,
and, in certain diseases, in human urine
(Baumann, Ber. 9, 1389; Stadeler,

es-A.]

PARACRESOL

131

Ann. 77, i8 ; Brleger, Zeit. physiol.
Ch. 4; 204 : see also under o-cresol
[ei] for further references).

A product of putrefaction of animal
proteids (Baumann and Brieger, Zeit.
physiol. Ch. 3, J 49; Ber. 12, 706), of
p-hydroxijphenylacetic and hydroparacou-
maric acids [Vol. II] (Baumann, Zeit.
physiol. Ch. 4, 304), and of tyro-sin
[Vol. II] (Weyl, Zeit. physiol. Ch. 3,
312; Baumann, Ibid. 4, 304).

The p-cresol complex may be con-
tained in podocarpic acid, which con-
stitutes the chief portion of the resin
of Podocarpns cupre-ssifta, var. imbricafa
(Oudemans, Ann. 170, 259)-

The methyl ether appears to exist in
the perfiime "^Canang-a Essence •* (ylang-
ylang') from Catianga odorafa (Reychler,
Bull. Soc. [3] 13, 140). p-Cresyl
acetate exists also in this oil (Darzens,
Bull. Soc. [3] 37, 83).

Synthetical Puocesses.

[A.] From toluene [54 ; A, &c.]
through p-nitrotoluene (see under ortho-
■cresol [ei; A]), p-toluidine by reduction,
and thediazo-reaetion with latter (Griess,
Jahresber. 1866, 458 ; Korner, Zeit.
[2] 4, 326).

Or p-nitrotoluene on mild reduction
gives p-toluylhydroxylamine (see under
toluquinol [72 ; A]), and this gives
p-cresol among the products of decom-
position by hot dilute sulphuric acid
(Bamberger, Ber. 28, 246; for produc-
tion of p-toluylhydroxylamine by the
oxidation of p-toluidine by monoper-
sulphuric acid see Bamberger and
Tsehirner, Ber. 32, 1677).

Or from toluene through the p-sul-
phonic acid and potash fusion of the latter
(Wurtz, Ann. 144, 122; 156, 258;
Engelhardt and Latschinoff, Zeit. [2]
6, 618).

From toluene through m-xylene (see
under orthocresol [61; A]), m-xylene-
4-sulphonic acid by sulphonation (Jacob-
sen, Ann. 184, 188; Ber. 10, 1015;
11, 19), and potash fusion of latter so
as to form 4-hydroxy-m-toluic (a-cre-
sotic = p-homosalicylic) acid (Engelhardt
and Latschinoff, loc. cit. 712). The
latter acid on heating with strong

k2

hydrochloric acid at 180-185° gives
p-cresol.

Or m-xylene may be oxidised to m-
toluic acid (TawildarofP, Zeit. [2] 7,
419; Ber. 4, 410 ; Briickner, Ber. 9,
406 ; Renter, Ber. 17, 2028), the latter
brominated (Jacobsen, Ber. 14, 2351),
and the 4-brom-m-toluic acid thus
formed fused with potash [Ibid.).

Or m-toluic acid may be sulphonated
(Jacobsen, loc. cit. 2355), the 4-sulpho-
m-toluic acid converted into 4-hydroxy-
m-toluic acid by potash fusion [Ibid.),
and then into p-cresol as before.

Or m-toluic acid may be nitrated
[Ibid. 2353), the 4-nitro- reduced to the
4 -amino -m- toluic (methylanthranilic)
acid [Ibid.), the latter converted into 4-
hydroxy-m- toluic acid by the diazo-
reaction {Ibid. : see also Panaotovic,
Journ. pr. Ch. [2] 33, 64), and into
p-cresol as before.

Or m-xylene-4-sulphonic acid (see
above) may be converted into 1:3:4-
xylenol by potash fusion (Jacobsen, Ber.
11, 28), or the corresponding 1:3:4-
nitroxylene into i :^ :4-xylidine and into
the same xylenol by the diazo-reaction
(Harmsen, Ber. 13, 1558). This 1:3:4-
xylenol (or its ^-sulphonic acid) gives 4-
hydroxy-m-toluic acid by potash fusion
(Jacobsen, Ber. 11, 375 ; Ann. 195, 283),
and this gives p-cresol as before.

Toluene may also be converted into 2 :
4-dinitrotoluene (Deville, Ann. 44, 307),
the p-nitro-group in the latter replaced
by bromine (Beilstein and Kuhlberg,
Ann. 158, 340), the 4-brom-2-nitro-
toluene heated with alcoholic potassium
cyanide at 220°, and the nitrile hydro-
lysed to 4-brom-m-toluic acid (Richter,
Ber. 5, 425), which can be converted
into 4-hydroxy-m-toluic acid and p-
cresol as above. 4-Brom-2-nitrotol-
uene is also formed (with 4-brom-3-
nitrotoluene) by the nitration of p-
bromtoluene (Wroblewski, Ann. 168,
176).

Or toluene may be converted into
methyl-m-toluyl ketone by the action
of acetyl chloride in presence of alu-
minium chloride (Essner and Gossin,
Bull. Soc. [2] 42, 95) ; or p-bromtoluene
into p-bromtoluyl-m-methyl ketone by
the same process. The latter on oxida-

132

AROMATIC ALCOHOLS AND PHENOLS

[63 A-F.

tion with potassium permanganate gives
4-brom-m-toluic acid (Claus, Journ. pr.
Ch. [2] 46^ 2,1), and this can be con-
verted into p-cresol as before.

Toluene or m- or p- xylene can^ by
further methylation, be converted into
pseudoeumene = i : 3 : 4-trimethylben-
zene (Fittig and Ernst^ Ann. 139, 187 ;
Fittig and Jannasch, Ann. 151, 286 ;
Fittig and Laubinger, I6id. 257 ; Jan-
nasch, Ann. 176, 286 ; Friedel and
Crafts, Ann. Chim. [6] 1, 461 ; Ador and
Rilliet, Ber. 12, 329), the sulphonic acid
of which (Jacobsen, Ann. 184, 199)
gives a sulphonamide, which, by oxida-
tion with alkaline permanganate, gives
4-sulphamidemethylbenzene-2 : 5-dicarb-
oxylic (methylterephthalic = a-xylid-
ic) acid (Jacobsen and Meyer, Ber.
16, 190). The latter (sulphamide) on
potash fusion gives methyl-4-phenol-
2 : 5-dicarboxylie (s-hydroxy methyltere-
phthalic) acid {Ibid.), and this on heat-
ing with lime gives p-cresol.

Note : — All generators of toluene thus become
generators of p-cresol,

[B.] From p-hydwxyphenylaeetlc acid
[Vol. II] by heating with lime (Sal-
kowski, Ber. 12, 1440).

[C] From acetone [IO6] through
mesitylene (see under benzyl alcohol
[54 ; D]), mesitylenesulphonic acid
(Jacobsen, Ann. 146, 95), 4-hydroxy-
mesitylenic (i : 3-dimethyl-4-phenol-5-
carboxylic) acid by potash fusion of the
sulphonic acid (Fittig and Hoogewerff,
Ann. 150, '^'^?), 4 -hydroxy uvitic (4-
methylphenol-3 : 5-dicarboxyhc) acid by
potash fusion of hydroxymesitylenic
acid (Jacobsen, Ann. 195, 285), and
decomposition of the hydroxyuvitic acid
by heating with hydrochloric acid at
200° [Ibid. 206, 196}.

Or from mesitylene through mesityl-
enic acid (see under o-cresol [61 ; B]),
4-nitro- and 4-aminomesitylenic acid
(Schmitz, Ann. 193, 162; 171), 4-hy-
droxymesitylenic acid by the diazo-reac-
tion (Jacobsen, Ber. 11, 2055), and then
4-hydroxyuvitic acid and p-cresol as
above.

Or 4-hydroxymesitylenic acid may
be converted into 1:3: 4-xylenol by
heating with hydrochloric acid at 200°

(Jacobsen, Ber. 11, 2052 ; Fittig and
Hoogewerff, Ann. 150, 330), and the
xylenol converted into 4-hydroxy-m-
toluic acid and p-cresol as under A.

Or mesitylene may be converted into
mesitol (1:3: 5-trimethyl-2-phenol) by
potash fusion of mesitylenesulphonic
acid, or by the diazo-reaction from
aminomesitylene (Biedermann and
Ledoux, Ber. 8, 59 and 250 ; Jacob-
sen, Ann. 195, 268). Mesitol on potash
fusion gives 4-hydroxymesitylenic acid
(Jacobsen, loc. cit. 274), from which
p-cresol can be obtained as above.

Or from mesitylenic acid through
a-sulphomesitylenic acid by sulphona-
tion (Remsen and Brown, Am. Ch.
Journ. 3, 218), 4-hydroxymesitylenic
acid by potash fusion [Ibid. 220), and
then as above.

Or mesitylene may be oxidised to
uvitic acid (see under benzyl alcohol
[54 ; D]), which, by distillation with
lime, gives m-toluic acid (Bottinger and
Ramsay, Ann. 168, 255). The latter
can be converted into 4-hydroxy-m-
toluic acid and p-cresol as under A.

Note : — Generators of mesitylene and uvitic
acid (see under benzyl alcohol [54 ; D to Q,])
thus also become generators of p-cresol.

Acetone may also be converted
through phorone into pseudoeumene
(see under o-cresol [61; B]), and the
latter into s-hydroxymethylterephthalic
acid and p-cresol as under A.

[D.] Tarahydroxyhenzoic aldehyde
[119] gives, among other products, p-
cresol when heated with acetic acid and
zinc dust (Tiemann, Ber. 24, 3170). ^

[E.] Mefacresol [62] on nitration
yields a mixture of 4- and 6-nitro-m-
cresol (Stiidel, Ann. 217, 51 ; 259, 210).
The ethyl ether of the former gives, on
heating with strong aqueous ammonia
at 140-150°, 4-nitro-m-toluidine (Stadel
and Kolb, Ann. 259, 224). The latter
on replacement of the NHg-group by
hydrogen by the diazo-method would
give p-niti-otoluene, which can be con-
verted into p-toluidine and p-cresol as
under A.

[P.] Anethole [68] when heated under
pressure to 250-275° gives, among other
products, p-cresol methyl ether (Orn-

63 F-64 C]

PARACRESOL

133

dorff^ Terrasse, and Morton, Am. Ch.
Journ. 19, 845).

Note : — Paracresol can be converted into p-
cresylsulphuric acid (potassium salt) byheating
the potassium salt with a solution of potassium
pyrosulphate (Baumann, Ber. 9, 1389).

64. Fhlorol; 2-Ethylphenol.

HO

C.Ho

Natural Sources,

The phlorol complex probably occurs
in gum-ammoniac, the dried sap of
Dorema ammoniacuw,, which jaelds
phlorol methyl ether on distillation
with zinc dust (Ciamician, Ber. 12,
1658).

Hlasiwetz obtained a phlorol by dis-
tilling barium phloretate with lime
(Ann. 102, 166), but since phloretic
acid is a para-hydroxybenzene deriva-
tive, it is doubtful whether the phlorol
thus obtained is the ortho-ethylphenol,
althovigh Oliveri concludes that it is
identical with this modification (Gazz.
13, 263).

Synthetical Processes.

[A.] Benzene [6 ; I, &c.] can be con-
verted into ethylbenzene by several
processes : —

By the action of sodium on a mixture
of brombenzene and ethyl bromide (Fit-
tig, Ann. 131, 310; 133, 223; 144,
278 ; Schramm, Ber. 24, 1333).

From benzene, ethyl iodide, bromide
or chloride, and aluminium chloride
(Friedel and Crafts, Ann. Chim. [6]
1, 457; Sollscher, Ber. 15, 1680 ;
Sempotowski, Ber. 22, 2662 ; Behal
and Choay, Bull. Soc. [3] 11, 207 ;
Radziewanowski, Ber. 27, 3235).

From benzene and ethylene in the
presence of aluminium chloride (Bal-
sohn. Bull. Soc. [2] 31, 540), or by
heating benzene with ethyl ether and
zinc chloride {Ibid. 32, 618).

From benzene and ehloracetic or
chloroformic ester and aluminium
chloride (Friedel and Crafts, Ann. Chim.

[6] 1, 527; Rennie, Trans. Ch. Soc.

From benzene and ethylene through
thedibromideof thelatter, vinyl bromide,
and the action of the latter on benzene
in presence of aluminium chloride (An-
schiitz, Ann. 235, 331).

Ethylbenzene when brominated (in
the dark) in presence of iodine gives a
mixture of o- and p-ethylbrombenzene
(Schramm, Ber. 18, 1273; Sempotowski,
Ber. 22, 2668). The latter on sulphona-
tion yields ethyl-4-brombenzene-2-sul-
phonic acid (Sempotowski, loc, cU.),
which on debi'omination by zinc dust
and ammonia gives ethylbenzene-o-
sulphonic acid (Idi/L). The latter yields
phlorol on fusion with potash (Beilstein
and Kuhlberg, Ann. 156, 311 ; Sempo-
towski, loc. cit. 3672).

Or ethylbenzene may be nitrated,
the o-nitro-derivative reduced, and the
amino -ethylbenzene converted into
phlorol by the diazo-method (Suida and
Plohn, Monats. 1, 175; B^hal and
Choay, Bull. Soc. [3] 11, 209 ; Sempo-
towski, loc. clt. 2672 ; for nitration of
ethylbenzene and separation of isomer-
ides see Schultz and Flachslander,
Journ. pr. Ch. [2] 66, 153).

[B.] From styrene [?] through ethyl-
benzene by heating with hydriodic acid
(Berthelot, Bull. Soc. [2] 9, 455), or by
passing the vapour mixed with hydrogen
over heated copper (Sabatier and Sen-
derens, Comp. Rend. 130, 1761 ; 132,
1254; 134, 1 1 27). Also by reduction
with sodium in alcoholic solution
(Klages and Keil, Ber. 36, 1633), and
then as under A.

[C] P/ienol [60] when heated with
absolute alcohol and zinc chloride gives
a mixture of ethylphenols (Auer, Ber.
17, 670 ; Errera, Gazz, 14, 484), among
which phlorol is present.

Or phenol may be converted into
phenoxylacetal by heating sodium
phenate with chloracetal at 160°
(Autenrieth, Ber. 24, 163 ; Pomeranz,
Monats. 15, 739).

[Chloracetal is prepared by the action
of chlorine on ethyl alcohol (Lieben,
Ann. 104, 114; Fritsch, Ann. 279,
288 : see also 54, p. i n)-]

Phenoxylacetal when heated with zinc

134

AROMATIC ALCOHOLS AND PHENOLS

[64 C-J.

chloride (in acetic acid solution) con-
denses to coumarone (Stoermer, Ber.
30^ T-yo^), and this can be reduced to
phlorol as below under D.

[D.] Prom conmarhi [Vol. II] through
the chloride or bromide (Perkin, Zeit.
[2] 7, 178; Journ. Ch. Soc. 17, 368;
24, 37; Ann. 157, 116; Pittig and
Ebert, Ann. 216, 163), a-chlor- or a-
bromcoumarin (Perkin, loc. c'lt. ; also
Journ. Ch. Soc. 23, 368), o-couma-
rilie acid by the action of alcoholic
potash (Ibid. Journ. Ch. Soc. 24,
45 ; Pittig and Ebert, loc. cit.),
coumarone by heating coumarilic acid
with lime (Fittig and Ebert, loc. cit.
168 and 226, 347), and reduction of
coumarone in hot alcoholic solution with
sodium, hydrocoumarone being simul-
taneously formed (Alexander, Ber. 25,
2410).

The conversion of hydrocoumarone
into o-ethylphenol can also be effected
by boiling with strong hydriodic acid
solution (Baeyer and Scuff ert, Ber. 34,
52). Coumarone also gives o-ethyl-
phenol among the products of its de-
composition by alcoholic alkali (Stoermer
and Kahlert, Ber. 35, 1630).

[E.] Prom salici/lic aldeliyde [117]
and acetic acid [Vol. II] through o-
aldehydophenoxyaeetic acid (aldehydo-
phenylglycollic acid) by the action of
chloracetic acid on the sodium compound
of the aldehyde (Rossing, Ber. 17, 2990),
coumarone by heating the aldehyde acid
with acetic anhydride and sodium ace-
tate {Itnd. 30C0), and then as under D.
[P.] Cinnatnic acid [Vol. II] when
nitrated gives a mixture of o- and p-
nitro-acids (Beilstein and Kuhlberg,
Ann. 163, 136; Morgan, Ch. News,
36, 269 ; Jahresber. 1877, 788; Miiller,
Ann. 212, 124; Drewsen, Ann. 212,
151 ; Pischer and Kuzel, Ann. 221,
265). The former, by the action of hypo-
chlorous acid on the sodium salt, yields
(with o - nitrophenylchlorlactic acid)
i2-chlor-2-nitrostyrene = o-nitrophenyl-
w-chlorethylene (Lipp, Ber. 17, 1070),
which, by reduction and the diazo-
method, gives i--chlorvinylphenol = o-
hydroxy-oo-chlorstyrene (Komppa, Ber.
26, 2970). The latter when heated
with strong potash solution yields

coumarone {Ibid. 2971), which can be
converted into phlorol as under D.

[G.] Benzoic aldehfde [ll4] on nitra-
tion gives (with much m-nitro-) a small
quantity of o-nitro-aldehyde (Rudolph,
Ber. 13, 310), which, on heating with
acetic anhydride and sodium acetate,
yields o-nitrocinnamic acid (Gabriel and
Meyer, Ber. 14, 830). The latter can
be converted into coumarone and phlorol
as under P.

Note : — For o-nifcrobenzaldehyde generators
see also under indigo [Vol. II].

[H.] Prom phenylacetic acid [Vol. II]
through the 2 : 4-dinitro-acid by nitra-
tion (Radziszewski, Ber. 2, 210; Gabriel
and Meyer, Bei*. 14, 823), 2-nitro-4-
amino-acid by reduction, the diazo-
chloride by the action of nitrous acid
in presence of hydrochloric acid, o-nitro-
benzaldoxime by heating the diazo-
chloride with alcohol, o-nitrobenzalde-
hy^de by oxidising the aldoxime with
chromic acid (Gabriel and Meyer, loc.
cit. and 15, 3057 ; Gabriel, Ibid. 16,
520), and then as under G.

[I.] Acetoacetic ester [Vol. II] and
benzene can give rise to phlorol by the
following steps : —

Benzene is brominated, the mono-
brombenzene converted by cold nitration
into brom-2 : 4-dinitrobenzene (Kekule,
Ann. 137, 167; Spiegelberg, Ann. 197,
257 : see also Walker and Zincke, Ber.
5, 117), the latter combined with
sodio-acetoacetic ester so as to form 2 :
4-dinitrophenylacetoacetic ester (Heck-
mann, Ann. 220, 131 : a bis-dinitro-
phenyl derivative is formed simul-
taneously). The dinitrophenyl ester on
heating in alcohol with 10 per cent,
sulphuric acid is converted into 2 : 4-
dinitrophenylacetic acid {Ibid. 134),
which can be treated as above.

[J.] llacemic or tartaric acid [Vol. II]
and n-prop'/l alcoJiol [l5] are generators
of ethylbenzene, and therefore of
phlorol, by the following steps : —

Pyroracemic acid is obtained from the
above acids by^ dry distillation or other
method (see under benzyl alcohol [54 ;
N]), and this, when mixed with propionic
aldehyde and barium hydroxide solution,
condenses to 1:3: 5-ethylisophthalic

64 J-66.]

PHLOROL

135

acid (Doebner, Bei% 23, 2379 ; 24,
1746)^ which g-ives ethylbenzene on
distilUng- the calcium salt [Ibid. 23,
238 ).

Note : — The generators of pyroracemic acid
referred to under benzyl alcohol [54 ; F ; I ;
O ; P] thus become, with n-propyl alcohol,
generators of phlorol.

[K ] AcetopTienone [7; D and 114; A]
j?ives dypnone [CH3 . qCgH^) : C :
CH . CO . CgHg] as the first product of
condensation, and this, on heating for
80 hours at 280°, yields ethylbenzene
(Ameye, Bull. Acad. Roy. Belg. [3] 37,
227 ; Delacre, Ib'ul. [3] 39, 68 ; Ch.
Centr. 19CO, 2, 256).

Ethylbenzene is also among the pro-
ducts of reduction of acetophenone by
sodium in alcohol (Klages and Allen-
dorff, Ber. 31, 1003).

65. 3-Etliylplienol ; Meta-ethyl-
phenol.

HO

\/

Natuhal SOUIICE.

A phlorol probably occurs as isobutyr-
ate in oil of arnica root from Arnica
wontana (Sigel, Ann. 170, 354) which
may be m-ethylphenol, but this requires
confirmation.

Synthetical Processes.

[A.] From elhylhe^izene (see under
pidoroi [64 ; A]) by bromination and
sulphonation, whereby (with the 4-
brom-2-sulphonic acid) there is formed
ethyl-2-brombenzene-3- or 5-sulphonic
acid. The latter on debromination with
zinc dust and ammonia gives ethyl-
benzene-m-sulphonic acid (Sempotowski,
Ber. 22, 2673), which yields m-ethyl-
phenol on potash fusion {Ibid. 2674).

Or the ethyl-p-nitrobenzene (obtained
as under phlorol [64 ; A]) can be re-
duced to ethyl-p-aminobenzene, acetyl-
ated, nitrated, and hydrolysed so as to
form 3-nitro-4-aminoethylbenzene, the
amino-group replaced by hydrogen by

the diazo-method, the ethyl-m-nitro-
benzene reduced to ethyl -m-amino-
benzene. and the latter converted into
m-ethylphenol by the diazo -method
(Behal and Choay, Bull. Soc. [3] 11,
212).

66. Carvacrol ; Cymophenol ;

6-Methyl-3-IsopropylpIienol ;

1 : 4-Methylmethoetliyl-2-Fhenol.

CH,

OH

CH3 . CH . CH3

Natural Soueces.

Occurs in oils of Origanum hirtum
from Trieste and 0. ^wyrncEum from
Smyrna (Jahns, Arch. Pharm. 215, I ;
Gildemeister, Ibid. 231, 182); in oil
from the pepperwort or summer savory,
Satureia /lortensis, and the mountain
savory, S. montana (Jahns, Ber. 15,
816; Haller, Comp. Rend. 84, 132;
Bull. Soc. [2] 37, 411) ; in oil of thyme
from T/iipniuH serpyllmn (Jahns, Arch.
Pharm. 216, 277; Ber. 15, 819); in
oil of wild bergamot from Monarda
Jistulosa (Kremers, Ch. Centr. 1897,
2, 41 j Pharm. Rund. 13, 207 ; Melzner
and Kremers, Pharm. Rev. 14, 198;
Kremers and Hendricks, Pharm. Arch.
2, 73), and in the oil from Tycnanthemum
lanceolaUcm = Thymus virginims (Correll,
Pharm. Rev. 14, 32; Ch. Centr. 1898,

1. 123)-

Occurs in small quantity in the
ethereal oil from the fruit of the Mexi-
can ScJiimis molle (Gildemeister and
Stephan, Arch. Pharm. 235, 582).

According to Duyk carvacrol occurs
with thymol in oil of thyme from T.
vulgaris (Ch. Centr. 1898, 1, 783;
Journ. Pharm. [6] 7, 190). The oil
of Monarda punctata (from Wisconsin)
probably contains (with thymol) carva-
crol (Kremers and Hendricks, Ch. Centr.
1899, 2, 125; Pharm. Arch. 2, 73).
The oil from the N. American wild
mint, Mentha canadensis, may contain
carvacrol (Gage, Pharm. Rev. 16, 412).

Carvacrol is among the phenolic eon-

136

AROMATIC ALCOHOLS AND PHENOLS [66-67 B.

stituents of oil of camphor (Sugijama ;
SchimmeFs Ber. Oct. 1903; Ch. Centr.
igo2,, 2, 1307).

Synthetical Processes.

[A.] Prom cj/mene [6] by sulphona-
tion (Gerhardt and Cahours^ Ann. Chim.
[3] 1, 106; Delalande, Ibid. 368;
Miiller, Ber. 2, 1 30 ; Jacobsen^ Ber.
11, 1 060; Glaus and Cratz, Ber. 13,
901; 14, 3141; Spica, Ber. 14, 6^^;
Gazz. 11, 201 ; Sieveking-, Ann. 106,
260 ; Beilstein, Ann. 170, 287 ; Paterno,
Ber. 7, 591; Gazz. 3, 544; Kraut,
Ann. 192, 226; Baur, Ann. 220, 18),
and potash fusion of the a-(2)-sulphonic
acid thus formed (Pott, Ber. 2, 121 ;
H. Miiller, Iljid. 130 ; Jacobsen, Ber.
11, 1060). Cymene on nitration gives
2-nItrocymene (CH3= i) (Barlow, Ann.
98, 245 ; Landoiph, Ber. 6, 937 ;
Fittica, Ann. 172, 314 ; Schumoff,
Journ. Buss. Soc. 19, 119; Widman,
Ber. 19, 584 ; Sbderbaum and Widman,
Ber. 21, 2126), and 2-aminocymene by
reduction (Soderbaum and Widman,
luc. cit. 2127). The cymidine thus
formed yields carvacrol by the diazo-
method (Semmler, Ber. 25, 3353)-

[B.] Carvone [l27] on heating with
acids or alkalis gives carvacrol (Volckel,
Ann. 85, 246; Kekule and Fleischer,
Ber. 6, 1088 j Lustig, Ber. 19, 12;
Reychler, Bull. Soc. [3] 7, 32 ; Tiemann,
Ber. 32, 109). With formic acid the
yield is quantitative (Klages, Ber. 32,
1516).

67. Thymol; Metacymophenol ;
5-Methyl-2-Isopropylphenol ;
1 : 4-Methylmethoethyl-3-Plienol.
CHs

/\

.'OH
CH3.CH.CH3

Natural Sources.

In oil of thyme from Thymus vulgaris
(Doveri, Ann. Chim. [3] 20, 174;
Ann. 64, 374 : Lallemand, Comp. Rend.
37, 498 ; Ann. Chim. [3] 49, 148 ;
Ann. 102, 119) and T.serpyilum (Jahns,

Ber. 15, 819; Arch. Pharm. 216, 277);
in oil from the seeds of bishop^s weed,
Ftychotis ajowan (Haines, Journ. Ch.
Soc. 8, 289; Stenhouse, Ann. 93, 269;
98,309; H. Miiller, Ber. 2, 130); in oil of
American horse-mint, Monarda punctata
(Arppe, Ann. 58, 41 ; SchimmeFs Ber.
Oct. 1885; Schumann and Kremers,
Ch. Centr. 1897, 2, 42; Pharm. Rev.
1896, 1); and in oil of Oswego tea
from Monarda didynia (Fliickiger, Arch.
Pharm. 212, 488).

Menthol [4l] or peppermint camphor,
which occurs in the oil of Mentha pipe-
rita and other species of Mentha, is a
hexahydrothymol. The phenols present
in the oil of wild bergamot from Mo-
narda fistidosa contain less than 2 per
cent, of thymol (Kremers, Ch. Centr.
1899, 2, 126; Pharm. Arch. 2, 73).

Thymol occurs in the N. American
oil of Cunila mariana (Millemann, Am.
Journ. Pharm. 38, 495 ; SchimmeFs
Ber. Oct. 1893), and (possibly) in the oil
of the N. American wild mint, Mentha
canademis (Gage, Pharm. Rev. 16, 412).

The oil from the Japanese Mosla
japonica contains 44 per cent, thymol
(Shimoyama ; see Gildemeister and
Hoffmann, p. 861).

Oil from the Algerian Origanum jiori-
liimluni = 0. cinereum contains thymol
(Battandier, Journ. Pharm. 16, 536 ;
Journ. Soc. Ch. Ind. 21, 155 1).

Synthetical Processes.

[A.] From cumic aldehyde [II6] by
nitration, conversion of the nitro-deriv-
ative into nitrocymylidene chloride
(CeH3.CHCl,.N02.C3H, = 1:3:4)
by the action of phosphorus penta-
chloride, reduction to the corresponding
3-aminocymene by zinc and hydro-
chloric acid, and conversion into thymol
by the diazo-method (Widman, Ber. 15,
166).

[B.] From menthone [129] through
the dibromo-derivative, the latter giving
thymol on heating with quinoline
(Beckmann and Eickelberg, Ber. 29,
418 : see also Oddo, Gazz. 27, 112).

Or menthone gives, among the pro-
ducts of bromination, pentabromdehydro-
thymol,and this yields thymol by reduc-

67 B-e9.]

THYMOL

137

tion with zinc dust and hydrochloric
acid followed by sodium in alcoholic
solution (v. Baeyer and Seuffert, Ber.
34, 47).

[C] C/jmene [6] is brominated and
then sulphonated. The bromsulphonic
acid on heating- with ammonia and zinc
dust is debrominated^ and the 3-cymene-
sulphonic acid thus obtained gives
thymol on fusion with alkali (Dines-
mann, Germ. Pat. 125097 of 1900 ;
Ch. Centr, 1901^ 2^ 1030 J ^^ng. Pat.
13745 of 1901; Journ. Soc. Ch. Ind.
20, 1 01 9).

68. Anethole ; Anisstearoptene ;

Fara-anol Methyl Ether ;

l^-Propenyl-4-Anisole.

CH : CH . CH3

OCH3

Natural Souhces.

In oil of aniseed from P'lmpinella
anham (De Saussure, Ann. Chim. [2]
13, 280 ; Dumas, Ann. 6, 245 ; Blan-
chet and Sell, Ibid. 287 ; Cahours,
Ibifl. 41, 56; 56, 177; Laurent, Ibid.
44, 313; Gerhardt, Ibid. 318 ; 48, 234 ;
Journ. pr. Ch. [i] 36, 267), and in oil of
star-anise from Illicium venim (Cahours,
Comp. Rend. 12, 1213; Ann. 35, 313;
Persoz, Comp. Bend. 13, 433 ; Ann. 44,
311); in Chinese oil of star-anise (Tardy,
Bull. Soc. [3] 27, 990).

In oil of anise-bark from a species of
Illicium (^ parvijlomtn) from Madagas-
car (SchimmePs Ber. April, 1892); in
oil of fennel from Fo&uiculum vulgar e
(Blanchet and Sell, Ann. 6, 287;
Cahours, Ann. 41, 74; Journ. pr. Ch.
24, 359);

In oil of French, Algerian, and
Galician bitter fennel (Tardy, Bull.
Soc. [3J 17, 660; 27, 994); in oil of
Japanese fennel (SchimmeFs Ber. Oct.
1893; Umney, Pharm. Journ. 57, 91);
in oil of Macedonian fennel and of
Indian fennel from F. paumoriiim
(Umney, loc. cit. 58, 226).

Anethole has been found in the

ethereal oil of Piper pellakm (Surie, Ch.
Centr. 1899, 1, 883), and in oil of Os-
morrltiza longistylts from N. America
(Eberhardt, Pharm. Rund. 5, 149).

Note : — The anethole which Gerhardt be-
lieved to exist in oil of tarragon from Artemisia
dracunculus (Comp. Rend. 19, 489) has since
been shown to be the isomeric methylchavi-
col = estragol (Schimmel's Ber. April, 1892 ;
Grimaux, Comp. Kend. 117, 1089 ; Hell and
Gaab, Ber. 29, 344).

Synthetical Processes.

[A.] From anisic aldehyde [l20]
through methylparapropiocoumaric acid
by heating the aldehyde with propionic
anhydride and dry sodium propionate,
and distilling the acid thus formed
(Perkin, Journ. Ch. Soc. 31, I, 411).

Or the anisic aldehyde may be heated
with sodium propionate and propionic
anhydride at 200°, when anethole is
directly formed (Moureu and Chauvet,
Comp. Rend. 124, 404 ; Moureu, Ann.
Chim. [7] 15, 135).

Or from anisic aldehyde and ethyl al-
cohol [14]. The aldehyde and magne-
sium ethiodide condense to form ane-
thole and a polymeride (Behal and Tif-
feneau, Comp. Rend. 132, 563 : see
also Bougault, Bull. Soc. [3] 25, 1160).
[B.] YxQxn. phenol \Q0\ pjropionic acid
[Vol. II], and methyl alcohol [l3]. Phe-
nol is converted into anisole (see under
anisic aldehyde [120; B]), and the latter
into j)-propionylanisole by treatment
with propionyl chloride in presence of
aluminium chloride (Gattermann, Ber.
22, II 29; Klages, Ber. 35, 2262).
Propiouylanisole reduces to a carbinol
[i-propylol-(i^)-4-methoxy benzene], of
which the acetate gives anethole on
boiling with pyridine (Klages, loc. cit.).

69. Catechol; Fyrocatechol ;

Orthodihydroxybenzeue ;

1 : 2-Fheuediol.

HO

OH

Natural Sources.

Said to have been found in various
parts of plants, especially in autumnal

138

AROMATIC ALCOHOLS AND PHENOLS

[69.

foliage (Kraus, N. Rep. Pharm. 22,
273; Journ. Ch. Soc. 26, 1049 : Preusse,
Bied. Centr. 1879, 874, denies the
existence of free catechol in plants).

Occurs in leaves of the Virginian
creeper, Ampelopsis hederacea (Gorup-
Besanez, Ber. 4, 905), in sap of the
kino plants, Butea frondosa, Eucalyptus
resinifera, Pterocarpus marsupium, P.
erinaceus, &c. (Eisfeldt, Ber. 4, 906 ;
Fliickiger, Ber. 5, i ; Gorup-Besanez,
Ibid. 47), in raw beet-sugar (v. Lipp-
mann, Ber. 20, 3298 : see also Ber. 26,
3061), and in the dry external scales of
the onion.

Catechol has been found in Puglia
olive oil (Canzoneri, Gazz. 27, 3), in the
colouring-matter of red grapes (Sostegni,
Journ. Ch. Soc. 70, II, 122), in the
aqueous distillate (tar water) from bitu-
minous shale (Germ. Pat. 58944 of
1892; Ber. 35, 4325 note) and from
coal (Bornstein, Ber. 35, 4324). In
these last cases the catechol may be
a product of destructive distillation.

A glucoside contained in the tansy,
Tanacetum vulgare, is a compound of
catechol with dextrose and Isevulose
(Nedra, Journ. Soc. Ch. Ind. 19, 686).

The catechol complex exists in many
products of vegetable origin : —

Quereetin and isomerides from Persian
berries (fruit of various species of Bkam-
mis) ; from the bark of Qiiercus imctoria',
from the fruit, flowers, and leaves of the
horse-chestnut ; from the berries of the
sea-buckthorn [Hippophae rJiamnoides) ;
from the flowers oi Reseda luteola ; from
Andromeda japonica ; ixovcvCarya iomen-
tosa ; from the bark of apple; from leaves
of the tea plant, vine, and ash; from
catechu, hops, and from rutin, a gluco-
side which is contained in the leaves of
rue, Puta graveolens.

Quereetin occurs also in flowers of
Capparis spinosa, in safSower, in rose
leaves, and leaves of buckwheat. Poly-
gonum fagopyrum. The colouring-matter
sophorin from Chinese berries, from
Sophora japotiica, may contain the
quereetin complex in the form of a
glucoside.

Note :— Quereetin exists in the above plants
sometimes free, but more generally in the form
of the glucosides queiNjitrin, rutin, robinin, &c.

According to Schmidt and Waljaschko (Ch.
Centr. 1901, 2, 121) the rutin from common
rue is not identical with robinin or quercitrin,
but resembles the glucoside from capers and
from Viola tricolor (violaquercitrin ? : see below).
For details of distribution of tliese colouring-
matters and glucosides see ' Die Glykoside,' by
Van Rijn, 1900, and ' Die Chemie der natur-
lichen Farbstoffe,' by Hans Kupe, 1900.

Quereetin occurs also as the glucoside
osyritrin or myrticolorin in Cape sumach
from the leaves of Colpoon cowpressum
(A. G. Perkin, Trans. Ch. Soc. 71,
1132), and in the leaves oi Ejicalyptus
tnacrorrhyiicha (Smith, Trans. Ch. Soc.
73, 697 ; A. G. Perkin, Proc. Ch. Soc.
18, 58), and in Viola tricolor variensis
as the glucoside violaquercitrin (Man-
delin, Jahresber. 1883, 1369 : accord-
ing to A. G. Perkin, Trans. Ch. Soc.
81, 477, violaquercitrin, myrticolorin,
and osyritrin are identical).

The presence of quereetin in catechu
from Uncaria (Nauclea) gambier and
Acacia catechu (Lowe, Zeit. anal. Ch.
12, 134) has been confirmed by A. G.
Perkin (Trans. Ch. Soc. 71, 1135), and
its existence in the colouring- matters
from the yellow wallflower, Cheiranthus
cheiri, from white hawthorn flowers,
Cratcegiis oxyacantha, and from Pumex
ofjiusif alius, shown by the same author
{loc. cit. 69, 1566; J 5 70; 71, 1 1 99).

The yellow colouring-matter of In-
dian and American podophyllum from
Podophyllum emodi and P. peltatum, is
quereetin (Dunstan and Henry, Ibid.
73, 221); the dyestuff from the Indian
Pelphiuium zald also contains a glu-
coside of quereetin (A. G. Perkin and
Pilgrim, Ibid. 273).

A colouring-matter from the leaves
and stem of Tamaris gallica and T.
africana is a methylquercetin (A. G.
Perkin and Wood, ibid. 380); the
leaves of Ailanthns glandulosa contain
quereetin [Ibid. 382); an isomeride of
quereetin exists in colouring-matters
from the leaves of Arctostaphylos nva-
ursi and from S. African 'broach leaves'
{Ibid. 384; also A. G.P. Proc. Ch. Soc.
14, 104; 16, 45; Trans. 77, 425)-

Quereetin is contained in the leaves
of Rhus rhodanthema from N. S.
Wales (A. G. P. Trans. Ch. Soc. 73,
1018); in common ling or heather.

69.]

CATECHOL

139

Calluna vtilgaris {Ibid. 75, 837) ; in
log-wood, IIcBmaioxylon campeachianum ;
in tlie leaves of Uhus metopinm and
Coriaria myrfifolia {Ibid. Proc. Ch. Soe.
16, 45; Trans. 77, 423); and (or an
isomeride) in the New Zealand Wius
thymifolia (Easterfield and Aston, Trans.
Ch. Soe. 79, 122).

Quereetin is contained in the ethereal
extract of the spotted knotweed, J?oly-
gonum persicaria (Horst, Ch. Zeit. 25,

1055)-

llhamnetin, which occurs as a gluco-
side (xanthorhamnin) in Persian berries,
is monomethylquercetin, and rhamnazin,
existing- also as a glucoside in the same
berries, is a quereetin dimethyl ether
containing the methylcatechol (guaiacol)
complex (A. G. Perkin and Geldard,
Trans. Ch. Soe. 67, 496; A. G. P. and
Martin, Ibid. 71, 81 8; A. G. P. and
Allison, Ibid. 81, 469).

Isorhamnetin from the yellow wall-
flower (see above) is also a methyl-
quercetin (A. G. P. and Hummel, Ibid.
69, i$6g). Isorhamnetin is also con-
tained as glucoside in the colouring-
matter from the flowers of Belphinium
zalil (A. G. P. and Pilgrim, Ibid. 73,
371).

The catechol complex is present in
fisetin from the wood of Qiierbracho
Colorado and from young fustic, the
wood of Rhim cot inns, in which it exists as
the glucoside fustin. Luteolin [l4l], the
colouring-matter of weld, from Heseda
luleola and from dyer^s broom, Genista
tinctoria, contains the catechol com-
plex (A. G. P. Rid. 69, 803 ; A. G. p.
and Newbury, Proc. 15, 179 ; 242 ; 16,
181 ; A. G. P. and Horsfall, Trans. 77,

1314).

A glucoside contained with apiin
[140] in parsley is a derivative of
luteolin metliyl ether (Vongerichten,
Ber. 33, 2334 ; 2904).

Scoparin is related to luteolin (see
under luteolin [l4l] : also A. G. P.
Proc. Ch. Soe. 15, 123; 16, 45).

The catechol complex is probably
contained in brazilin from Brazil wood
from Cffsa/pinia crista, C. brasiliensis,
&c. (Gilbody and W. H. Perkin, junr..
Ibid. 15, 28 ; Feuerstein and v. Kosta-
necki, Ber. 33, io:j8 ; Schall, Ibid.

1046; Gilbody and W, H. Perkin, junr.,
Proc. Ch. Soe. 16, 107; W. H. P., junr.,
and Yates, Trans. 79, 1396 ; W. H. P.,
junr., Proc.Ch. Soe. 17, 257 ; Trans. 81,
221; 236; 1008; 1040; 1057; Herzig
and Pollak, Monats. 23, 165 ; v. Kosta-
necki and Lampe, Ber. 35, 1667;
Bollina, v. Kostanecki, and Tambor,
Ibid. 1675); and in gossypetin from
the flowers of Gossypmim herbaceum
(A. G. Perkin, Trans. Ch. Soe. 75,
828).

Haematoxylin, the colouring-matter
of logwood, appears to contain the
catechol and pyrogallol complexes (Gil-
body and W. H. Perkin, junr., Proc.
Ch. Soe. 15, 241 ; 16, 108 ; W. H. P.,
junr., and Yates, Trans. 81, 235, &c., as
under brazilin).

The glucoside coniferin, found in
the cambial fluid of coniferous trees,
in beet and asparagus, and in the
root of Scorzonera hispanica, contains,
through coniferyl alcohol, the guaiacol
complex.

The catechol complex is probably
contained in maelurin from old fustic,
the wood of Morus tinctoria = Madura
aurantiaca from Jamaica, Cuba, &c.
(Konig and v. Kostanecki, Ber. 27,
1996), and in fragarianin, a glucoside
from the root of Fragaria vesca.

The catechol complex may exist also
in some form in the catechins, com-
pounds obtained from catechu from
various sources, such as the twigs and
vmripe pods of Acacia catechu, from
U?icaria {Nancled) gambier, 'cortex lokri'
from Hymenma courbaril, &c. (see for
instance A. G. Perkin and Yoshitake,
Trans. Ch. Soe. 81, 11 72).

The complex may be contained in
kino'in and kino-red from gum kino
from Pterocarpus marsupium (Malabar),
and in certain resins and gum-resins,
such as guaiacum from G. officinale, and
gum-ammoniac from iJorema atmnouia-
cum; also in tormentilla red from the
root of Potentilla tormentilla, and in
many tannins, such as those from horse-
chestnut and from Fersea {Lanrus)
lingue, and in fraxitannic acid from ash
leaves.

The dimethylcatechol (veratrole) com-
plex is contained in the opium alkaloids.

140

AROMATIC ALCOHOLS AND PHENOLS

[69-A.

papaverine and narcotine, in pseud-
aconitine from the root of Aconitum
ferox, in berberine from Berberis vul-
garis, Xantlioxijlon clava, Hydrastis cana-
densis, %LQ,., in hydrastine from Hydra-
stis canadensis, and in corydaline from
the roots of Coryd alls [Aristolochia) cava.

The colouring-matter of red grapes
appears to contain the catechol complex
(Sostegnij Gazz. 32_, 17).

The following synthesised natural
products contain the catechol, guaiacol,
or veratrole complex : — Isoengenol [79] ;
methylisoeugenol [80] ; methyletigenol
[8I] ; vanillin [l2l] ; luteolin [l4l] ;
alizarin [l45] ; Itystazarin [147] ; proio-
catechuic acid [Vol. II] ; veratric acid
[Vol. II] j piperonylic acid [Vol. II] ;
liydrocaffeic acid [Vol. II] ; caffe'ic acid
[Vol. II] ; fertila'ic acid [Vol. II] ;
hesperetinic acid [Vol. II] ; piperic acid
[Vol. II].

Catechol has been found (as a salt of
catechol sulphate) in the urine of man
and herbivorous animals (Baumann,
Pfliiger^s Arch. 12, 6^ ; Baumann and
Herter, Zeit. physiol, Ch. 1, 244; Bau-
mann and Preusse, Ibid. 3, 157 ; Miiller,
Ber. 7, 1526 ; Nencki and Giacosa,
Zeit. physiol. Ch. 4, ^'^S; Schmiede-
berg, Ibid. Q, 189).

According to Halliburton (Journ.
Physiol. 10, 247), it is contained in the
cerebrospinal fluid. A phenolic sub-
stance extracted from the kidneys has
been considered to be catechol, but
according to O. v. Fiirth it is not this
compound (Zeit. physiol. Ch. 24, 142 ;
26, 15 ; 29, 105).

Synthetical Processes.
[A.] Phenol [6O] by various iodising
processes gives (with para-) ortho-iodo-
phenol (Schiitzenberger and Sengen-
wald, Comp. Rend. 54, 197; Korner,
Ann. 137, 197 ; Hlasiwetz and Wesel-
sky, Sitzungsber. Wien. Akad. 60 [2]
290; Lobanoff, Ber. 6, 1251; Schall,
Ber. 16, 1897; Willgerodt, Journ. pr.
Ch. [2] 37, 446). The latter on fusion
with potash gives catechol (Korner,
Zeit. [2] 4, 322 ; Lautemann, Ann.
120, 315; Noel ting and Strieker, Ber.
20, 3019).

Or phenol when chlorinated or bromi-
nated at 150-180° gives orthochlor- or
bromphenol (Merck, Germ. Pat. 76597
of 1893). These derivatives give catechol
on heating with caustic soda-lye under
pressure {Ibid. Germ. Pat. 84828 of

1893)-

Or phenol may be nitrated, the ortho-

(separated from the para-) nitrophenol
reduced, and the o-aminophenol con-
verted into o-iodophenol by the diazo-
method (Noelting and Wrzesinski, Ber.
8, 820 ; Noelting and Strieker, Ber.
20, 3018 ; Neumann, Ann. 241, 68).

o-Aminophenol is also converted
(partially) into catechol by heating to
a high temperature with dilute mineral
acids (Meyer, Ber. 30, 2569).

Or o-nitrophenol can be converted
into its methyl ether by methylation
(Brunck, Zeit. [2] 3, 204 ; Miihlhauser,
Ann. 207, 237; Willgerodt and Ferko,
Journ. pr. Ch. [2] 33, 153), into o-
anisidine by reduction (Miihlhauser,
loc. cit. 239), into guaiacol by the diazo-
method (Kalle, Eng. Pat. 7233 of
1 897 ; Journ. Soc. Ch. Ind. 17, 269),
and into catechol as below under P.

Or o-aminophenol can be converted
into o-chlorphenol by the diazo-method
(Schmitt and Cook, Ber. 1, 67), and
the chlorphenol sulphonated (Kramers,
Ann. 173, 331). The 2-chlorphenol-
4-sulphonic acid on heating at 250°
with caustic soda solution gives cate-
cholsulphonic acid, from which catechol
can be obtained by hydrolysis (Soc.
Chim. d. Usines du Rhone, Germ. Pat.
97099 of 1896; Ch.Centr. 1898,2,521).

Or a-phenoldisul phonic acid gives on
fusion with alkali catecholsulphonic
acid, from which catechol is obtained
by heating with 50 per cent, sulphuric
acid to 200° (Merck, Germ. Pat. 80817
of 1893). Or phenoltrisulphonic acid
(Senhofer, Ann. 170, iio; Arche and
Eisenmann, Germ. Pat. 51 321 of 1889)
on fusion with alkali at 230-260° gives
catecholdisulphonic acid (Tobias, Germ.
Pat. 81210 of 1894), the sodium salt of
which yields catechol when the concen-
trated aqueous solution is heated to 2 1 o-
215° {Ibid. Germ. Pat. 81209 of 1894).

Or phenol may be sulphonated (Ke-
kule, Zeit. [2] 3, 199), and the o-sul-

69 A-M.]

CATECHOL

141

phonic acid fused with alkali {IL'ul.
643 ; Deg-ener, Journ. pr. Ch. [3] 20,
30H).

Catechol is among* the products or
the fusion of phenol with caustic soda
(Barth and Schreder, Ber. 12, 419);
and also among* the products of the
electrolysis of a solution of phenol in
presence of magnesium sulphate and
acid carbonate by an alternating current
(Drechsel, Journ. pr. Ch, [3] 29, 249).
Catechol is among the products of the
action of hydrog-en peroxide on phenol
(Martinon, Bull. Soc. [2] 43, 156).

[B.] Salicylic acid [Vol. II] when
iodised by various methods g-ives, among
other products, an iodosalicylic acid,
which on rapid heating yields an iodo-
phenol, from which catechol can be
obtained as above (Kolbe and Laute-
mann, Ann. 115, 157 ; Lautemann, Ann.
120, 299 ; Hlasivvetz and Weselsky,
Ber. 5, 380 ; Ann. 174, 99 ; Liechti,
Ann. Suppl. 7, 129; Demole, Ber. 7,
1437 ; Fischer, Ann. 180, 346 ; Birn-
baum and Reinherz, Ber. 15, 458 ;
Miller, Trans. Ch. Soc. 41, 406).

Or salicylic acid may be nitrated
(Hiibner, Ann. 195, 6; 31; Schau-
mann, Ber. 12, 1346 ; Deninger, Journ.
pr. Ch. [2] 42, 551; Hirsch, Ber. 33,
3238), the 3-nitrosalicylic acid reduced,
the NHg-group replaced by iodine by
the diazo-method, and the 3-iodosali-
cylic acid fused with potash so as to
form catechol-o-carboxylic acid, which
on dry distillation gives catechol (Miller,
loc. cit.).

[C] Benzoic acid [Vol. II] gives
catechol among the products of its
fusion with potash (Hlasiwetz and
Barth, Ann. 130, 352; 134, 282).

[D.] Profocatecfmic acid [Vol. II] on
dry distillation gives catechol (Strecker,
Ann. 118, 285) ; also by fusion with
alkali (Barth and Schreder, Ber. 12,
1258).

[E.] Tijieronylic acid [Vol. II] when
heated with water at 210^ gives catechol
(Fittig and Remsen, Ann. 159, 143).

[F.] Veratric acid [Vol. II], when
heated with dilute hydrochloric acid,
gives a mixture of vanillic (3-methoxy-
protocatechuic) acid and the 4-meth-
oxy isomeride (Tiemann, Ber. 8, 514).

Vanillic acid on distillation with lime
yields guaiacol (catechol methyl ether)
\lljid. 1 123), and this, on heating with
aqueous hydriodic acid or by the action
of aluminium chloride, gives catechol
(Miiller, Jahresber. 1864, 525 ; Gorup,
Ann. 143, 166; Baeyer, Ber. 8, 153;
Tiemann and Koppe, Ber. 14, 2017;
W. H. Perkin, junr.. Trans. Ch. Soc. 57,
587 ; Hartmann and Gattermann, Ber.
25, 3532). Or veratric acid on distilling
its barium salt with baryta gives veratrole
(Merck, Ann. 108, 60; Koelle, Ann.
159, 243; Tiemann, Ber. 14, 30i6),
which by heating with alcoholic potash
at 180-190° yields guaiacol (Bouveault,
Bull. Soc, [3] 19, 75). The latter can
be converted into catechol as above.

[G.] Vanillin [l2l] on oxidation by
moist air gives vanillic acid (Tiemann,
Ber. 8, 1 1 23), which can be converted
into guaiacol and catechol as above.

Or vanillin can be converted into
acetferulai'c acid, oxidised by potassium
permanganate to acetvanillic acid, hy-
drolysed to vanillic acid (Tiemann,
Ber. 9, 420), and then treated as
above.

[H.] Glucuronic acid [Vol. II] on
long boiling with potash solution gives
(with oxalic acid, &c.) catechol (Thier-
felder, Zeit. physiol. Ch. 13, 280).

{!.] Besorcinol [70] gives catechol
among other products when fused with
caustic soda (Barth and Schreder, Ber.
12, 504).

[J.] Anisic acid [Vol. II] gives ani-
sole on distillation with baryta (Cahours,
Ann. 41, 69), and this on nitration yields
(with p-) o-nitroanisole, and by reduc-
tion anisidine (Miihlhauser, Ann. 207,
237 ; 239 ; Brunck, Zeit. [2] 3, 205).
The latter by the diazo-reaction gives
guaiacol (Kalle & Co., Germ. Pat. 95339
of 1 896, and under A above), from which
catechol can be obtained as under P.

[K.] Ilydrojuglone [90] gives catechol
among the products of its fusion with
potash (Mylius, Ber. 18, 475).

[L.] Dextrose [l54] is said to give
catechol among the products formed
when heated with water under pressure
(Munk, Zeit. physiol. Ch. 1, 362).

[M.] Mannose [156] gives (with lactic
acid) catechol on boiling with caustic

142

AROMATIC ALCOHOLS AND PHENOLS [69 M-70.

soda solution (Araki_, Zeit. physiol. Ch.
19, 460).

[N.] Benzene [6] when combined
with chlorine gives a hexachloride
which yields catechol, among- other pro-
ducts, when heated with water at 200°
(Meunier, Ann. Chim. [6] 10, a66 ;
Comp. Rend. 100, 1591)-

Or chlorbenzene on nitration gives
(with para-) orthochlornitrobenzene
( Jungfleisch, Ann. Chim. [4] 15, 1 86 ;
Laubenheimer, Ber. 7, 1765; 8, 1621 ;
Sokoloff, Zeit. [2] 2, 621 ; Lesimple,
Ibid. [2] 4, 225), and this by the action
of sodium methylate in methyl alcohol
yields o-nltroanisole (Lobry de Bruyn,
Rec. Tr. Ch. 9, 200), from which 0-
anisidine, guaiacol, and catechol can be
obtained as under A and P.

Catechol is among the products of
the oxidation of benzene with hydrogen
peroxide in the presence of ferrous
sulphate (Young, Proc. Ch. Soc. 15,
131 ; Cross, Bevan, and Heiberg, Ber.
33, 2018).

Nitrobenzene gives o-nitrophenol
when warmed with finely divided
potassium hydroxide. The transforma-
tion takes place slowly even at ordinary
temperatures (Wohl, Ber. 32, 3486).
Subsequent steps as above under A.

Or nitrobenzene by mild reduction
gives phenylhydroxylamine, which oxi-
dises to nitrosobenzene (Bamberger and
Storch, Ber. 26, 472 ; Bamberger and
Landsteiner, Ibid. 482 ; Bamberger,
Ber. 27, 11 82; 1273; 1347; 1548;
1555; Wohl, Ibid. 1432). The latter
gives o-aminophenol among the pro-
ducts of the action of hot aqueous alkali
(Bamberger, Ber. 33, 1939).

Or aniline (by nitration of acetani-
lide) gives (with p-) o-nitraniline, which
reduces to o-phenylenediamine. The
latter yields catechol on heating with
10 per cent, hydrochloric acid to 180°
(Meyer, Ber. 30, 2569).

[O.] From furfural [l26] through
pyromucic and mucobromic acids and
nitromalonic aldehyde (see under phloro-
glucinol [86 ; l]). The latter condenses
with acefoacetic ester [Vol. II] to form
3-nitrosalicylic acid (Hill, Soch, and
Oenslager, Am. Ch. Journ. 24, i).
Subsequent steps as above under B.

[P.] Caffeic acid [Vol. II] decom-
poses at 200° with the formation of
3 : 4-dihydroxystyrene = vinylcatechol
(Kunz-Krause, Ber. 30, 161 8). The
latter gives catechol on distillation under
reduced pressure {Ibid. 1620).

70. Resorcinol ;

Metadihydroxybenzeue ;

1 : 3-Fhenediol.

HO

;0H

Natural Sources.

The compound itself has not yet been
found as a natural product, but the
complex apparently, with the catechol
complex, enters into the constitution
of fisetin (for sources of fisetin see imder
catechol), and also into the constitution
of morin, the yellow colouring-matter
from old fustic, the wood of Moriis
{Machiva) tinctoria, and in the Indian
dyestuff from jack-fruit, Artocarpns
integrifolia (A. G. Perkin and Cope,
Trans. Ch. Soc 67, 937 ; Bablich and
A. G. Perkin, Ibid. 69, 798; A. G. P.
and Horsfall, Proc. Ch. Soc. 16, 182).

The complex exists in the glucoside,
lotusin, of the Egyptian vetch, Lotus
aralncus, through lotollavin (Dunstan
and Henry, Proc. Roy. Soc. 68, 374).

The resorcinol complex may be con-
sidered to exist also in pceonol [l33],
gentisin [137], purpuroxanihin [146],
methylpurpuroxanihin [l50], umbelli-
ferone and methylumbelliferoiie [Vol.
II], evxanihone [136], and possibly in
brazilin from Brazil wood {CfPsalpitiia
crista, C. brasitiensis, &c.) and sapan
wood (C. sapan).

Compounds containing this complex
may also exist in many resins and gum-
resins, such as galbanum, gum-ammoniac,
asafoetida, acaroid, sagapenum, &c. (For
references to constitution of brazilin see
under catechol [69] ; also Herzig, Mo-
nats.16,906; 19,738; GilbodyandW.H.
Perkin, junr., Proc. Ch. Soc. 16, 105;

70-B.J

RESORCINOL

143

Gilbody, W.H. Perkin^ junr.j and Yates,
Trans. Cli. Soc. 79, 1396.)

Synthetical Processes.

[A.] Benze7ie can be converted into
resorcinol by various processes : —

Ey nitration and partial reduction
m-dinitrobenzene and m-nitraniline can
be obtained (Deville, Ann. Chim. [3] 3,
187 ; Muspratt and Hofmann, Ann. 57,
214; Beilstein and Kurbatoff, Ann. 176,
43 ; Anschiitz and Heusler^ Ber. 19, 21 6 1 ;
Wiilfing", Germ. Pat. 67018 of 1891;
Ber. 26, Ref. 421). The latter gives m-
iodonitrobenzene by the diazo-method
(Griess, Zeit. [2] 2, 218), m-iodaniline
by reduction {Ibid.), and m-iodophenol
by the diazo-method (Noel ting and
Strieker, Ber. 20, 3020). The latter on
fusion with potash gives resorcinol
(Korner, Zeit. [2] 4, 322).

Or m-nitraniline can be converted
into m-nitrophenol by the diazo-method
(Fittig and Bantlin, Ber. 7, 179; 11,
2099 ; Henriques, Ann. 215, 323 ;
Wagner, Journ. pr. Ch. [2] 32, 70),
m-aminophenol by reduction (Bantlin,
Ber. 11, 2101), and resorcinol by the
diazo-method {Ibid.).

Or m-dinitrobenzene can be reduced to
m-])henylenediamine, which, on heating
with dilute acids to a high temperature,
is converted (partially) into resorcinol
(Meyer, Ber. 30, 2569).

Metadinitrobenzene when boiled with
potassium cyanide and methyl alco-
hol is converted into the nitrile of 6-
nitro-2-methoxybenzoic acid (Lobry de
Bruyn, Rec. Tr. Ch. 2, 212). The
latter on heating with methyl alcohol
and potash is converted into the nitrile
of 2 : 6-dimethoxybenzoic acid {Ibid.
219), which, on heating with strong
hydrochloric acid at 1 70°, splits up into
carbon dioxide, methyl chloride, am-
monium chloride, and resorcinol. Or
by potash fusion the nitrile is converted
into 2 : 6-dihydroxybenzoic acid, which
splits up into carbon dioxide and resor-
cinol on heating above 167°.

Or benzene may be nitrated, the mono-
nitrobenzene converted into m-nitro-
sulphonic acid by fuming sulphuric
acid (Limpricht and Bernthsen, Ann.

177, 82), into m-sulphanilic acid by
reduction, and m-aminophenol by fusing
the latter with caustic soda (Gesell. f.
Ch. Ind., Germ. Pat. 44792 of 1888 ;
Meyer and Sundmacher, Ber. 32, 2 1 1 2).
Benzene when sulphonated under
appropriate conditions gives p- and m-
disulphonic acids, the proportions vary-
ing according to the conditions of
sulphonation (Buckton and Hofmann,
Journ. Ch. Soc. 9, 255 ; Barth and
Senhofer, Ber. 8, 754; I477 ; 9, 969 j
Egli, Ber. 8, 817; Limpricht, Ber.
9, 550 ; Korner and Monselise, Ibid.
583 ; Binschedler and Busch, Monit.
Sci. 1878, 3169). Both p- and m-
benzenedisulphonic acid (the former by
isomeric transformation) give resorcinol
on fusion with caustic alkali, this being
the technical process (Garrick, Zeit.
[2] 5, 551 ; Barth and Senhofer, Ber. 8,
1483 ; Degener, Journ. pr. Ch. [2] 20,
319 ; Genvresse, Bull. Soc. [3] 15, 409 ;
Fahlberg, Am. Ch. Journ. 2, 195 ; Bin-
schedler and Busch, Jahresber. 1878,
1 137 and 1184; Schoop, Zeit. ch.
Ind. 1887, II, I; Miihlhiiuser, Ding.
Poly. Journ. 263, 154 ; Journ. Soc. Ch.
Ind. 6, 284).

[B.] From toluene (see under benzyl
alcohol [54; A, &c.]) through p-nitro-
toluene by nitration, 4-nitrotoluene-2-
sul phonic acid by sulphonation (Beilstein
and Kuhlberg, Ann. 155, 8 ; Jenssen,
Ann. 172, 230), the amino-acid by reduc-
tion (B. and K. Ann. 172, 230 ; Jenssen,
loc. cit. 233 ; Brackett and Hayes, Am.
Ch. Journ. 9, 400), p-cresol-2-sulphonic
acid by the diazo-method (Jenssen, loc.
cit. 237), and 2 : 4-dihydroxybenzoic
(2 : 4-phenediolcarboxylic or/3-resorcylic)
acid by potash fusion of the cresolsul-
phonic acid (Ascher, Ann. 161, 11).
/3-Resorcylic acid on heating with sodium
hydroxide, or per se, gives resorcinol
(Senhofer, Ber. 12, 1259).

Or toluene may be converted into the
2 : 4-disulphonic acid by sulphonation
(Hakanson, Ber. 5, 1085 ; Gnehm and
Forrer, Ber. 10, 542 ; Gnehm, ibid.
1276 ; Fahlberg, Ber. 12, 1052; Klason
and Berg, Ber. 13, 1 1 70; Senhofer, Ann.
164, 1 26 ; Klason, Ber. 19, 2890), the
disulphonic acid oxidised to 2 : 4-di-
sulphobenzoic acid (Blomstrand, Ber. 5,

144

AROMATIC ALCOHOLS AND PHENOLS

[70 B-F.

1088; Brunner^ Jahresber. 1879, 759 j
Fahlbevg-, Am. Ch. Journ. 2, 188), and
the latter converted by potash fusion
(below 250°) into /3-resorcylic acid (Blorn-
strand^ loc. c/L ; Fahlberg^ he. cit. 1 96),
from which resorcinol can be obtained
as above.

[C] From phenol [6O] through p-
bromphenol (Hiibner and Brenken, Ber,
6, 170 ; Gordon^ Proc. Ch. Soc. 1, 64. ;
Meldola and F. H. Streatfeild, Trans.
Ch. Soc. 73, 681), and fusion with
potash (Fittig and Mager, Ber. 7, 1 1 7 7 ;
8, 362), the resorcinol in this case being
formed by isomeric transformation.

Or phenol may be converted into 0-
and p-nitrophenol by nitration, the
latter reduced to p-aminophenol, and
the NH2-group replaced by iodine or
chlorine by the diazo-method (Noelting
and Strieker, Ber. 20, 3018; Schmitt,
Ber. 1, 6j : for references to direct
iodising of phenol see under catechol
[69 ; a] ; for direct chlorination of
phenol see Petersen and Bahr-Praderi,
Ann. 157, 1 23 ; also Dubois, Zeit. [2] 2,
705; 3, 205). Both p-chlor- and p-
iodophenol give resorcinol (by isomeric
transformation) when fused with potash,
the latter above 165° (Faust, Ber. 6,
1022 j Noelting and Wrzesinsky, Ber.
8, 820).

Resorcinol is also among the products
of fusion of phenol with caustic soda
(Barth and Sehreder, Ber. 12, 420).
The phenolsulphonic acids (see under
catechol [69 ; A]) also (by isomeric
transformation) give resorcinol when
fused with potash (Kekule, Zeit. [2] 3,
301).

[D.] Benzoic acid [Vol. II] when sul-
phonated with fuming sulphuric acid in
the presence of phosphorus pentoxide
gives 3 : 5-disulphobenzoic acid (Barth
and Senhofer, Ann. 159, 217), from
which by potash fusion 3 : 5-dihydroxy-
benzoic (3 : 5-phenediolcarboxylic or a-
resorcylic) acid is obtained (Ibid. 222).
This acid, on heating with sodium
hydroxide above 350°, yields resorcinol
(Barth and Sehreder, Ber. 12, 1258).

Or benzoic acid may be converted
directly or indirectly into m-bromben-
zoic acid (Peligot, Ann. 28, 246; Griess,
Ann. 117, 25 ; Reinecke, Zeit. [2] 1,

J 16; 2, 367; 5, 109; Hiibner, Ohly,
and Philipp, Ann. 143, 233 ; Hiibner
and Peterniann, Ann. 149, 131 ; An-
gerstein, Ann. 158, 2 and 5 ; Friedburg,
Ibid. 2,6; Hiibner, Ann. 222, 100),
the latter sulphonated by sulphuric an-
hydride (Hiibner and Upmann, Zeit.
[2] 6, 29.5), the 3-brom-5-sulphobenzoic
acid thvas formed converted into a-resor-
cylic acid by potash fusion (Bottinger,
Ber. 8, 374), and then into resorcinol as
above.

[E.] Umhelliferone [Vol. II] on fusion
with potash gives /3-resorcylic acid
(Tiemann and Reimer, Ber. 12, 997 ;
Tiemann and Parrisius, Ber. 13, 2358),
and finally resorcinol (Hlasiwetz and
Grabowski, Ann. 139, 99).

[F.] FAhyl alcohol [l4], gh/cerol [48],
and acetic acid [Vol. II] furnish the
resoi'cinol complex by the following pro-
cesses : —

Acetic acid and alcohol give acetic
ester, and the latter acetoacetic ester.
Glycerol on oxidation with nitric acid
or other oxidising agents gives glyceric
acid (Debus, Phil. Mag. [4] 15, 195; Ann.
106, 79 ; 109, 227 ; Sokoloff, Ann. 106,
95 ; De la Rue and Miiller, Ann. 109,
122 ; Beilstein, Ann. 120, 228 ; Barth,
Ann. 124, 341 ; Moldenhauer, Ann.
131,324; Mulder, Ber. 9 1902; Bbrn-
stein, Ber. 18, 3357 ; Lewkowitsch,
Proc. Ch. Soc. 5, 14 ; Wohlk, Journ.
pr. Ch. [2] 61, 200 ; Zinno, Monit. Sci.
16, 493 : see also under benzyl alcohol
[54 ; F]). Glyceric acid by the action
of phosphorus iodide yields /3-iodopro-
pionic acid (Beilstein, Ann. 120, 226 ;
122, 366 ; Erlenmeyer, Ann. 191, 284;
Rosenthal, Ann. 233, 16; Meyer, Ber.
19, 3294; 21, 24). The ester of /3-
iodopropionic acid condenses with sodio-
acetoacetic ester to f\;'m acetoglutaric
diethyl ester (Wislicer s and Limpach,
Ann. 192, 128), which on heating with
hydrochloric acid gives y-acetobutyric
(5-hexanonic) acid (Fittig and Wolff,
Ann. 216, 129; Fittig and Christ,
Ann. 268, i.i'^; W. H. Perkin, junr..
Trans. Ch. Soc. 69, 15 10). y-Aceto-
butyric ester condenses under the in-
fluence of sodium ethoxide to diketo-
hexamethylene or dihydroresorcinol,
from which resorcinol can be obtained

70 F-I.]

RESORCINOL

145

by bromination and subsequent removal
of hydrogen bromide (Merling, Ann.
278, 38 ; Vorlander, Ber. 28, 3348 ;
Ann. 294j 269).

Or the g-lycerol may be converted into
allyl bromide and trimethylene bromide
(see under n-prcpyl alcohol [15 ; E]).
The latter interacts with sodio-acetoace-
tic ester to form brompropylacetoacetic
ester (Lipp, Ber. 18, 3279)^ which gives
acetylbutyl alcohol on heating with
dilute hydrochloric acid {Ibid. 3280;
Colman and W. H. Perkin, junr., Trans.
Ch. Soc. 55, 354). The alcohol yields
y-acetobutyric acid on oxidation with
chromic acid mixture.

Or from ethyl alcohol through iodo-
form and methylene iodide [14; 1, p. ^^'\
and the action of the latter on sodio-
acetoacetic ester, which gives a product
(consisting of two methylketohexenyl-
enecarboxylic esters, CjoHj^Og) which,
on boiling with dilute sulphuric acid,
yields m ethyl- i-cyclohexenone-3. The
latter on oxidation with alkaline per-
manganate gives y-acetobutyric acid
(Hagemann, Ber. 26, 876, &c.; Harries,
Ber. 35, 1176 : see also Hagemann and
Knoevenagel, Ann. 297, 138). Subse-
quent steps as above.

The glycerol in the above synthesis
might be replaced by lactic acid [Vol.
II], which gives acrylic acid (among
other products) when the calcium salt
is heated (Glaus, Ann. 136, 288 : for
production of acrylic acid from lactic
acid via a-chlorpropionic acid see Michael
and Garner, Ber. 34, 4050). Ethyl
acrylate condenses with sodio-acetoaeetie
ester to form acetoglutaric ester (Vor-
lander, Ber. 28, 2349), which can be
converted into y-acetobutyric acid, &c.,
as above.

Or succinic ac [Vol. II] gives y3-
iodopropionic acii by electrolysing the
sodium salt with potassium iodide for
the negative electrolyte (v. Miller and
Hofer, Ber. 28, 2436). /3-Iodopropionic
acid and acetoacetic ester give y-aceto-
butyric acid and resorcinol as above.

Or the glycerol may be replaced by
acetic aldehyde [92], which on chlorina-
tion gives butyrochloral = 2:2: 3-tri-
chlorbutanal (Kramer and Pinner, Ber.
3, 383 ; Pinner, Ann. 179, 26). The

latter on heating with potash solution
gives an allylene dichloride (GaH^Cl^),
which on heating with water yields
acrylic acid (Pinner, Ber. 7, 66). Sub-
sequent steps as above.

Note : — Propionic acid [Vol. II] gives aa- and
a)3-dibroino-acid (see under benzyl alcohol [54 ;
O]). The aiS-acid yields acrylic acid on treating
the solution with zinc and sulphuric acid
(Caspaiy and Tollens, Ann. 167, 241 ; Melikoff,
Journ. Russ. Soc. 13, 156).

The propyl alcohols [15 ; 16] also give acrylic
acid through propylene and acrolein [101] (see
under benzyl alcohol [54 ; E]), and mannitol
[51] gives acrolein among the products of its
oxidation by manganese dioxide and sulphuric
acid (54 ; AA).

[G.] Euxanthone [136] gives resor-
cinol among the products of fusion with
potash.

[H.] Yrom. furfural [l26] and acetone
[IO6] through pyromucie acid, muco-
bromic acid, and nitromalonic alde-
hyde (see under phloroglucinol [86 ; l]).
The latter condenses with acetone in
the presence of alkali to form p-nitro-
phenol (Hill and Torrey, Ber. 28, 2598 ;
Am. Ch. Journ. 22, 89). Subsequent
steps as above under C.

[I.] From malonic and citric acids

tVol. II] and alcohol [l4]. Ghloroform
1 ; D, &c.] reacts with sodium ethoxide
to form orthoformic triethyl ester
(Williamson and Kay, Ann. 92, 346;
StapfP, Zeit. [2] 7, 186; Deutsch, Ber.
12, 116; Wichelhaus and Ladenburg,
Ann. 152, 164; Arnhold, Ann. 240,
1 93). This ester condenses with diethyl
malonate (acetic anhydride as condens-
ing agent) to form ethoxymethylene-
malonic ester (Glaisen, Ber. 26, 2729).
The latter condenses with acetonedi-
carboxylic ester (from citric acid; see
under glycerol [48; M]) under the
influence of sodium ethoxide to form
ace tonedicarboxylmethenylmalonic ester,
which undergoes further condensation
with the elimination of alcohol and the
formation of resorcinoltricarboxylic ester
(dihydroxytrimesic ester). The latter
on boiling with sodium hydroxide solu-
tion gives resorcinoldicarboxylic = ^-
dihydroxybenzoic acid (Errera, Gazz.
31, 139; Gh. Gentr. 1901, 1, 1092).
The acid yields resorcinol on heating
(Senhofer and Brunner, Ber. 13, Ref.

930)-

146

AROMATIC ALCOHOLS AND PHENOLS [70 J-71 C.

[J.] From quincl [71] through hy-
droxyquinol by alkaline fusion (Barth
and Schreder, Monats. 4, 176 ; 5, 59o)'
Hydroxy quinol (or its carboxylic acid)
gives dihydroresorcinol on reduction
with sodium amalgam (Thiele and
Jaeger, Ber. 34, 2841). Subsequent
treatment as above under P.

71. Quiuol ; Hydroquinone ;

Faradihydrozybenzene ;

Fyrogentisic acid ;

1 : 4-Fhenediol.

HO

HO

Natural Sources.

Occurs to the extent of from 2 to
5 per cent, in the S. African ' sugar
bush/ Protea mellifera (Hesse, Ann.
290, 317), and as glucoside (arbutin)
in the berries of the red whortleberry,
Vaccinium vitis-ideea, in leaves of the
red bearberry, Afctostaphylos uva-ursi,
and A. glauca, and of Fyrola umbellata,
P. rotundifolia, P. cklora7dJia,P. elllptica,
Calluna vulgaris, Ledum palustre, EjjigfBa
repenSy Gaultheria procumhens, and
Ckimaphila maculata (Kawalier, Ann.
82, 241 ; 84, '^S^ ; Zwenger and Him-
melmann, Ann. 129, 203; Claassen,
Jahresber. 1870, 877; 1885, 1761;
Schiff, Ann. 206, 165; Schunck and
Marchlewski, Ann. 278, 354; Maisch,
Am. Journ. Pharm. 46, 319).

Arbutin is decomposed by the moulds
Aspergillus niger, A. glaucus, and Peni-
cillium glaucum with the liberation of
quinol (Puriewitsch, Ber. deutsch. bot.
Gesell. 16, 368).

The quinol complex is contained in
euxantfione [l36], gentisiti [l37], homo-
getdisic acid [Vol. II], methylarhutin
[159], and (possibly) in saponarin, a
glucoside contained in Saponaria offici-
nalis (Barger, Ber. 35, 1296).

Quinol occurs as a constituent of
normal urine (Piatt, Am. Ch. Journ.
19, 382).

Synthetical Processes.

[A.] From phenol through p-iodo-
phenol by various iodising processes
(see under catechol [69 ; A]), and fusion
of the latter with potash at a tempera-
ture below 165° (Kbrner, Zeit. [2] 2,
662; 731; 4, 322).

Or from phenol through p-nitrophenol
by nitration, p-aminophenol by reduc-
tion, and the diazo-reaction with the
latter (Weselsky and Schuler, Ber. 9,
1 160).

From phenol by the action of potas-
sium persulphate in alkaline solution
(Ch. Fab. vorm. E. Schering, Germ.
Pat. 81068 of 1894; Ber. 28, Ref.
666).

Quinol is among the products of
electrolysis of a solution of phenol by
an alternating current in presence of
magnesium sulphate and acid carbonate
(Drechsel, Journ. pr. Ch. [2] 29, 249),
and also among the products of the
oxidation of phenol by hydrogen per-
oxide (Martinon, Bull. Soc. [2] 43,

156).

From phenol through p-nitrosophenol
= quinone-oxime (Bridge, Ann. 277, 85;
Wurster, Ber. 20, 2632), and the action
of hydroxylamine on the latter (Hepp,
Ber. 10, 1654).

From phenol and carhon tetrachloride
[l; L] through 5-nitrosalicylic and
gentisic acids as under euxanthone
[136 ; C]. From gentisic acid as under
C below.

[B.] Qtmione [l42] gives quinol on
reduction (Wbhler, Ann. 51, 152). The
reduction can be effected by alcohol
under the influence of light (Ciamician
and Silber, Ber. 33, 291 1 ; 35,3594).
Also by isopropyl alcohol and formic
acid under similar circumstances {Ibid.
34, 1542). Quinol (and p-diethoxy-
quinone) is formed, by heating quinone
with alcohol in the presence of zinc
chloride (Knoevenagel and Biickel,
Ber. 34, 3798).

[C] Salicylic acid [Vol. II] can by
various processes be iodised or bromi-
nated so as to form 5-iodo- or 5-brom-
salicylie acid (Gerhardt, Ann. Chim. [3]
7, 217; Cahours, Ibid. 10, 341; 13,
99; Henry, Ber. 2, 275; Lautemann,

71 C-P.]

QUINOL

147

Ann. 120^ 302; Demole, Ber. 7, 1437 ;
Goldberg-, Journ. pr. Ch. [2] 19, 368;
Hiibner, Ber, 12, 1347; Birnbaum and
Reinherz, Ber, 15, 458 ; Hiibner and
Heinzerling-, Zeit, [2] 7, 709 ; Hand,
Ann, 234, 133)^ which on fusion with
potash gives 2 : 5-dihydroxybenzoic (5-
hydroxysalieylic, gentisic, or 2 :5-pbene-
diolcarboxyHc) acid (Lautemann, loc. cit.
311 ; Liechti, Ann, Suppl, 7, 144;
Demole, loc. cit. ; Goldberg, loc. cit.
371 ; Miller, Ann. 220, 124 ; Rakowski
and Leppert, Ber, 8, 789). The latter
on dry distillation yields quinol among
other products (Herrmann, Ann, 211,

Or salicylic acid may be nitrated
(Hiibner, Ann, 195, 6; 31 j Schiff and
Masino, Ann, 198, 258 ; Deninger,
Journ. pr, Ch. [2] 42, 550 ; Hirsch,
Ber. 33, 3238), the 5- (separated from
the 3-) nitro-acid reduced to 5-amino-
salicylic acid (Beilstein, Ann. 130,
243 ; Hiibner, Ann, 195, 1 8 ; Schmitt,
Jahresber, 1864, 383), the latter con-
verted into 2 : 5-dihydroxybenzoic ( =
gentisic) acid by the diazo-method (Gold-
berg, loc. cit. 368), and then into quinol
as before.

Note : — f-Aminosalicylic acid is best pre-
pared by the reduction of benzeneazosalicylic
acid (Fischer and Schaar-Rosenburg, Ber. 32,
8i). 5-NitrosalicyIic acid also on heating with
lime gives p-nitrophenol, which can be reduced
to p-aminophenol and treated as above under
A. Salicylic acid yields gentisic acid by direct
oxidation with potassium persulphate in alka-
line solution (Ch. Fab, vorm. Sobering, Germ,
Pat. 81297 of 1894 ; Ber. 28, Ref, 692).

[D,] Benzoic acid [Vol. II] when
nitrated gives chiefly m-nitrobenzoic
acid (Mulder, Ann. 34, 297 ; Garland,
Ann. 91, i86j Griess, Ann. 166, 129;
Hiibner, Ann. 222, 72 ; Holleman,
Zeit. physik. Ch. 31, 79). A solution
of this acid in sulphuric acid gives
5-aminosalicylic acid on electrolysis
(Gattermann, Ber. 26, 1850), and from
this 2 : 5-dihydroxybenzoic acid and
quinol can be obtained as above.

m-Nitrobenzoic acid also gives 5-
aminosalicylic acid by reduction in
strong sulphuric acid with zinc dust
at a low temperature (Germ. Pat.
96,853 of 1896; Ch. Centr. 1898, 2,
160).

l2

Benzoic acid also gives among the
products of its nitration some o-nitro-
acid (Griess, loc. cit. and Ber, 8, 526 ;
10, 1871 ; Ernst, Jahresber. 1860, 299 ;
Liebermann, Ber. 10, 862 ; Widnmann,
Ann. 193, 204; Holleman, Rec. Tr.
Ch. 18, 267), which by reduction gives
o-aminohenzoic {antkranilic) acid [Vol, II]
(Beilstein and Kuhlberg, Ann. 163,
138). The latter by the action of
potassium emanate [172] on the hydro-
chloride yields o-uraminobenzoic acid
(Griess, Journ. pr. Ch, [2] 5, 371), and
this on nitration gives a dinitro-uramino-
benzoic acid (Griess, Ber, 11, 1730),
which on boiling with water yields
5-nitro-2-aminobenzoic acid {Ibid.). The
latter on heating with potash solution
gives 5-nitrosalicylic acid {Ibid.), which
can be treated as under B.

Note : — Crenerators of antkranilic acid [Vol. II]
thus become generators of quinol.

Or benzoic acid may be brominated
(Peligot, Ann. 28, 246 ; Angerstein,
Ann. 158, 2 ; Reinecke, Zeit. [2] 1,
116; 5, 109; Hiibner, Ohly, and
Philipp, Ann. 143, 233 ; Hiibner and
Petermann, Ann. 149, 131 ; Angerstein,
Ann. 158, 5) so as to give m-brom-
benzoic acid. The latter on nitration
gives (with the 3-brom-2-nitro-acid)
3-brom-6-nitrobenzoic acid (Hiibner,
Ohly, and Philipp, loc. cit.; Hiibner
and Petermann, loc. cit.), which by
reduction yields 6-amino-3-brom- (= 5-
brom-2-amino) benzoic acid (H., O., and
P. loc. cit. 241), from which by the
diazo-method 5-bromsalicylic acid can
be obtained (Hiibner and Emmerling-,
Zeit, [2] 7, 709). The latter can be
converted into 2 : 5-dihydroxybenzoic
(gentisic) acid, &c., as under C.

[E,] Cinnamic acid [Vol, II] on nitra-
tion gives a mixture of p- and o-nitro-
acids (Beilstein and Kuhlberg, Ann.
163, 126), from the latter of which
o-nitrobenzoic acid can be obtained by
oxidation with chromic acid {Ibid. ;
Widnmann, Ber, 8, 393), o-aminoben-
zoic acid by reduction, and then as
under C.

[P.] Benzoic aldehyde [ll4] on nitra-
tion gives chiefly m-nitro-, but also some
o-nitrobenzoic aldehyde (Rudolph, Ber.

or TMl '^

UNIVERSITY
or

148

AROMATIC ALCOHOLS AND PHENOLS

[71 F-O.

13, 310; Fittiea, Ber. 10, 1630). The
latter can be oxidised to o-nitrobenzoic
acid, and then treated as under C.

Or from benzoic aldehyde through
toluene by heating with strong- hy-
driodic acid solution at 380° (Berthelot,
Jahresber. 1867, 346), o-nitrotoluene
by nitration (see under o-cresol [61;
a]), o-nitrobenzoie acid by oxidation
(Weith, Ber. 7, 1 058 ; Widnmann,
Ann. 193, ;i:^5 ; Monnet, Reverdin,
and Noelting, Ber. 12, 443 ; Noyes,
Ber. 16, ^^), and then as above,

[G.] The creftols [61; 62; 63] by
distillation with hot zinc dust (Baeyer,
Ann. 140_, 395 ; Marasse, Ann. 152,
64), or by heating with phosphorus
trisulphide (Kekule and Fleischer, Ber.
6, 1088; Geuther, Ann. 221, 55), give
toluene, from which o-nitrobenzoic acid,
&c., can be obtained as above.

[H.] Benzyl alcohol £54] heated with
hydriodic acid and phosphorus at 140°
is reduced to toluene (Graebe, Ber. 8,
1 054), which can be treated as above.

Note : — All generators of toluene (see under
benzyl alcohol [54 ; A, &c.]) thus become
generators of quinol.

[I.] Phenylacetic acid [Vol. II] when
nitrated gives the a : 4-dinitro-acid
(Radziszewski, Ber. 2, 210 ; Gabriel
and Meyer, Ber. 14, 823), and this by
reduction the 2-nitro-4-amino-acid {G.
and M. loc. cit. 824). The latter, on
replacing the NHg-group by hydrogen
by the diazo-method and the simul-
taneous action of nitrous acid, gives the
oxime of o-nitrobenzoic aldehyde {Ibid.
826 ; 15, 3057 ; 16, 520), from which
the nitro-aldehyde can be obtained by
oxidation with chromic acid mixture
{Ibid. 14, 829), and finally o-nitrobenzoic
acid by oxidation with potassium per-
manganate. Subsequent steps as above.

Or the 2 : 4-dinitro-acid in alkaline
solution decomposes into 2 : 4-dinitro-
toluene (Radziszewski, Ber. 2, 210;
3, 648 ; Gabriel and Meyer, Ber. 14,
824), which on reduction with am-
monium sulphide gives 2-nitro-4-tolui-
dine (Beilstein and Kuhlberg, Ann. 155,
14). The latter by the diazo-method
yields o-nitrotoluene, from which o-
nitrobenzoic acid can be obtained by
oxidation (see above under F).

[J.] Indigo [Vol. II] when boiled
with aqueous potash gives o-aminoben~
zoic {aulhranilic) acid [Vol. II] (Fritz-
sche, Ann. 39, 83; Liebig, Ibid. 91),
which can be converted into quinol as
under D.

[K.] Homogentisic acid [Vol. II] gives
quinol on fusion with potash,

[L.] Gentisin [l37] when fused with
potash gives 2 : 5-dihydroxybenzoic
(gentisic) acid (Hlasiwetz and Haber-
mann, Ann. 175, 62 ; 180, 345 ; Tie-
mann and Miiller, Ber. 14, 1988), which
can be converted into quinol as under B.

[M.] Euxanthone [l36] gives quinol
among the products of fusion with
potash (Baeyer, Zeit. [2] 5, 569).

[N.] Succinic acid [Vol. II] gives
quinol among other products by the dry
distillation of its salts (v. Richter, Journ.
pr. Ch. [2] 20, 207).

Or succinic acid (ester) by the action
of sodium in presence of alcohol or of
dry sodium ethoxide can be converted
into succinyl succinic (cyclohexanedione-
2 : 5-dicarboxylic- 1 : 4) ester (Fehling,
Ann. 49, 186 ; Herrmann, Ber. 10, 107 ;
Ann. 211, 306 ; Duisberg, Ber. 16, 133 ;
Volhard, Ibid. 1 34 ; Piutti, Gazz. 20,
167; Vorlander, Ann. 280, 186). The
latter on oxidation by air or bromine
gives p-dihydroxyterephthalic (quinol-
dicarboxylic or 2 : 5-phenedioldicarboxy-
lic) ester (Herrmann, loc. cit. 11 1; Ann.
211, 327), and the acid on dry distilla-
tion or on fusion with potash yields
c^inol {Ibid. Ber. 10, 112 j Ann. 211,

Or succinylsuccinic ester can be con-
verted into dihydroxyterephthalie acid
by the action of phosphorus pentachloride
(Levy and Curchod, Ber. 22, 2108).

Or from succinic acid through laevulic
acid (see under erythritol [50 ; C]) and
then through the dibromo-acid and di-
acetyl as below under O,

[O.] From acetoacetic ester [Vol. II]
and its dibromo-derivative by brominff-
tion (Duisberg, Ann. 213, 143 ; Schon-
brodt, Ann. 253, 177 ; Epprecht, Ana.
278, 85). The latter when acted on in
dry ethereal solution by sodium gives
dihydroxyterephthalie ester (Wedel,
Ann. 219, 74).

Or acetoacetic ester can be converted

71 O-R.]

QUINOL

149

into m ethyl acetoacetic ester (Geuther,
Jahresber. 1865, 303; Isbert, Ann. 234,
188; Koubleff, Ann. 259, 254; Nef,
Ann. 260, 90), and the latter converted
by the action of nitrous acid into iso-
nitrosomethylethyl ketone = butadione-
oxime (Meyer and Ziiblin, Ber. 11, 322).
The latter on decomposition by heating
with dilute sulphuric acid gives diacefyl
[113] (v. Pechmann, Ber. 20, 2539 ;
2904; 3162; 3213; 21, 141 1 ; 22,
2115; 24,3954). On heating diacetyl
with excess of dilute caustic soda solu-
tion it yields p-xyloquinone [Ibid. 21,
1420), from which dihydroxyterephthalie
acid and quinol can be obtained as below
under R.

Or diacetyl under the influence of
hydrochloric acid gives a trimolecular
polymeride, and this yields p-xyloquinol
among other products on reduction with
sodium amalgam (Diels and Jost, Ber.
35, 3292).

Note : — Generators of diacetyl [113] thus be-
come generators of quinol.

Or acetoacetic ester can be converted
into acetosuccinic ester by the action of
ethyl chloracetate on the sodium com-
pound (Conrad, Ann. 188, 218), and
then into /S-isonitrosolsevulic acid by the
action of nitrous acid (Thai, Ber. 25,
17 1 8). The isonitroso-compound gives
diacetyl on boiling with dilute sulphuric
acid (Ibid. 1723), and this can be con-
verted into p-xyloquinone, &c., as above.

Or methylacetoacetic ester can be
brominated and the y-bromo-derivative
converted into tetrinic = o-methyl-
tetronic acid by heating with alcoholic
potash, or j)e7' se at 100" (Demar^ay,
Ann. Chim. [5] 20, 451 ; Bull. Soc.
[2] 33, 518; Pawloff, Ber. 16, 486;
Conrad and Kreichgauer, Ber. 29, 1047 >
Wolff, Ann. 288, 16). Tetrinic acid
gives diacetyl on oxidation with nitric
acid, potassium permanganate, or with
chromic acid (Wolff, Ber. 26, 2220 ;
Ann. 288, 27).

Or from acetoacetic ester through
Isevulic acid (see under erythritol [50 ;
D]). The latter on bromination gives
the ^-dibromo-acid (Hell and Kehrer,
Ber. 17, 1981 ; Wolff, Ann. 229, 266),
and this on boiling with water yields

diacetyl among other products (Wolff,
loc. cit. ; Ber. 26, 22x6).

Or from acetoacetic acid and glycerol
[48] via allylacetone (see under ery-
thritol [50; G]), Isevulic acid, and
diacetyl as above.

Or from acetoacetic ester through the
y-bromo-derivative and succinylsuccinic
acid (see under n-propyl alcohol [15 ;
AA]), and then through dihydroxytere-
phthalie ester, &c., as above.

[P.] Thymol [67] can by various pro-
cesses of oxidation be converted into
thymoquinone (Lallemand, Jahresber.
1854, 592 ; Carstanjen, Journ. pr. Ch.
[2] 3, ^"i, ; 15, 410 ; Andresen, Journ.
pr. Ch. [2] 23, 172; Armstrong, Ber.
10, 297 ; Liebermann and Ilinski, Ber.
18, 3 1 94), which easily reduces to thymo-
quinol [82]. The latter on heating with
phosphorus oxychloride gives a diphos-
phoric ester, the potassium salt of which
on oxidation with potassium perman-
ganate yields dihydroxyterephthalie acid
(Heymann and Konigs, Ber. 20, 2393).

[Q.] Carvacrol [66] on oxidation also
gives thymoquinone (Claus, Journ. pr.
Ch. [2] 39, 356 ; Reychler, Bull. Soc.
[3] 7, 32), which can be treated as
above.

[R.] From acetone [IO6] through
pseudocumene (see under o-cresol [61 ;
B]), nitropseudocumene, and pseudo-
cumidine (5-amino-i : 2 : 4-trimethyl-
benzene) by nitration and reduction
(Schaper, Zeit. [2] 3, 12). The latter
on oxidation gives p-xyloquinone (Noel-
ting and Baumann, Ber. 18, 1151 ;
Sutkowski, Ber. 20, 977), which reduces
to p-xyloquinol. The latter is converted
by phosphorus oxychloride into a di-
phosphoric ester of which the potassium
salt is oxidised by permanganate to
dihydroxyterephthalie acid (Heymann
and Konigs, Ber. 20, 2396).

Or from acetone and ethyl acetate
through acetylacetone and Isevulic acid
(see under erythritol [50 ; G]). From
the latter through diacetyl [ll3] as above
under O.

Note: — Xylidines derived from the xylenes
(61, A ; 62, A ; 63, A) can, by heating their
fiydrochlorides with methyl alcohol at a high
temperature (300-320°), be made to furnish
pseudocumidino (Hofmann, Ber. 15, 2895 ;
Noelting and Forel, Ber. 18, 2680).

150

AROMATIC ALCOHOLS AND PHENOLS [71 R-X.

Also amino- and diamino-p-xylene give xylo-
quinone on oxidation (Carstanjen, Journ. pr.
Ch. [2] 23, 423 ; Noelting, Witt, and Forel, Ber.
18, 2667 ; Nietzki, Ann. 215, i68). Generators
of the xylenes (see under o-cresol [61 ; A and B]
and p-cresol [63 ; A and B]) thus become
generators of dihydroxyterephthalic acid and
quinol.

[S.] From oxalic and acetic acids
[Vol. II] and alcohol [l4] through
ketipic acid (diacetyldicarboxylic or
3 : 4-hexadionediacid) by the action of
ethylchloracetate on oxaHc diethyl ester
in the presence of zinc, and hydrolysis
of the ketipic ester formed (Fittig,
Daimler, and Keller, Ann. 249, 183).
Ketipic acid on dry distillation or on
heating with dilute sulphuric acid gives
diacetyl {Ibid. 200), which can be con-
verted into p-xyloquinone, &c., as under
N and Q.

Ketipic acid can also be obtained from
oxalic and acetic esters in ethereal solu-
tion by the action of dry sodium ethylate
(Wislicenus, Ber. 20, 5H9 ; Ann. 246,
328).

[T.] Benzene [6], irrespective of the
compounds of which it is the generator
under the preceding headings (phenol
[a], quinone [B], &c.), can be made to
turnish quinol directly by electrolysing
a solution of the hydrocarbon in alcohol
in presence of sulphuric acid (Gatter-
mann and Friedrichs, Ber. 27, 1942).
Or by electrolysis in suspension in
sulphuric acid (Kempf, Germ. Pat.
1 17251 of 1899; Ch. Centr. 1901, 1,

34H). .

Quinol is among the products of the
oxidation of benzene by hydrogen per-
oxide in presence of ferrous sulphate
(Cross, Bevan, and Heiberg, Ber. 33,
2018).

Nitrobenzene in strong sulphuric acid
solution gives p-aminophenol on electro-
lysis (Gattermann and Koppert, Ber.
26, 2810; Noyes and Clement, HAd.
990 ; Gattermann, Ibid. 1 844 ; 27,
1927), and this can be converted as
under A.

Or benzene might be converted into
nitrobenzene, aniline, acetanilide, p-
nitraniline, and p-phenylenediamine.
The latter on heating with acids to
a high temperature gives quinol (Meyer,
Ber. 30, 2569). Aniline yields quinol

(16-18 per cent.) on oxidation with
chromic acid mixture (Nietzki, Ber. 10,

1934)-

Nitrobenzene on mild reduction gives
phenylhydroxylamine (Bamberger, Ber.
27, 1347; I54«; Wohl, Ibid. 1432),
and this on electrolysis in alcoholic
sulphuric acid solution (Haber, Zeit.
Elektroch. 4, 506), or by heating with
the same solution (Bamberger, Ber. 27,
1349 ; Bamberger and Lagutt, Ber.
31, 1 500), yields, among other products,
p-aminophenol, which can be converted
into quinol as under A.

Aniline gives, among other products,
p-aminophenol on oxidation with hydro-
gen peroxide (Prudhomme, Bull. Soc.
[3] 7, 621), or with hypochlorous acid
(Bamberger and Tschirner, Ber. 31,
1522).

Or phenylhydroxylamine can be oxi-
dised to nitrosobenzene, and this gives
p-aminophenol among the products of
the action of hot aqueous alkali (see
under catechol [69 ; M]).

Aniline on methylation gives di-
methylaniline, which by the action of
nitrous acid yields the p-nitroso-deriva-
tive. The latter on decomposition by
alkali gives (with dimethylamine) p-
nitrosophenol (Baeyer and Caro, Ber. 7,
809 ; 967), which can be treated as
under A. p-Nitrosophenol is among
the products of the action of aqueous
alkali at ordinary temperatures on
nitrosobenzene (Bamberger, Ber. 33,

1954)-

[U.] Yrom. furfural \\^Q] 3ind acefotie
[106] through p-nitrophenol (see under
resorcinol [70; H]), and then as under
A above.

[v.] From la>vulose [l55] or mannose
[15 6] through lievulic acid (see under
erythritol [50; H; l]), and then through
diacetyl as above under O.

[W.] From isoliexoic acid [Vol. II]
through Isevulic acid [50 ; E], and
then as above through diacetyl.

[X.] From malonic or acetic acid
[Vol. II] and (jlycerol [48] through
laevulic acid [50 ; F ; G]. Or from
glycerol through glyceric acid and
pyroracemic acid (see under benzyl
alcohol [54; F]), and then as below
under BB.

71 Y-72 B.]

QUINOL

151

[Y.] From crotonic aldehyde [l02]
throug-h Isevulic acid [50 ; O].

[Z.] From methylheptenone [ill]
throug-h Isevulic acid [50 ; Q].

[AA.] From dimefhi/lheptenol [35]
through Isevulic acid [50 ; N].

[BB.] From tartaric or racemic acid
[Vol. II] through pyroracemic acid
(see under benzyl alcohol [54 ; N]).
Potassium pyroracemate gives diacetyl
among- the products of electrolysis
(Hofer and Uhl, Ber. 33, 653).

[CO.] From ethyl alcohol [14] and
hydrogen cyanide [l72] through propio-
nitrile (see under benzyl alcohol [54 ; l]
and acetone [IO6 ; S]), aa-dichlorpro-
pionic and pyroracemic acids, and then
diacetyl as above.

[DD.] From acetic or acetoacetie acid,
[Vol. II] and hydrogen cyanide [l72]
throug-h acetyl cyanide and pyroracemic
acid [54 ; l], and then as above.

[EE.] From citric acid [Vol. II]
through citraconie or mesaconic acid
and pyroracemic acid [54 ; M] (see also
other generators of citraconie acid, p. 63).

[PF.] From propionic acid [Vol. II]
through the aa-dibromo-acid and pyro-
racemic acid [54 ; O].

[GQ.] From lactic acid [Vol. II]
through pyroracemic acid [54 ; P].

[HH.] From normal or isopropyl
alcohol [15 ; 16] through propylene,
acrolein [lOl], acrylic acid, a-chlorlactic
acid, glyceric acid, and pyroracemic acid
[54; E].

Note : — For generators of propylene see under
glycerol [48 ; B ; O ; D, &c.].

72. Toluquinol ; Hydrotoluquinoue ;

Methylquiuol ;

Faradihydrozytoluene ;

Methyl- 2 : 5-Fhenediol.

HO

CH,

HO

Natural Source.

The complex is possibly contained in
excoecarin, a colouring-matter obtained
from green ebony, the wood of Excoe-

caria glandulosa or Jacaranda ovalifolia
(A. G. Perkin and Briggs, Proe. Ch.
Soc. 18, II ; Trans. 81, 210).

Synthetical Processes.

[A.] From tolnene [54 ; A, &c.]
through o-nitrotoluene and o-toluidine.
The latter gives toluquinone on oxida-
tion with ferric chloride (Ladenburg,
Ber. 10, 1 1 28), or with sulphuric acid
and manganese dioxide (Clark, Am. Ch.
Journ. 14, ^6^ : see also Schniter, Ber.
20, 22^^ ; Nietzki, Ann. 215, 158).
Toluquinone is reduced to the hydro-
quinone by sulphurous acid (Nietzki,
lac. cit.).

o-Toluidine gives toluquinone on
oxidation with chromic acid mixture
(Nietzki, Ber. 10, 1935). Or o-toluidine
can be acetylated and nitrated, the
nitro-derivative hydrolysed to 5-nitro-
a-toluidine (Beilstein and Kuhlberg,
Ann. 158, 345), and the latter reduced
to 2 : 5-toluylenediamine, which gives
toluquinone on oxidation with sulphuric
acid and manganese dioxide (Nietzki,
Ber. 10, 833).

Note : — Both o- and p-nitrotoluene are gene-
rators of m-nitrotoluene through the correspond-
ing toluidines and nitrotoluidines (see under
vanillin [121 ; J]). m-Nitrotoluene gives 5-
aminocresol by electrolytic reduction in sul-
phuric acid solution (Gattermann, Ber. 27,
19.^0) and this yields toluquinol by the diazo-
method as below under B. p-Nitrotoluene on
mild reduction gives p-toluylhydroxylamine
(Bamberger, Ber. 28, 245 ; 1221 ; Lumifere and
Seyewitz, Bull. Soc. [3] 11, 1040), and this on
heating with dilute sulphuric acid yields tolu-
quinol (Bamberger, loc. cit. 246). p-Toluidine
also gives p-toluylhydroxylamine on oxidation
by monopersulphuric acid (Bamberger and
Tschirner, Bey. 32, 1677).

[B.] From 0- or m-cresol [61; 62]
through toluquinone by oxidation with
sulphuric acid and manganese dioxide
(Carstanjen, Journ. pr. Ch. [2] 23,
425). Also by oxidation with alkaline
potassium persulphate and hydrolysis
of the sulphate formed (Ch. Fab. Sober-
ing, Germ. Pat. 81068 of 1894; Ber.
28, Ref. 666).

Or o-cresol on nitration in acetic
acid gives (with 3-nitro-) 5-nitrocresol
(Hirsch, Ber. 18, 151 2), which reduces
to 5-aminocresol (Nevile and Winther,
Ber. 15, 2979). The latter gives tolu-
quinol by the diazo- method (^ILid.). Or

152

AROMATIC ALCOHOLS AND PHENOLS [72 B-75.

o-cresol can be converted into tolu-
quinone-oxime (nitroso-o-cresol) by
nitrosylsulphate (Noelting and Kohn,
Ber. VJ, 370), and this gives 5-amino-
cresol on reduction {Ibid.).

73. Qninol Methyl Ether ;

p-Hydroxyanisole ;

p-Methoxypheuol.

HO

CH3

Natural Source.

Occurs with the glucoside of quinol
(arbutin) as the glucoside methylarhutin
[159] (see under quinol [71 j for botanical
sources).

Synthetical Process.

[A.] From quinol [71] and methyl
alcoJwl [13] by heating the potassium
compound of the former with potassium
methyl sulphate (Hlasiwetz and Haber-
mann, Ann. 177^ ?)?)^)) or by heating
the potassium compound with methyl
iodide diluted with methyl alcohol
(HessC;, Ann. 200^ 354).

74. Quinol Ethyl Ether; p-Hydrozy-

phenetole ; p-Ethoxypheuol.

HO

.O.C.Hs

Natural Sources.

Occurs in small quantity in oil of
star-anise from lilic'mm verum (Oswald
in Beilstein^s ' Handb. d. org. Chem.'
3rd ed. II, 939) ; in Chinese oil of star-
anise (Tardy, Bull. Soc. [3] 27, 990).

Synthetical Processes.

[A.] From qidnol [7l] and alcohol [l4]
by heating the potassium compound of
the former with ethyl iodide (Wichel-
haus, Ber. 12, 1501).

[B.] From phenol [6O] and alcohol
[14] through the ethyl ether, phenetole
(Cahours, Ann. 78, 226 ; Kolbe, Journ.
pr. Ch. [2] 27, 424), p-nitrophenetole
by nitration (Hallock, Am. Ch. Journ.
1, 271), phenetidine by reduction (Wag-
ner, Journ. pr. Ch. [2] 27, 206), and the
diazo-reaction with latter (Hantzsch,
Ibid. 22, 462). Or phenol can be
nitrated, the p-nitrophenol converted
into p-nitrophenetole by heating the
potassium salt with potassium ethyl
sulphate in alcohol (Willgerodt and
Ferko, Journ. pr. Ch. [2] 33, 153), and
then into phenetidine, &c., as before.

[C] From salicylic acid [Vol. II] and
alcohol [14] through ethyl salicylate
(Cahours, Ann. 52, 332; 74, 314;
Gottig, Ber. 9, 1473). The latter,
according to Baly (Ann. 70, 269), gives
phenetole on distillation with baryta,
and this can be treated as under B.

[D.] Benzene [6] can be converted
into p-nitrophenetole by boiling p-chlor-
nitrobenzene with alcoholic potash
(Willgerodt, Ber. 15, 1002), and this
can be converted as under B.

75. Orcinol ; 3 : S-Dihydroxytolueue ;
Methylresorcinol ; Methyl-3 : 5-
Pheuediol.

CH,

HO

H

Natural Sources.

Orcinol does not occur in the free
state in the vegetable kingdom, but the
complex is contained in certain acids
obtained from lichens. Hoccclla tinctoria,
R.fiiciformis, and R. montaqnei have long
been known to yield orcinol. The com-
plex exists in the following com-
pounds : —

Evernic acid from Evernia prunastri,
var. vulgaris, Ramalina polUnaria (Sten-
house, Ann. 68, 84 ; 155, ^$ ; Hesse,
Ann. 117, 297 ; Journ. pr. Ch. [2] 57,
250 ; Zopf, Ann. 297, 300 ; 306), and
Rhyscia ( = Anaptychia) ciliaris (Hesse,
Journ. pr. Ch. [2] 58, 465).

75-A.]

ORCINOL

153

Erythrin = erythrie acid from lioc-
cella montagnei, R. peruetisis, and other
species ; from Parmelia olivetoruvi and
Aspicilia calcarea (Heeren, Berz. Jahres-
ber. 11, 279; Kane, Ann. 39, 35;
Schunck, Ann. 61, 64 ; Stenhouse,
Ann. 68, 72; Hesse, Ann. 117, 397 ;
139, 32 ; Journ. pr. Ch. [3] 57, 333 j
2,^6', 62, 470; Zopf, Ann. 297, 376;
303 ; 313, 343 : see also De Luynes,
Ann. Chim. [4] 2, 385 ; Menschutkin,
Bull. Soe. [3] 2, 434).

/3-Erytlirin from certain forms of
Roccella fuciformis contains (through
orsellic acid) the orcinol complex (Men-
schutkin, loc. cit. ; Lamparter, Ann. 134,

^43):

Divaricatic acid from Evernia di-

varicata, E. prunastri, var. thamnodes,

and Hccmatomma tentosum (Zopf, Ann.

297,398; 300,353; 317,137; Hesse,

Ber. 30, 364 ; Journ. pr. Ch. [3] 57,

346; 58,465; 62,439; 65,537).

Diffusin from Tlatysma diffusum and
Parmelia sorediata (Zopf, Ann. 306,
383; 313, 317; 317, 110).

Gyrophoric acid from Umhilicaria
{Gyropliord) pnstulata, G. proboscidea,
G.hirsuta, G. deusta^ G. vtllea, G.poJy-
jaJiylla, G. spiodochroa, var. depressa, Le-
canora tartarea (?), Blastenia arenaria,
var. teicholytum, Parmelia locarnensis,
inndi Lecidea grisella (Stenhouse, Ann. 70,
318 ; Zopf, Ann. 300, 333 ; 313, 332 ;
336; 317, 1 10; Hesse, Journ. pr. Ch.
[3] 58, 475; 62, 463; 466; 473;
63, 533).

Glomelliferin from Parmelia glomelli-
fera (Zopf, Ann. 306, 383 ; 321, '^'j).

Lecanoric (= parmelic) acid from
Lecanora parella, Evernia prunastri, Roc-
cella tinctoria, Psora ostreata, Parmelia
fuliginosa, var. ferruginasoeiis, P. verru-
culifera, P. borreri, P. tiliacea, var.
scortea, P. sorediata, P. tinctoriimy
P. perlata (trace), P. perforata (trace),
P. olivetorum, P. tinctorum = coral-
lo'ides, P. glabra {= P. olivacea and
P. glabra), P. sordida, Urceolaria cretacea,
U. scruposa, var. arenaria, Pachiolepia
decussata,2in^Pertusaria lactea (Schunck,
Ann. 41, 158 ; 54, 364 ; Rochleder and
Heldt, Ann. 48, 3 ; Stenhouse, Ann.
68, 59 ; Zopf, Ann. 295, 378 ; 306,
304; -^^T, 318; 319; 313,331; 317,

no; 321, '>^'] ; Hesse, Journ. pr. Ch.
[3] 57, 364 ; 409 ; 41 1 ; 58, 473 ; 499 ;

SS^; 62, 451; 453; 453 i 472; 63,
S?,'^ ) 5S^ ;. 65, S^-i, : Hesse was unable
to find this acid in Lecanora parella,
S chaer = Ochrolechia pallescens- y -parella,
and suggests that Schunck must have
had some other species in hand).

Patellarie acid from Urceolaria {Pa-
tellar ia) scruposa (Weigelt, Jahresber.
1869, 768: see also Hesse, Journ. pr.
Ch. [3] 58, 558; Zopf, Ann. 324,

39)-

Ramalic acid from Ramalina polli-

naria and many species of Evernia

(Hesse, Journ. pr. Ch. [3] 57, 333 ;

353 ; Ber. 30, 364 ; Zopf, Ann. 297,

Usnetic = stereocaulic ( = lobaric acid)
acid from Usnea barbata, Stereocaulon
alpinum, S. corallo'ides, S.pileatum, Lepra
cholerina, Lecanora badia, Parmelia saxa-
tilis, var. panniformis, var. phceotropa, P.
aleurites, P. omphalodes (Hesse, Ber, 10,
1336; Journ. pr. Ch. [3] 62, 445;
459 ; Zopf, Ann. 288, 57 ; 295, 371 ;
397; 306, 300; 314: see also Sal-
kowski, Ann. 319, 391).

Umbilicaric acid from Gyrophora poly-
phylla, G. deusta, G. hyperborea (Zopf,
Ann. 300, '^fZl '^ 317, 139; Hesse,
Journ. pr. Ch. [3] 63, 545).

Orcinol can be liberated from the
lichen acids which contain the complex by
the action of micro-organisms (Czapek,
Ch. Centr. 1898, 1, 684, from Centr.
Bakter. II, 4, 49).

The dimethylorcinol complex may be
contained in podophyllotoxin from the
Indian Podophyllum emodi and the
American P. peltatum (Dunstan and
Henry, Trans. Ch. Soc. 73, 333).

Synthetical Processes.

[A.] From toluene [54 ; A, &c.]
through p-chlortoluene. The latter on
sulphonation gives (with the 3-sulphonic
acid) p-chlor-3-sulphonic acid (Vogt and
Henninger, Ann. 165, 363; Wynne,
Trans. Ch. Soc. 61, 1078), which on
fusion with potash yields orcinol among
other products (V. and H. loc. cit. 366 ;
Bull. Soc. [3] 21, ^T^). There must
be isomeric transformation in this case.

154

AROMATIC ALCOHOLS AND PHENOLS

[75 ArC.

Or toluene may be nitrated, the o-
nitrotoluene reduced to o-toluidine, the
latter sulphonated (Gerver, Ann. 169,
374 ; Pagel, Ann. 176, 392 ; Nevile
and Winther, Trans. Ch. Soc. 37,
626; Ber. 13, 1941), the 2-toluidine-
5-sulphonic acid brominated, and thus
converted into 3-brom-2-toluidine-5-
sulphonic acid (N. and W. Ber. 13,
1942). The latter on replacing the
NHg-group by hydrogen by the diazo-
method gives 3-bromtoluene-5-sulphonic
acid {Ibid. 1944), from which orcinol
can be obtained by potash fusion [Ibid.
Ber. 15, 2990).

Or 2-toluidine-5-sulphonic acid may
be converted into 2-toluidine-3 : 5-di-
sulphonic acid by further sulphonation
{Ibid. 2992 ; Hasse, Ann. 230, 288),
the disulphonie acid into toluene-3 : 5-
disulphonic acid by replacing the
NHg-group by hydrogen (Limprieht and
Hasse, Ber, 18, 2177; Ann. 230, 295;
Nevile and Winther, Ber. 15, 2992),
and the disulphonie acid into orcinol by
potash fusion (N. and W. loc. cit. 2993).

Or o-toluidine may be converted into
3 : 5-dibrom-2-toluidine by bromination
(Wroblewski, Ann. 168, 162), into
3 : 5-dibromtoluene by replacing the
NHg-group by hydrogen (N. and W.
Ber. 13, 966), and the dibromtoluene
into orcinol by potash fusion {Ibid. 15,
2992).

Toluene may also be nitrated, the
p-nitrotoluene reduced, the p-toluidine
converted into 3 : 5-dibrom-4-toluidine
by bromination (Wroblewski, Ann.
168, 188), the NHg-group replaced by
hydrogen {Ibid.), and the 3 : 5-dibrom-
toluene converted into orcinol as above.

Or p-toluidine may be converted into
3 : 5-dinitro-4-toluidine by nitration and
hydrolysis of the acetyl- or benzoyl-
derivative (Beilstein and Kuhlberg, Ann.
158,341; Hiibner, Ann, 208, 312; 222,
74), the NHg-group replaced by hydro-
gen (Stadel, Ber. 14, 901 ; Ann. 217,
189; Hiibner, Ann. 222, 74; Nevile
and Winther, Ber. 15, 2984 ; Honig,
Ber. 20, 2418), the 3 : 5-dinitrotoluene
reduced by ammonium sulphide to 5-
nitro-3-toluidine (Stadel, Ann. 217, 189;
N. and W. loc. cit. 2985), and the latter
converted into 5-nitro-3-cresol by the

diazo-method (N, and W. loc. cit. 2986).
The nitrocresol on reduction and re-
placement of theNHg-group byhydroxyl
by the diazo-method gives orcinol {Ibid.
2987).

p- Acettoluide may also be brominated
and then nitrated, or nitrated and then
brominated so as to give on hydrolysis
3-brom-5-nitro-4-toluidine (Wroblew-
ski, Ann. 192, 202 ; N. and W. Ber. 13,
968). The latter on replacement of the
NHg-group by hydrogen gives 3-brom-
5-nitrotoluene, and by reduction 5-
brom-3-toluidine, from which, by the
diazo-method, 5-brom-3-cresol can be
obtained, and this also gives orcinol on
fusion with potash (N, and W. Ber.
15, 2991 : see also Nevile, Eng. Pat.
4389 of 1881).

[B,] Paracresol [63] when the ethyl
ether is nitrated is converted into the
3 : 5-dinitro-p-cresol ether (Stadel, Ann.
217, 161). Or p-cresol may be nitrated
(Frische, Ann. 224, 139 : see also Arm-
strong and Field, Ber. 6, 974), and
converted into the dinitro-ether by the
action of ethyl iodide on the silver salt
(Noelting and Salis, Ber. 15, 1859).
The dinitro-ether on treatment with
alcoholic ammonia is converted into
3 : 5-dinitro-4-toluidine (Stadel, loc. cit.
186), from which 3 : 5-dinitrotoluene,
5-nitro-3-toluidine, 5-nitro-3-cresol, 5-
amino-3-cresol and orcinol can be
obtained as under A.

[C] Citric acid [Vol. II] when heated
with sulphuric acid gives acetonedi-
carboxylic (/3-ketoglutaric or 3-penta-
nonedicarboxylic) acid (v. Pechmann,
Ber. 17, 2543 ; 18, 2289 ; 19, 1446,
2465 ; 2694 ; 20, 145 ; 24, 857 ; 3250;
4095 ; Ann. 261, 151 ; v. P. and Neger,
Ann. 273, 186; Henry and v, P. Ber.
26, 997 ; also Germ. Pat. 32245 of
1884), The diethyl ester of this acid
by the action of sodium gives dihydr-
oxyphenyltricarboxylic triethyl ester
(Cornelius and v. P. Ber, 19, 1448;
V. P. and Wolman, Ber. 31, 2014), and
the latter on hydrolysis by alcoholic
potash gives s-dihydroxyphenylacetic
(3 : 5-phenediolethylic) acid (C. and v, P.
loc. cit. 1449), the silver salt of which
yields orcinol on dry distillation {Ibid.
1450-

75 C-76 A.]

ORCINOL

155

The dihydrox3q)henyltricarboxylic ester
(ethyl orcinoltricarboxylate) is also ob-
tained (with a 'lactone'') by the action
of sodium ethoxide on an alcoholic
solution of acetonedicarboxylic ester
(Jerdan, Proc. Ch. Soc. 15, 151 ; Trans.
75, 808). Methyl acetonedicarboxylate
undergoes condensation to an orcinol
derivative more readily than the ethyl
ester (Dootson, Trans. Ch. Soc. 77,
1 196).

Note : — Citric acid gives acetonedicarboxylic
acid when oxidised by potassium permanganate
at 30-35° (Denigfes, Comp. Rend. 130, 32 ; Ann.
Chim. [7] 18,413).

Citric acid can also be converted into
dehydracetic acid by the action of acetic
anhydride on acetonedicarboxylic acid
(v. Pechmann, Ber. 24, 3600). Dehy-
dracetic acid can be converted into
orcinol as below under D.

[D.] Acetoacetic ester [Vol. II] on
chlorination gives (with a-) y-chloraceto-
acetic ester (Haller and Held, Comp.
Rend. 108, 516; 111, 647; 114, 400,
453; Ann. Chim. [6] 23, 157: see
also Genvresse, Comp. Rend. 107, 687 ;
Ann. Chim. [6] 24, 46 ; Hantzsch,
Ber. 23, 2339 ; Hantzsch and Schiffer,
Ber. 25, 728) ; the corresponding y-
cyan acetoacetic ester obtained by the
action oi potassmm cyanide [172] on the
chloro-ester gives, on hydrolysis with
hydrochloric acid and alcohol, acetone-
dicarboxylic ester (Haller and Held,
Comp. Rend, 111, 682), which can be
converted into orcinol as above under C.

Or acetoacetic ester can, by the action
of heat, be converted into dehydracetic
acid (Geuther, Zeit. [2] 4, 655 ; Oppen-
heim and Precht, Ber. 9, 324 ; W. H.
Perkin, junr., Trans. Ch. Soc. 51, 489),
and the latter gives orcinol on heating
with baryta water or (better) with
syrupy caustic soda solution at ]5o°
(Oppenheim and Precht, loc. cit. ; Collie,
Trans. Ch. Soc. 59, 183; Collie and
Myers, Ibid. 63, 124).

Dehydracetic acid is formed also by
the action of pyridine on acetyl chloride
(Dennstedt and Zimmermann, Ber. 19,
76), or of triethylamine or ferric chloride
on acetyl chloride (Wedekind, Ch. Centr.
1900, 2, 561 ; Ann. 323, 246).

[E.] From malouic acid [Vol. IIJ

through acetonetricarboxylic and dicar-
boxylic acid (see under phloroglucinol
[86 ; E]), and then as above under C.

76. Cresorcinol;
2 : 4-Dihydroxytoluene ;
Metliyl-2 : 4-Fhenediol.

CH,

OH

HO

Natural Source.

The cresorcinol complex probably
exists in cyanomaclurin, which occurs
with morin in the wood of Artocarpus
integrifolia from India and Java (A. G.
Perkin and Cope, Trans. Ch. Soc. 67,

939)-

Synthetical Processes.

[A.] From toluene [54; A, &e.]
through p-toluidine, 2-nitro-4-toluidine
by nitration (Noelting and Collin, Ber.
17, 263), 2-nitro-4-cresol by the diazo-
method (Neville and Winther, Ber. 15,
2980 ; Knecht, Ann. 215, 87), 2-amino-
4-cresol by reduction (Knecht, loc. cit.
91 ; Wallach, Ber. 15, 2833), and the
diazo-reaction with the latter (Knecht,
loc. cit. 92).

Or directly from toluene through the
2 : 4-disulphonic acid (Hakanson, Ber.
5, 1085 ; Gnehm and Forrer, Ber. 10,
542 ; 1 276 ; Claesson and Berg, Ber. 13,
J 170; Fahlberg, Ber. 12, 1052; Sen-
hofer, Ann. 164, 126 ; Klason, Ber. 19,
2890), and fusion with potash (Hakan-
son, loc. cit. 1087; Noelting, Ber. 19,

136).

Or from o-toluidine through 4-mtro-
2-toluidine by nitration (Noelting and
Collin, loc. cit. 265), 4-nitro-2-cresol by
the diazo-method (nitroindazole is
simultaneously formed : Noelting and
Collin, loc. cit. 269 ; Witt, Noelting,
and Grandmougin, Ber. 23, 3636 ;
Michel and Grandmougin, Ber. 26,
2351), 4-amino-2-cresol by reduction
(Noelting and Collin, Ber. 17, 270),
and the diazo-reaction with the latter
(Wallach, Ber. 15, 2835).

The two nitrotoluidines required for

156

AROMATIC ALCOHOLS AND PHENOLS [76 A-78.

this synthesis are also obtainable from
a : 4-dinitrotoluene by partial reduction
(Beilstein and Kuhlberg-, Ann. 155, 14 ;
Graeff, Ann. 22 9, 343 ; Anschiitz and
Heusler, Ber. 19, 2161); or the 2:4-
toluylenediamine may be monaeetylated,
converted into 4-acetamino-2-cresol by
the diazo-method, hydrolysed, and the
4-amino-3-cresol converted into cresor-
cinol as before (Wallach, Ber. 15, 2832
and 2835).

[B.] From resorcinol [70] and carbon
disulphide [I6O]. A mixture of these
compounds on heating in presence of
potassium sulphide solution gives resor-
cinoldithiocarbonic acid. The latter on
reduction with zinc dust and acetic
acid gives cresorcinol (Schall, Journ. pr.
Ch. [2] 54, 415)-

77. j3-Orcinol;

3 : 5-Dihydroxy-p-xylene ;

p-Xylorcin ;

1 : 4-Diiuethyl-3 : 5-Fhenediol.

CH,

H0\ /OH
CH3

Natural Sources.

The /3-orcinol complex is contained
in ^-erythrin from the lichen Roccella
fuciformis, in barbatic acid from the
lichen Ustiea barbata, and in /3-usnic
or cladonic acid from the lichen Cla-
donia rangiferma. (For occurrence of
/3-erythrin, which yields /3-orcinol
through picroerythrin, see under orcinol
[75] ; for barbatic acid, Stenhouse and
Groves, Ann. 203, 302 ; for /3-usnic =
cladonic acid, Stenhouse, Ann. 68, 98 ;
155, 58 ; Hesse, Ann. 117, 346 : cla-
donic acid may be a mixture of usnic
and barbatic acids, Paterno, Gazz. 6,
1 13 ; 12, 331 ; Stenhouse, loc. cit. 285 :
for barbatic acid in various species of
Usnea see Hesse, Ber. 30, 357 : accord-
ing to the latter author cladonic acid is
a mixture of usnic and atronoric acids :
for barbatic acid in Usnea longissima
see Zopf, Ann. 297, 293 ; Hesse, Journ.
pr. Ch. [2] 57, 239 j in Alectoria ochro-

leuca, Zopf, Ann. 306, 298 ; in Us7iea
barbata ^-hirta, Hesse, loc. cit, 65, ^'>^'] ;
in TJsnea ceratina and U. dasypoga (?),
Zopf, Ann. 324, 39).

Atranorin = atranoric acid, which is
contained in a large number of lichens
(for occurrence see under methyl alcohol
[13]) ; and ceratophyllin = atraric acid
= physcianin, which is a decomposi-
tion product of atranorin, also contain
the /3-orcinol complex (Hesse, Ber. 30,
1988).

The complex is contained in rhizonic
and rhizoninic acids from RMzocarpon
geograjihicum, var. contiguum {Ibid. 31,
664 ; Journ. pr. Ch. [2] 58, 527).

Coccellic acid from Cladonia cocci/era,
C. amauracraa, and C. jioerkeana = C.
hacillaris, contains the rhizoninic and
therefore the /3-orcinol complex {Ibid.
Ann. 284, 107; Journ. pr. Ch. [2] 57,
274 ; 58, 472 ; 62, 447 ; Zopf, Ann.
300, 330).

Synthetical Process.

[A.] From toluene [54 ; A, &c.] and
p-xylene (see under metacresol [62 ; A]).
The xylene on nitration gives (with
other isomerides) 3 : 5-dinitro-p-xylene,
which by reduction with nascent am-
monium sulphide yields 5-nitro-3-amino-
p-xylene = m-nitro-p-xylidine (Fittig,
Ahrens, and Mattheides, Ann. 147, 22).
The latter by the diazo-method gives
5-nitro-p-xylenol-3 (Kostanecki, Ber.
19, 2320), the corresponding amino-
xylenol by reduction with tin and
hydrochloric acid, and /3-orcinol by the
diazo-method {Ibid. 2321).

78. Mesorcinol;
1:3: 5-TriiiietIiyl-2 : 6-Fheuediol.

CH3
HO^ ,0H

CH

CH3

Natural Source.

Coccellic acid from the lichens Cla-
donia coccifera, &c. (see under yS-orcinol
[77]), hydrolyses to rhizonic and coccel-

78-81.]

MESORCINOL

157

linic acids. The latter may be a mesor-
einol derivative (Hesse^ Journ. pr. Ch.
[3] 62, 447).

Synthetical Process.

[A.] From mesit^lene (see under
benzyl alcohol [54 ; D ; E ; P ; G ; H,
&c.]), which on nitration gives a dinitro-
derivative, and this by mild reduction
nitromesidine (Fittig, Ann. 141, 133;
Maule, Ann. 71, 137 ; Knecht, Ann.
215, 98 ; Klobbie, Rec. Tr. Ch. 6, 33 ;
Kiister and Stallberg, Ann. 278, 314).
Nitromesidine gives by the diazo-
method nitromesitol, and the latter
aminomesitol by reduction (Knecht, loc.
cit.). Aminomesitol by the diazo-method
gives mesoreinol (Knecht, Ann. 215, 100).

Note : — For production of nitromesidine
from mononitromesitylene and mesidine see
papers by Fittig, Ann. 141, 132 ; Fittig and
Storer, Ann. 147, 2 ; Schultz, Ber. 17, 477 ;
Ladenburg, Ann. 179, 165 ; Biedermann and
Ledoux, Ber. 8, 58 ; Noelting and Stoeckling,
Ber. 24, 570).

79. Isoeugenol;

l^-Propenyl-3 : 4-FhenecLiol S-Metliyl

Ether.

CH:CH.CH,

•OCH,

HO

Natural Souece.

In ylang-ylang oil (SchimmeFs Ber.
Oct. 1 901 ; Ch. Centr. 1901, 2, 1007).

Synthetical Process.

[A.] From vanillin [121] and pro-
pionic acid [Vol. II]. vanillin is con-
verted into propionylhomoferulaic acid
by heating with propionic anhydride
and sodium propionate (Tiemann and
Kraaz, Ber. 15, 3060). Homoferulaic
acid obtained from the propionyl com-
pound by hydrolysis gives isoeugenol
on heating with lime {Ibid. 3063). Or
from vanillin and ethyl alcohol [14] by
the interaction of the aldehyde and
magnesiiim ethiodide (Behal and Tiffe-
neau, Comp. Rend. 132, ^^'^.

80. Methylisoeugenol ;

Isoeugenol Methyl Ether ;

l^-Propenyl-3 : 4-Fheuediol

Dimethyl Ether.

CH : CH . CH3

OCH3
OCH3

Natural Source.

A constituent of the oil of Asarum
arifolium (Miller, Arch. Pharm. 240,
371 j Ch. Centr. 1903, 2, 643).

Synthetical Process.

[A.] From isoeugenol [79] and methyl
alcohol [13] by methylation of the
phenol with methyl iodide and alcoholic
potash (Ciamician and Silber, Ber. 23,
1164).

Note : — ^The synthetical product was obtained
from eugenol, but this undergoes isomeric trans-
formation into isoeugenol under the influence
of the alcoholic potash.

81. Methylengenol ;

3 : 4-Diiuethoxyallylbenzene ;

l^-Propenyl-S : 4-Fhenediol Dimethyl

Ether.

CHj . CH : CHi,

OCH3

OCH3

Natural Sources.

In oil of paracoto bark, Bolivia
(Wallach and Bheindorff, Ann. 271,
300) ; in oil from the root of Asarum
europcBum (Petersen, Arch. Pharm. 226,
89 ; Ber. 21, 1057 : compare Mittmann,
Arch. Pharm. 227, 543, who suggests
methylisoeugenol), and A. canadense
(Power, Pharm. Eund. 6, 101 ; Proc.
Am. Pharm. Assoc. 28, 464 ; Power
and Lees, Proc. Ch. Soc. 17, 3 1 o ;
Trans. 81, 6']). Also in oil of bay

158

AROMATIC ALCOHOLS AND PHENOLS [81-83 A.

from Myrcia {Eugenia) acris, W.
Indies (Mittmann_, Arch. Pharm. 227^

529)-

Occurs also in the oil from the
' clove bark ' of Amboyna from Cinna-
momum culilawan (Gildemeister and
Stephan, Arch. Pharm. 235, 582), and
in certain oils of lemon poor in ^era-
niol (Schimmel's Ber. Oct. 1898 ;
Ch. Centr. 1898, 2, 985). Methyleu-
g-enol probably occurs in matico oil
from the leaves of Piper angustifolium
{Ibid.).

The betelphenol or chavibetol of the
ethereal oil of Piper hetle (Bertram and
Gildemeister, Journ. pr. Ch. [2] 39,
349) is possibly identical with this
methyleugenol. Occurs in Ceylon
' Lana Batu ' and in Java eitronella
oils (SchimmeFs Ber. Oct. 1899; Ch.
Centr. 1899, 2, 880 ; Joum. Soc. Ch.
Ind. 19, Sb^)'

Methyleugenol is a constituent of the
oil of Asarum arifolium (Miller, Arch.
Pharm. 240, 371 j Ch. Centr. 1902,
2, 642).

Synthetical Process.

[A.] From catechol [69], glycerol
[48], and methyl alcohol [13]. Catechol
is by methylation converted into vera-
trole (Behal and Choay, Bull. Soc. [3]
9, 143; Gorup, Ann. 147, 248; Mar-
asse, Ann. 152, 74). Glycerol is con-
verted into allyl iodide by distilling
with iodine and phosphorus (for refer-
ences see under isobutyl alcohol [18 ;
D]), and veratrole when heated with
allyl iodide and zinc gives methyl-
eugenol (Moureu, Comp. Rend. 121,
721).

82. Thymoquinol ;

Hydrothymoquiuoue ;

1 : 4-Methylmetlioetliyl-2 : 5-

Fhenediol.

lOH

Natural Sources.

In oil of wild bergamot from Monarda
Jistulosa (Brandel and Kremers, Pharm.
Rev. 19, 200 ; 244), and probably in
Algerian oil of bitter fennel (Tardy,
Bull. Soc. [3] 27, 994).

Synthetical Processes.

[A.] From thymol [67] through
thymoquinone and reduction of latter
(see below under the dimethyl ether
[83; A]).

[B.] From carvacrol [66] through
thymoquinone, &c. [83 ; B].

83. Dimethylthymoquinol ;

Thymoquinol Dimethyl Ether ;

1 : 4-Methylmethoethyl-2 ; 5-

Fheuediol Dimethyl Ether.

CH,

HO

CH3 . CH . CH3

O.CH,

CH3 . 0-

CH3 . CH . CH3

Natural Source.

Occurs with phloryl isobutyrate in oil
of arnica root from Arnica montana
(Sigel, Ann. 170, o^6c^.

Synthetical Processes.

[A.] Thymol and derivatives [67] on
oxidation give thymoquinone (Lalle-
mand, Jahresber. 1854, 592 ; Paternb,
Ber. 8, 440; Steiner, Ber. 11, 289;
Andresen, Journ. pr. Ch. [2] 23, 172;
Bayrae, Bull. Soc. [3] 7, 99; Arm-
strong, Ber. 10, 297 ; Liebermann and
Ilinski, Ber. 18, 3194), and this on
reduction gives thymoquinol (Carstan-
jen, Journ. pr. Ch. [2] 3, 54 ; Lalle-
mand, Comp. Rend. 37, 498; Ann.
101, 121). The dimethyl ether should
be obtainable by methylation, but the
identity of the natural product with
the synthetical ether remains to be
established.

83 B-84 C]

DIMETHYLTHYMOQUINOL

159

[B.] Carvacrol [66] on oxidation also
gives thymoquinone (Carstanjen, loc.
cif. 15;, 410; Claus, Journ. pr. Ch. [2]
39;, '^^6 ; Eeychler^ Bull. Soe. [3] 1, 33).
Subsequent steps as above.

84. Pyrogallol ; Pyrogallic Acid ;
1:2: 3-Fhenetriol.

HO

OH

OH

Natural Sources.

The pyrogallol complex exists in gallic
acid [Vol. II], and in myricetin from
the bark of the box-myrtle, Myrica nagi
= M. sapida — M. integrifolia = 31. rubra,
&c., from India, China, Singapore, and
Japan (A. G. Perkin and Hummel,
Trans. Ch. Soc. 69, 1293 > ^' ^- ^- ^"^
Clifford, Ibid. 81, 203).

Myricetin is contained also in Sicilian
sumach from Ji/ius coriaria (A. G. P.
and A\\en,Ibid. 1302), in the colouring-
matter from the leaves of Pisiacia
lentiscus, in ' gambruzzo ' from the
stalk of RJius coriaria, and in the galls
of Pistacia terebinthus (A. G. P. and
Wood, Proc. Ch. Soc. 14, 104; Trans.
73, 374 et seq.). Myricetin is present
in Venetian sumach from the leaves of
Rhus cotinus (A. G. P. Trans. Ch. Soc.
73, 1 01 7), in the leaves of Pkus
metopiwm, Myrica gale, and (probably)
of logwood, Hcematoxylon campeachianum
{Ibid. Proc. 16, 45; Trans. 77, 426).
A rhamnoside of myricetin is contained
in the bark of Myrica nagi {Ibid. Proc.
18, II).

The pyrogallol complex is probably
contained in haematoxylin from logwood
(see under catechol [69]).

Mezcalin, one of the cactus alkaloids
from Echinocactus letvinii, probably con-
tains the pyrogallol complex (Heffter,
Ber. 34, 3009).

The dimethyl- (methyl) pyrocatechol
complex exists in iridin, a glucoside

found in the orris-root from Iris jloren-
Una from Macedonia, coasts of Black
Sea, and Asia Minor (G. de Laire and
Tiemann, Ber. 26, 2011).

Sinalbin, a glucoside which occurs in
the seed of white mustard [l7l], con-
tains the sinapic acid complex, and the
latter is a derivative of dimethylpyro-
gallol (Gadamer^ Arch. Pharm. 235,
570; Ch. Centr. 1898, 1, 500; Ber.
30, 2330).

Syringin, a glucoside found in the
bark of Syringa vulgaris, Ligustrum vul-
gare, and Robinia pseudacacia, also con-
tains (through syringenin) the same
complex.

The alkaloid narcotine from opium
contains the methyl-methylene-pyro-
gallol complex. Anthragallol [148]
dimethyl ether contains the dimethyl-
pyrogallol complex. The pyrogallol
complex is possibly contained in kinoin
from Malabar kino from Pterocarpus
marsupium.

Synthetical Processes.

[A.] From phenol [6O] through p-
chlorphenol by various chlorinating
processes (Dubois, Zeit. [2] 2, 705;
3, 205 ; Schmitt and Cook, Ber. 1, 67 ;
Petersen and Bahr-Praderi, Ann. 157,
123), a- and /8-p-chlorphenolsulphonie
acid by sulphonation (Petersen and
Bahr-Praderi, loc. cit. 128), and potash
fusion of either sulphonic acid {Ibid.

[B.] Salicylic acid [Vol. II] can by
various iodising processes be converted
into 3 : 5-diiodosalicylic acid (Laute-
mann, Ann. 120, 304 ; Liechti, Ann.
Suppl. 7, 141 ; Demole, Ber. 7, 1439 ;
Weselsky, Ann. 174, 103; Birnbaum
and Reinherz, Ber. 15, 459). Accord-
ing to Lautemann {loc. cit. 317), this
diiodosalicylic acid when heated with
aqueous potash gives pyrogallol (? by
isomeric change).

[C] Gallic acid [Vol. II] gives pyro-
gallol when heated (Braconnot, Ann. 1,
26; Pelouze, Ann. 10, 159; Liebig,Ann.
101, 47 ; De Luynes and Esperandieu,
Zeit. [2] 1, 702 ; Thorpe, Pharm. Journ.
[3] 11, 990; Cazeneuve, Bull. Soc. [3]
7, 549)-

160

AROMATIC ALCOHOLS AND PHENOLS

[85-86.

85. Hydroxyquiuol ;

Hydroxyhydroquinone ;

1:2: 4-Fhenetriol.

HO

lOH

\/

HO

Natural Source.

The complex is probably contained in
the colouring-matter of red grapes
(Sostegni, Gazz, 32^ 17).

Synthetical Processes.

[A.] From quinol [7l] by fusion with
caustic soda (Barth and Schreder,
Monats. 4, 176; 5, 590).

[B.] Quinone [142] on treatment with
acetic anhydride and strong sulphuric
or phosphoric acid gives hydroxyquinol-
triacetatCj from which the phenol is
liberated by acid hydrolysis (Thiele,
Ber. 31, 1347; Bayer & Co., Germ.
Pat. 101607 of 1897 ; Ch. Centr. 1899,
1, 1094 ; and Suppl. Pat. 107508 of
1898; Ch. Centr. 1900, 1, 1087).

86. Fhloroglucinol ;
1:3: 5-Plieuetriol.

HO

HO

0
Hoi Ho

OH

O:

H

;0

H,

Natural Sources.

Phloroglucinol has been said to occur
in the free state in many plants (Wein-
zierl, Lindt, and Waage, Ber. deutsch.
bot. Gesell. 8, 250), but according to
Moller (Ch. Centr. 1897, 2, 1151) this
observation is erroneous. Occurs in
the colouring-matter of red grapes
(Sostegni, Journ. Ch. Soc. 70, II, 123).
Said to have been found in the bark
of 8tyrax heiizo'in and (as dibutyrate) in
the root oi Aspidium Jilix mas.

The phloroglucinol complex is con-
tained in the glucosides : —

Hesperidin; widely distributed in
fruit of the genus Citrus, such as C.
aurmitiuin, C. liwonum, O. limetta, C.
meclica, &c. In fruit of Dlosma alba
and other species. Hesperidin is de-
composed by certain moulds, such as
Aspergillus niger, &c. (Puriewitsch, Ber.
deutsch. bot. Gesell. 16, 368).

Glyeyphyllin (through phloretin) ;
from leaves of Smilax glycyphylla from
Australia.

Phloridzin (through phloretin) ; from
root-bark of apple, cherry, plum, pear,
&c.

Naringin or aurantiin ; from all parts,
and especially from the full-blown
flowers, of Citrus decumana from Java.

Loka'in ; the colouring-matter of
Chinese green from the berries of the
buckthorns Rhanmus utilis and R. chloro-
phorus.

The phloroglucinol complex exists
in quercetin, rhamnetin, isorhamnetin,
rhamnazin, luteolin [l4l], and con-
sequently in glucosides such as xantho-
rhamnin, quercitrin, rutin, osyritrin,
violaquercitrin, and robinin. (For
occurrence see under catechol [69].)

69], morin (see
), and myricetin
84]) ; in chrysin

Also in maclurin
under resorcinol [70
(see under pyrogallol
[138], the yellow colouring-matter of
poplar buds from Populus nigra, P. hal-
samifera, and P. pyramidalis (Kosta-
necki, Ber. 26, 2901) ; in apiin (through
ajngenin [l40]), a glucoside found in the
stem, seeds, and leaves of parsley, Apinm
petroselium (A. G. Perkin, Trans. Ch.
Soc. 71, 817). Apigenin has been
found also (with luteolin) in weld
(A. G. Perkin and Horsfall, Proc. Ch.
Soc. 16, 183).

Cyanomaclurin, obtained from Arto-
carpus integrifolia (A. G. P. and Cope,
Trans. Ch. Soc. 67, 939), contains the
phloroglucinol group, and is related to
the catechins of Gambir and Acacia
catechu, which also contain this com-
plex (A. G. P. and Yoshitake, Proc. Ch.
Soc. 18, 139; Trans. 81, 1172).

Lotusin, a glucoside contained in
Lotus arahicus from Egypt and N.
Africa, gives on hydrolysis lotoflavin.

86.]

PHLOROGLUCINOL

161

a yellow colouring-matter related to
luteolin and fisetin_, and which contains
the phloroglucinol complex (Dunstan
and Henry, Proc. Roy. Soc. 67, 325;
68, 374).

A glucoside occurring with apiin in
parsley is a derivative of luteolin methyl
ether (Vongerichten, Ber. 33, 3334 ;
3904; Ann. 318, t2i).

Acacetin, a colouring-matter con-
tained in leaves of Rohinia psei td acacia ,
is probably apigenin methyl ether
(A. G. Perkin, Trans. Ch. Soc. 77,

43°)-

Kampheride from the root of Chinese

galangal [Alphiia officinarum) contains
the phloroglucinol complex (Gordin,
Dissert. Bern, 1897; Testoni, Gazz.
30, '^'Z'])- The same root contains
galangin and its methyl ether, which
also probably contain the phloroglucinol
complex {Ibid. : see also A. G. Perkin
and Allison, Trans. Ch. Soc. 81, 472).
A colouring-matter related to kam-
pheride occurs as glucoside in the
flowers of IDeJphinium consoUda (A. G.
Perkin, Trans. Ch. Soc. 73, 275;
A. G. P. and Wilkinson, Proc. Ch.
Soc. 16, 182). The colouring-matter
from the glucoside of Delphinium con-
soUda is kampherol (A. G. P. and
Wilkinson, Trans. Ch. Soc. 81, 589).
Kampheride is the methyl ether of
kampherol, and the latter is identical
with the colouring-matter contained in
the glucoside robinin from the flowers
of Rohinia pseudacacia (A. G. Perkin,
Proc. Ch. Soc. 17, 87; Trans. 81,

473)-

Scutellarin from Scutellaria altissima

and other Labiates contains (through

scutellarem) the phloroglucinol complex

(Molisch and Goldschmiedt, Monats.

22, 679).

Cotoin from coto bark contains the
methylphloroglucinol complex (Ciami-
cian and Silber, Ber. 27, 409) ; hydro-
cotoin [134] from the same source, the
dimethylphloroglucinol complex, and
methylhydrocoto'in [l35] from paracoto
bark contains the trimethylphloro-
glucinol complex.

The phloroglucinol complex is con-
tained in gentisin [l37], and exists
possibly in catechin, kino, and in

dragon's blood, a resin from the W.
Indian Pterocarpns {Bmmonorops) draco ;
in gummigutt resin from Garcinia
morella from Siam, Singapore, and
Ceylon ; in tormentilla red from the
root of Poientilla tormentilla ; possibly
also in the tannin from Persea lingue,
in the tannins from horse-chestnut, from
the root-bark of apple, from the needles
of Abies pectinata, from Epacris leaves,
from Ledum palvstre, and from other
sources.

Vitexin and homovitexin, colouring-
matters existing as glucosides in the
New Zealand dye wood, 'puriri,' from
Vitex littoralis probably contain the
phloroglucinol complex (A. G. Perkin,
Trans. Ch. Soc. 73, 1029). Vitexin is
probably a stable glucoside of apigenin
{Ibid. Proc. Ch. Soc. 16, 45 ; Trans. 77,
422).

Scoparin, the colouring-matter of
broom, Spartium scoparium, which may
be a stable glucoside of luteolin methyl
ether, contains this complex {Ibid. Proc.
Ch. Soc. 15, 123; 16, 45; Trans. 77,

423)-

The complex is probably contained in

gossypetin, a colouring-matter which

occurs, as glucoside, in the cotton

flowers of Gossi/pium herhaceum {Ibid.

Trans. Ch. Soc. 75, 828), and in genis-

tein, a colouring-matter contained in

dyer's broom. Genista tinctoria (A. G. P.

and Newbury, Trans. 75, 837 ; A. G. P.

and Horsfall, Ibid. 77, 13 10).

The complex is contained in filixic

and flavaspidic acids, in aspidinol and

albaspidin, compounds obtained from

the rhizome of Aspidium jilix maSy

A. spinnlosum, and Athyrinm jilix fmnina

(Boehm, Ann. 302, 181 ; 307, 249;

318, 230 ; 245 ; 253 : see also Herzig

and Wenzel, Monats. 23, 81 ^^5 seq)).

Filixic acid may contain the complexes

of homologues of phloroglucinol, such

as dimethyl- and trimethylphloroglu-

cinol.

Note : — For synthesis of dimethylphloro-
glucinol from trinitro-m -xylene seeWeidel and
Wenzel, Monats. 10, 237 ; of trimethylphloro-
glucinol from trinitromesitylene, Ihid., and
Cassella & Co., Germ. Pats. 102358 of 1897 ;
Ch. Centr. 1899, 1, 1263, and 103683 of 1898 ;
Ch. Centr. 1899, 2, 503.

M

162

AROMATIC ALCOHOLS AND PHENOLS [86 A-G.

Synthetical Processes.

[A.] From acetylene [l ; A], acetylene
dibromide by bromination (Sabanejeff^
Ann. 178, ii6), bromacetylene by the
action of alcoholic soda on the dibromide
{Iljich Journ. Euss. Soc. 17, 175). Brom-
acetylene undergoes (partial) photo-
chemical polymerisation to 1:3: 5-tri-
brombenzene {Ibid. Jy6), and this on
treatment with sodium methylate in
methyl alcohol gives 3 : 5-dibromphenol
methyl ether, which on treatment with
sulphuric acid yields 3 : 5-dibromphenol
(Blau, Monats. 7, 630). The latter
gives phloroglucinol on fusion with
potash [Ibid. 6^2,).

Bromacetylene can also be obtained
from ethylene through various bromine
derivatives (Sawitsch, Ann. 119, 183;
Reboul, Ann. 124, 367 ; 125, 81), so
that generators of ethylene [l; A; D, &c.]
become generators of phloroglucinol.

[B.] From phenol [6O], being among
the products of fusion with caustic
soda (Barth and Schreder, Ber. 12, 417).

Or from phenol through picric acid
(2:4: 6-trinitrophenol) by nitration of
the phenol or (better) its sulphonic
acids (Laurent, Ann. 43, 319; Schmitt
and Glutz, Ber. 2, 52 ; Vidal, Fr. Pat.
315696 of 1901 ; Journ. Soc. Ch. Lid.
21, 544), 3:4: 6-chlortrinitrobenzene
(picryl chloride) by the action of phos-
phorus pentachloride (Pisani, Ann. 92,
336 ; Clemm, Journ. pr. Ch. [3] 1, 145),
and 1:3: 5-triaminobenzene by reduc-
tion of picryl chloride by tin and hydro-
chloric acid. By the action of boiling
water on the hydrochloride of the
triamine in an atmosphere of hydrogen
phloroglucinol is produced (Flesch,
Monats. 18, 755; also Eng. Pat. 445
of 189H : see further Weidel and Pollak,
Monats. 21, 3o).

Note : — The following synthesised products
give picric acid by the action of nitric acid and
thus become generators of phloroglucinol : —
salicylic aldehyde [117] ; saligenin [55] ; sali-
q/lic acid, coumarin, and indigo [Vol. II].

[C] From resorcinol [70] by fusion
with caustic soda (Barth and Schreder,
Ber. 12, 503 ; Tiemann and Will, Ber.
14, 954; 18, 1333).

[D.] From orcinol [75] by fusion with
caustic soda (Barth and Schreder,
Monats. 3, 649).

[E.] From 7nalomc acid [Vol. II] and
alcohol [14] ; the diethyl ester of the
acid on heating with sodium gives
phloroglucinoltricarboxylic ethyl ester
(Baeyer, Ber. 18, 3457 ; Bally, Ber.
21, 1767), and this by fusion with
potash yields phloroglucinol (Baeyer,
loc. cit. 3458 : see also Willstatter, Ber,
32, 1373).

Note : — According to Moore (Trans. Ch. Soc.
85, 165) the ester formed as the first product
of condensation of ethyl malonate is ethyl
phloroglucinoldicarboxylate.

The tricarboxylic ester can also be
obtained by the action of zinc methyl
or ethyl on malonic ester (Lang, Ber.
19, 3038).

Or from malonic ester through
acetonetricarboxylic ester by the action
of sodium and the distillation of the
monosodium compound of the latter
under reduced pressure, which gives
acetonedicarboxylic ester (Willstatter,
Ber. 32, 1374). The latter can be con-
verted into phloroglucinol as under P
below. Acetonetricarboxylic ester is
directly convertible into phloroglucinol-
tricarboxylic ester by the action of
malonic ester and dry sodium ethylate
in ethereal solution {Ibid. 1385),

[P.] From citric acid [Vol. II] and
ethyl alcohol [14] through acetonedi-
carboxylic diethyl ester (see under
orcinol [75 ; C]). The latter, on treat-
ment with sodium in benzene solution,
gives a ^ lactone/ which on boiling with
baryta water splits up into ethyl alcohol,
malonic acid, and phloroglucinol ( Jerdan,
Trans. Ch. Soc. 71, 1106). The lactone
is also produced by the action of sodium
ethylate on acetonedicarboxylic ester in
alcoholic solution {IIAd. Proc. Ch. Soc.
15, 151).

Acetonedicarboxylic ester and malonic
ester condense under the influence of
sodium ethylate with the formation of
phloroglucinoldicarboxylic ester (Rimi-
ni, Gazz. 26, 374).

[G.] From acetoacetic ester [Vol. II]
through acetonedicarboxylic ester (see
under orcinol . [75 ; D]), and then as
above under P.

86 H-87 B.]

PHLOROGLUCINOL

163

[H.] Benzene [6] can^ by processes
other than those comprised under B, C,
and D, be converted into phloroglu-
cinol : —

1 :3 :5-Benzenetrisulphonic acid (Sen-
hofer, Ann. 174, 343 ; Jackson and
Wing", Am. Ch. Journ. 9, 339) gives
phlorog-lucinol when fused with caustic
soda (Barth and Schreder^ Ber. 12,

417)-

Or benzene can be converted into

nitrobenzene and aniline, the latter
into i:\\ 6-tribromaniline by bromina-
tion (Fritzsche, Ann. 44, 291 ; Hof-
mann, Ann. 53, 50 ; Silberstein, Journ.
pr. Ch. [3] 27, loi), the NH^-group
replaced by hydrog-en by the diazo-
method (Meyer and Stiiber, Ann. 165,
173"; Baessmann, Ann. 191, 306;
Jackson and Moore, Am. Ch. Journ.
12, 167; 14, -^.'i^S)- The I :3:5-tri-
brombenzene thus formed can be con-
verted into 3 : 5-dibromphenol and
phloroglucinol as under A.

Or from aniline through sulphanilic
acid and benzenediazosulphonic acid,
the latter giving picric acid by the
action of nitric acid (Wenghofer, Germ.
Pat. 135096 of 1900 j Ch. Centr. 1901,
2, 1105).

Or benzene can be converted into
1:3: 5-trinitrobenzene by extreme nitra-
tion (Hepp, Ann. 215, 345), the latter
reduced to the corresponding triamine,
and then converted into phloroglucinol
as under B.

Or toluene on nitration gives 3:4:6-
trinitrotoluene (Wilbrand, Ann. 128,
178), and this on oxidation with nitric
acid yields 3:4: 6-trinitrobenzoic acid
(Tiemann and Judson, Ber. 3, 324).
The 3:4: 6-triaminobenzoic acid gives
phloroglucinol on heating with water
(Cassella & Co., Germ. Pat. 103358
of 1897; Ch. Centr. 1899, 1, 1363).

Note : — Generators of toluene (see under
benzyl alcohol [54 ; A ; &c.]) thus become
generators of phloroglucinol.

[I.] Furfural [l26] on oxidation with
silver oxide or alkaline permanganate,
or on treatment with alcoholic potash,
gives pyromucic acid (Schwanert, Ann.
114, 6-3, ; 116, 357 ; Ulrich, Jahresber.
1860, 369; Beilstein and Schmelz,

Ann. Suppl. 3, 375 ; Limpricht, Ann.
165, 379 ; Bieler and Tollens, Ann.
258, i30j Schiff, Ann. 239, 374;
261, 355). This acid, by the action of
bromine in water, yields mucobromic
acid (Beilstein and Schmelz, loe. cit.
376 ; Jackson and Hill, Am. Ch. Journ.
3, 105), and this, by the action of
nitrites, gives nitromalonic aldehyde
(Hill and Sanger, Ber. 15, 1906 ; Hill
and Torrey, Ber. 28, 3597 } ^^- Ch.
Journ. 22, 89). The latter, on decom-
position by aqueous hydrochloric acid,
yields (with formic acid) 1:3: 5-trinitro-
benzene {Ibid.), which can be converted
into phloroglucinol as above under B.

[J.] Iretol [88] is reduced to phloro-
glucinol by sodium amalgam (Tiemann
and G. de Laire, Ber. 26, 3036).

87. Antiarol;

l-Hydroxy-3 :4: 5-trimethozybenzene;

1:3:4: S-Fhenetetrol 3:4: 5-Tri-

methyl Ether.

HO

HsCO^^ /OCH3
OCH3

Natural Source.

The sap of the upas tree, Antiaris
toxicaria (Kiliani, Arch. Pharm. 234,

438).

Synthetical Processes.

[A.] From pyrogallol [84] through
the trimethyl ether by methylation,
3 : 5-dimethoxyquinone by oxidation
with nitric acid, 3 : 5-dimethoxyquinol
by reduction, and methylation of the
latter by the usual method (Will, Ber.
21, 613 j 3030).

[B.] From catechol [69] through
guaiacol. The latter, on sulphonation
at a low temperature, gives a consecu-
tive monosulphonic acid which yields
pyrogallol methyl ether on fusion with
alkali (Hoffmann, La Roche & Co.,

M 3

164

AROMATIC ALCOHOLS AND PHENOLS '[87B-89A.

Germ. Pat. 109789 of 1898; Ch.
Centr. 1900^ 2,460). The monomethyl
ether might be converted into the tri-
methyl ether by further methylation,
and then treated as above.

[C] 'FrorOi johloroglucinol [86] through
the trimethyl ether by methylation
(Will, Ber. 21, 603; Pollak, Monats.
18, 736), 3 : 5-dimethoxyquinone by
oxidation with chromic acid (Ciamician
and Silber, Ber. 26, 786), and then as
under A.

[D.] From benzene [6] through 1:3:
5-trinitrobenzene (see under phloro-
glucinol [86 ; H]), which, on heating
with sodium methoxide, gives 3 : 5-di-
nitroanisole (Lobry de Bruyn, Bee. Tr.
Ch. 9, 309). The latter on reduction
yields diaminoanisole, and this,onheating
with water, gives phloroglucinol methyl
ether (Herzig and Aigner, Monats. 21,

433)-

acids (Cahours, Ann. 69, 23 8), the 3:4:6-
trinitroanisole reduced by tin and hy-
drochloric acid to diaminohydroxyani-
sole and the latter (hydrochloride) heated
with dilute stannous chloride in an
atmosphere of carbon dioxide (Kohner,
Monats. 20, 933).

Or from phenol through picric acid
(see under phloroglucinol [86 ; B]) and
the methyl ether of the latter by
methylation. Subsequent steps as
above.

Note : — Generatoi-s of picric acid, viz. sali-
cylic aldehyde [117], saligenin [55], salicylic acid,
coumarin, and indigo [Vol. II], thus become
generators of iretol (see under phloroglucinol
[86 ; B]).

[B.] Anisic acid [Vol. II] gives trini-
troanisole on nitration as under A
(Cahours, loc. cit.). Subsequent steps
as above.

88. Iretol; l-Methoxy-2 : 4 : 6-

trihydrozybeuzeue ; 2:4:6-

Trihydroxyanisole ; 1:2:4:6-

Fheuetetrol 1- Methyl Ether.

OCH,

OCH,

HO

lOH

HO

H,

:0

H,

Natural Souece.

The complex is possibly contained in
orris root from Iris fiorentina, which
contains a glucoside, iridin, which is
decomposed, on heating with dilute sul-
phuric acid and alcohol, into glucose
and irigenin. The latter gives iretol
among other products (iridic and formic
acids) on heating with strong potash
solution (G. de Laire and Tiemann,
Ber. 26, 2015).

Synthetical Processes.

[A.] From phenol [60] and methyl
alcohol [13] through anisole (see under
anisic aldehyde [120 ; B]). The latter
is nitrated with nitric and sulphuric

89. Asarone ;

l^-Propenyl-2 ; 4 : 5-trimethoxy-

benzene.

CH : CH . CH3
OCH,

CH3O

OCH3

Natural Sources.

In the root of Asarum europium
(Petersen, Ber. 21, 1057). Also in
certain matico oils from the leaves of
Piper angustifolium (Schimmers Ber.
Oct. 1898; Ch. Centr. 1898, 2, 985),
in sweet flag oil from the root of Acorus
calamus (Thoms and Beckstroem, Ber.
34, 102IJ Thoms, Zeit. angew. Ch.
14, 1019; T. and B. Ber. 35, 3190),
and in the oil of Asarum arfolium
(Miller, Arch. Pharm. 240, 371).

Synthetical Processes.

[A.] YxQxa. phenol [60], propionic acid
[Vol. II], melhi/l alcohol [13], and
hydrogen cyanide [172]. Phenol is
nitrated, the o-nitrophenol converted

89 A-90 A.]

ASARONE

165

into its methyl ether, and then reduced
to o-anisidine (Miilhauser, Ann. 207,
239). The latter, on oxidation with
sulphuric acid and potassium dichro-
mate, gives methoxyquinone {Ibid. 25 1 ;
Will, Ber. 21, 605), and this by reduc-
tion methoxyquinol (Will, loc. cit. 606).
The latter, on further methylation with
methyl iodide and potassium hydroxide,
yields the i : a : 4-trimethoxybenzene
(Will). By the action of hydrogen
cyanide on the latter in conjunction
with hydrogen chloride in presence of
aluminium chloride the 2:4: 5-trimeth-
oxybenzaldehyde = asaryl aldeliycle [125]
is formed (Gattermann and Eggers, Ber.
32, 289), and this, on heating with
propionic anhydride and sodium pro-
pionate at 150°, gives asarone {Ibid.
290).

[B.] JResorcuiol [70] may replace
phenol in the above synthesis. Diazo-
tised aniline is combined with resor-
cinol, the azo-compound methylated by
heating with potassium hydroxide and
methyl iodide (Bechold, Ber. 22, 2375),
and the dimethyl ether reduced to 1:3-
methoxy-4-aminobenzene. The latter,
on oxidation with sulphuric acid and
sodium dichromate, gives methoxyqui-
none {Ibid. 2381), which can be reduced,
methylated, and treated as under A.

[C] Quinol [71] may replace phenol
in this synthesis since, on fusion with
sodium hydroxide, it gives i : 2 : 4-tri-
hydroxybenzene {hydroxy quinol [85])
(Barth and Schreder, Monats. 4, 176;
5, 590), and this can be converted into
the trimethyl ether by methylation, and
then treated as above under A.

[D.] Quifione [142] gives hydroxy-
quinol triacetate on treatment with
acetic anhydride and a little sulphuric
acid (Thiele, Ber. 31, 1247 • ^^e also
[85]). The triacetate hydrolysesto the
trihydroxy-compound, which can be
treated as above.

[E.] From asaryl aldehyde [125] and
proj)ionic acid [Vol. II] by heating the
aldehyde with propionic anhydride and
sodium propionate (Gattermann and
Eggers, as under A above).

90. a-Hydrojuglone ;

1:4: 5-Triliydroz3rnaphtlialeue ;

1:4: S-Naphthaleuetriol.

HO HO

HO

Natural Source.

In all green parts of the walnut
tree, luglans regia (Mylius, Ber. 17,
241 1 ; 18,475; '2'S^I)'

Synthetical Processes.

Syntheses of Naphthalene.

[A.] From benzene through tokiene
and benzyl chloride (see under benzyl
alcohol [54 j A, &c.]). The latter, when
mixed with allyl iodide (see under iso-
butyl alcohol [18 ; D]) and treated in
ethereal solution with sodium, gives
phenylbutylene (Aronheim, Ann. 171,
225), the dibromide {Ibid. 229) of which
yields naphthalene on passing the vapour
over hot lime {Ibid. 233).

From be^izyl chloride and isopropyl
alcohol [16] by acting with sodium on
a mixture of isopropyl iodide and ben-
zyl chloride in ether so as to form
isobutylbenzene (Kohler and Aronheim,
Ber. 8, 509). The latter gives naph-
thalene on passing the vapour over
heated lead oxide (Wreden and Snato-
wicz, Ber. 9, 1606).

Benzene and isobutyl alcohol [18] also
give isobutylbenzene by the action of
sodium on brombenzene and isobutyl
bromide or iodide in ether or benzene,
(Riess, Ber. 3, 779 ; Wredin and Snato-
wicz, loc. cit.), or directly by heating
benzene with the alcohol and zinc chloride
at 300° (Goldschmidt, Ber. 15, 1066;
1425). Also by the action of aluminium
chloride on a mixture of benzene and
isobutyl chloride (Gossin, Bull. Soc, [2]
41, 446).

From toluene, 7nalonic acid [Vol. II],
and alcohol [l4]. Malonic acid is con-
verted into its diethyl ester and the

166

AROMATIC ALCOHOLS AND PHENOLS

[90 A.

latter into clilormalonic ester by chlori-
nation (Conrad and Bisehoff, Ann. 209^
319). By the action of chlormalonic
ester on sodiomalonic ester in alcoholic
solution the tetra-ethyl ester of s-
ethanetetracarboxylic (butanediacid-2 :
3-dimethylic or acetylenetetracarboxylic)
acid is formed {Ibid. 214^ 68 ; Ber. 13^
601 ; 21, 3087 ; Bischoff and Rach,
Ber. 17, 2785).

The same tetracarboxylie ester is also
formed by the action of iodine on ma-
lonic ester in presence of sodium eth-
oxide (Bischoff, Ber. 16, 1046 ; Bischoff
and Rach, Ber. 17, 3781), by the elec-
trolysis of an alcoholic solution of sodio-
malonic diethyl ester (Mulliken, Am.
Ch. Journ. 15, 523; Weems, Ibid. 16,
569), by the interaction of acetylene
tetrabromide, malonic ester^ and sodium
ethoxide (Crossley, Proc. Ch. Soc. 14,
348), and also from nitromalonic ester
(see under hydrogen cyanide [l72 ; AA])
through ethanedinitro-tetracarboxylic
ester by electrolysis : the dinitro-ester
gives the tetracarboxylie ester by reduc-
tion (Ulpiani and Gasparini, Gazz. 32,

Toluene can be converted into 0-
xylene (see under m-cresol [62 ; A]) by
methylation, and the latter into o-xylyl-
ene dibromide (i^ : 2^-dibromxylene) by
bromination (Radziszewski and Wispek,
Ber. 18, 1281J Schramm^ Ibid. 1279;
W. H. Perkin, junr.^ Trans. Ch, Soc.
53, 5). The xylylene dibromide and
ethanetetracarboxylic ester react when
heated in alcoholic solution in the pre-
sence of sodium ethoxide with the for-
mation of 1:2:3: 4-tetrahydronaph-
thalene-2 : 2 : 3 : 3 -tetracarboxylie tetra-
ethyl ester (Baeyer and W. H. Perkin,
junr., Ber. 17, 450 ; W. H. P., junr.,
Trans. Ch. Soc. 53, 12), and this on
hydrolysis yields the free acid which, on
heating at 185", gives the anhydride of
tetrahydronaphthalene-dicarboxylicacid
(B. and P. loc. cit.). The latter, when
passed through a red-hot tube, or when
the silver salt of the free acid is heated,
yields naphthalene {Ibid. 451).

Or sodio-chlormalonic ester and o-
xylylene dibromide may be heated in
alcoholic solution so as to form o-xylyl-
enedichlordimalonic tetra-ethyl ester

{Ibid. 452), and this, by treatment with
zinc dust and acetic acid, gives o-xylyl-
enedimalonic tetra-ethyl ester {Ibid, and
W. H. Perkin, junr.. Trans. Ch. Soc.
53, 16). By the action of iodine (ethe-
real solution) on the sodium derivative
of the latter ester the tetrahydronaph-
thalene derivative is formed, and can be
treated as above (Baeyer and W. H.
Perkin, junr., Ber. 17, 452).

Note : — The ethanetetracarboxylic ester re-
quired for this synthesis of naphthalene can
also be obtained from the amyl alcohol of fusel
oil [22] by converting the latter into amylene
(see under acetone [106 ; E]) and its dibromide.
The latter on heating with sodiomalonic ester
gives (with trimethylethylene) ethanetetra-
carboxylic ester (Ipatiefif, Journ. Russ. Soc. 30,
391). Alkylene dibromidesof the general form
KjCBr. CH2 • CHaBr give the tetracarboxylie
acid as a by-product by the action of sodio-
malonic ester {Ihid. 31, 349 ; also Ipatieff and
Swiderski, lUd. 33, 532 ; Ipatieff, Ibid. 34,
351)-

The conversion (partial) of benzene
into naphthalene may also be effected
through nitrobenzene, aniline, dimethyl-
aniline by methylation, and the action
of bromine on the latter at 110-120°
(Brunner and Brandenburg, Ber. 11,
698).

Naphthalene is among the aromatic
hydrocarbons formed when the copper
compound of acetylene [l ; A] is dis-
tilled with zinc dust (Erdmann and
Kothner, Zeit. anorg. Ch. 18, 48).
Naphthalene is formed with other pro-
ducts by pyrogenic synthesis from : —

Alcohol (Reichenbach, Berz. Jahres-
ber. 12, 307) ; methane ; acetic acid ;
toluene; xylene; pseudocumene ; ethyl-
ene and benzene ; ethylene and styrene ;
ethylene and anthracene (Berthelot,
Bull. Soc. [2] 6, 272; 279; Ferko,
Ber. 20, 660); ethylene (Norton and
Noyes, Am. Ch. Journ. 8, 362) ; acetyl-
ene or acetylene and benzene (Berthelot,
Comp, Rend. 62, 905; 93,613; Bull.
Soc. [2] 6, 268; 7, 218; 274; 303;
9, 456) ; ethylene and diphenyl (Barbier,
Comp. Rend. 79, 121); heptane;
octane; n-hexyl alcohol (Worstall and
Burwell, Am. Ch. Journ. 19, 815); iso-
butylene (Noyes; Beilstein, I, 115).

Naphthalene is formed from certain
metallic carbides, e. g. of barium, by

90 A.]

a-HYDROJUGLONE

167

heating to 600-800° with the metallic
hydroxide (Bradley and Jacobs, Germ.
Pat. 125936 of 1898; Ch. Centr. igoo,,

1. 77)-

Conversion of Na^ihthalene into
Hydrojuglone.

By oxidation with chromic acid in
acetic acid naphthalene is converted
into a-naphthaquinone (Groves, Journ.
Ch. Soc. 26, 309; Plimpton, Trans.
37, 634; Japp and Miller, Ibid. 39,
220 ; by electrolytic oxidation, De Bot-
tens, Zeit. Elektroch. 8, 673). The
latter on standing in dilute sodium hy-
droxide solution in presence of air gives
the 5-a-hydroxyquinone = juglone
(Kowalski, Ber. 25, 1659), and this on
reduction yields hydrojuglone (Mylius,
Ber. 17, 2412; 18, 463 ; 2567).

Naphthalene on sulphonation under
appropriate conditions gives (with i : 6-)
the I : 5 -disul phonic acid (Armstrong,
Ber. 15, 200 ; Armstrong and Wynne^
Proc. Ch. Soc. 2, 231 ; 3, 42 and 146;
Bernthsen and Semper, Ber. 20, 934;
Bernthsen, Ber. 22, 3327). The latter
on fusion with alkali yields i : 5-dihy-
droxynaphthalene (Armstrong and
Wynne, Proc. Ch. Soc. 3, 43 ; Bernth-
sen and Semper, loc. cit. ; Erdmann,
Ann. 247, 306), and this on oxidation
with chromic acid mixture gives 5-
hydroxy-a-naphthaquinone, which can
be treated as above.

Or naphthalene may be nitrated and the
a-nitronaphthalene sulphonated, when
the I : 5-nitrosulphonic acid is formed
(wi th other isom er ides) (Laurent, Ann . 72,
298 ; Comp. Kend. 31, 537 ; Schmidt
and Schaal, Ber. 7, 1367; Palmaer,
Ber. 21, 3260; Erdmann, loc. cit.; Cleve,
Bull. Soc. [2] 24, 506). The latter
gives 1 : 5-naphthylaminesulphonic acid
by reduction (references as before, and
Schoellkopf Anilin Co., Germ. Pat.
40571 of 1885; Ekbom, Ber. 23,
1 1 18; Bernthsen, Ibid. 3088; Schultz,
Ber. 20, 3158; Erdmann, 2/jid. 3185;
Ann. 247, 306 ; 275,192; 262). This
aminosulphonic acid by the diazo-method
is converted into 1 : 5-naphtholsulphonic
acid (Cleve, loc. cit. ; Schultz, Ber. 20,
31 61; Erdmann, loc. cit.), which on

fusion with potash gives i : 5-dihydroxy-
naphthalene (Cleve, loc. cit. ; Ewer
and Pick, Germ. Pat. 41934 of 1887).
The latter can be converted into juglone,
&c., as above.

Or naphthalene-a-sulphonic acid can
be nitrated and the i : 5-nitrosulphonic
acid (which is formed with the i : 4 and
I : 8 isomerides) reduced and converted
as above (Cleve, loc. cit. ; Schoellkopf
Co., loc. cit. ; Cleve, Ber. 23, 958 ;
Bernthsen, Ibid. 3088 ; Erdmann and
Silvern, Ann. 275, 230).

Or naphthalene can be converted into
a-nitronaphthalene and a-naphthylam-
ine. The latter (or its acetyl-deriva-
tive) gives (with other isomerides) the
I : 5-aminosulphonic acid on sulphona-
tion (Witt, Ber. 19, 578 ; Lange, Ber.
20, 2940; Schultz, Ibid. 3158; Erd-
mann, Ibid. 3185 ; Ann. 247, 306 ;
275, 192; 262; Mauzelius, Ber. 20,
3401 ; Ewer and Pick, Germ. Pat.
42874 of 1887), and this sulpho-acid can
be treated as above.

The I : 8-nitrosulphonic acid obtained
by the nitration of naphthalene-a-sul-
phonic acid as above gives the 1:8-
aminosulphonic acid on reduction
(Schoellkopf Co., loc. cit. ; Schultz, Ber.
20, 3158 j Erdmann, Ann. 247, 306 ;
275, 262 ; Bernthsen, Ber. 23, 3088),
and this by the diazo-reaction gives the
1 : 8-sultone (references as before). The
latter on fusion with potash yields i : 8-
dihydroxynaphthalene (Erdmann, loc.
cit.), and this on oxidation with chromic
acid mixture gives juglone (Bernthsen
and Semper, Ber. 20, 939).

Or the I : 8 -aminosulphonic acid on
fusion with alkali gives i : 8-amino-
naphthol (Bad. An. Sod. Fab., Germ.
Pat. 55404 of 1889; Ber. 24, Ref.
481). The latter on combination with
diazosulphanilic acid gives an azo-com-
pound which on reduction yields 1 14-
diamino - 8 - naphthol, and this gives
juglone on oxidation with ferric chloride
(Friedlander and Silberstern, Monats.
23, 513)-

Note : — Further references to processes for
obtaining i : 8-aminonaplithol or its generators
are given in Germ. Pats. 54662 ; 62289 ; 77937 ;
84951 and 112778 of the Bad. An. Sod. Fab. ;
Germ. Pats. 71836 ; 75055 ; 753^7 5 80668 and

168

AROMATIC ALCOHOLS AND PHENOLS [90 AG.

109102 of Bayer & Co. ; Germ. Pats. 73381 and
73607 of Cassella & Co. See also Dressel and
Kothe, Bar. 27, 2139.

The conversion of naphthalene into
the a-quinone^ and thence (as above)
into juglonCj can also be effected through
a-naphthylamine, a-acetnaphthalide^ 1 :
4-nitroacetnaphthalidej 1 : 4-nitronaph-
thylamine, i : 4-naphthylenedianiinej
and oxidation of the latter by chromic
acid mixture (Liebermann, Ann. 183^
24a : all azo-derivatives of a-naphthyla-
mine g-ive the i : 4-diamine on reduc-
tion ; Perkin, Ann. 137, 359 j Griess,
Ber. 15, 2183).

1 : 4-Nitronaphthylamine is also ob-
tained by the action of hydroxylamine
on a-nitronaphthalene in the presence
of sodium ethoxide (Angeli and Angelico,
Atti Real. Accad. [5] 8, II, 28 ; Ch.
Centr. 1899, 2, 371).

Or a-acetnaphthalide can be converted
into I : 4-nitronaphthol by boiling the
I : 4-nitro-derivative with potash solu-
tion (Andreoni and Biedermann, Ber. 6,
342 ; Liebermann and Dittler, Ber. 7,
240; Hiibner and Ebell, Ber. 8, 562;
Ann. 208, 324). The nitronaphthol on
reduction gives i :4-aminonaphthol, and
this also oxidises to a-naphtbaquinone
(Liebermann, Ann. 183, 24a ; Ber. 14,
1796 ; Zincke, Ann. 286, 70).

a-Naphthylamine can also be directly
oxidised to the a-quinone by chromic
acid mixture (Monnet, Reverdin, and
Noelting, Ber. 12, 2306).

[B.] From benzoic aldehyde [114] and
succinic acid [Vol. II] by heating the
aldehyde with succinic anhydride and
sodium succinate so as to form phenyl-
isocrotonic (/3-benzalpropionic = phene-
i^-butenylic) acid (Perkin, Journ. Ch.
Soc. 31, 394; Jayne, Ann. 216, 100;
Erdmann, Ann. 227, 258 ; Leoni, Ann.
256, 64). The latter on boiling with
water gives a-naphthol (Fittig and Erd-
mann, Ann. 227, 242), from which a-
naphthaquinone, and thence juglone
and hydrojuglone, can be obtained by
converting the naphthol into i :'4-nitro-
sonaphthol (a-naphthaquinoneoxime) by
the action of nitrous acid (2-nitroso-
I -naphthol is formed simultaneously)
(Fuchs, Ber. 8, 626 ; Ilinsky, Ber. 17,
2590 ; Henriques and Ilinsky, Ber. 18,

706}. The nitrosonaphthol reduces to
I : 4-aminonaphthol (Grandmougin and
Michelj Ber. 25, 972), and this can be oxi-
dised to a-naphthaquinone as under A.

The azo-derivatives of a-naphthol also
give I : 4-aminonaphthol on reduction
(Liebermann and Jacobson, Ann. 211,
^6; Seidel, Ber. 25, 423; Grandmougin
and Michel, loc. cit.). a-Naphthyl ace-
tate gives some a-quinone on oxidation
(Miller, Ber. 14, 1600).

[C] From cinnaviic and malonic acids
[Vol. II], and methyl alcohol [13]. Cin-
namic acid is converted into its methyl
ester and brominated so as to form the di-
bromide. The latter, when heated with
sodio-malonic methyl ester in methyl
alcohol solution, gives Fai-phenyltri-
methylene-2 : 2 : 3 - tricarboxylic tri-
methyl ester, from which the free acid
can be obtained by hydrolysis (Buchner
and Dessauer, Ber. 25, 1153)- The acid
on heating (in COg) at 180-200°, and
finally by distillation in a vacuum, yields
phenylisocrotonic acid {Ibid. 1 155), which
can be converted into a-naphthol, &c.,
as under B.

[D.] Furfural [126] and benzene [e]
give a-naphthylamine by heating pyro-
mucic acid (see under erythritol [50 ;
N]) with aniline, zinc chloride, and
lime at 300° (Canzoneri and Oliveri,
Gazz. 16, 493). The naphthylamine
can be converted into a-naphthaquinone,
&c., as under A.

[E.] Manuitol [5l] and benzene [6]
can be made to give a small quantity
of a-naphthylamine by heating the al-
cohol with aniline hydrochloride at
200-240° (Effront, Jahresber. 1885,
1210 j Ber. 18, Ref. 383).

[F.] From cinnamic aldehyde [123]
and hippuric acid [Vol. II], which con-
dense to form an anhydride which, by
the action of sodium hydroxide, gives
cinnamylidenehippuric acid [CgHg. CH :
CH . CH : C(COOH)NH . CO . C^HJ,
and this on heating with hydrochloric
acid to 1 1 o-i 20° yields (with a-naphthoic
acid) naphthalene (Erlenmeyer, junr.,
and Kunlin, Ber. 35, 384).

[G.] Pi/rogallol [84] on oxidation gives
a product (purpurogallin) which yields
naphthalene on distillation with zinc dust
(Nietzkiand Steinmann, Ber. 20, 1278).

91-C.]

FORMIC ALDEHYDE

169

ALDEHYDES AND KETONES : FATTY GROUP.

91. Formic Aldehyde ; Formalde-
hyde ; Methaual.

H .CHO

Natural Sources.

The aldehyde may possibly exist in
plant cells containing chlorophyll (Rein-
ke, Ber. 14, 2148; Mori, Jahresber.
1882, 1143)5 but this observation re-
quires confirmation. The distilled
extract of witch - hazel, Ilamamelis
virginica, N. America, is said to contain
formic aldehyde (Gunn, Ch. Drug-.
59, 796). Polacci claims to have ob-
tained distinct evidence of the presence
of the aldehyde in the distillate from
the leaves of plants which have been
exposed to light (Ch. Centr. 1899, 2,
881, from Boll. Chim. Pharm. 38, 601 ;
also Ch. Centr. 1900, 1, 833 ; 1901, 2,
938).

Synthetical Processes.

[A.] From carbon dioxide and hydro-
gen by the silent electric discharge
(Brodie, Proc. Roy. Soc. 22, 172); from
carbon dioxide and water under the
influence of sunlight in presence of
uranium acetate (Bach, Comp. Rend.
116, 1 145; 1389). From, carbon mon-
oxide and hydrogen by the silent electric
discharge (Losanitsch and Jovitschitsch,
Ber. 30, 136; De Hemptinne, Bull.
Acad. Roy. Belg. 34, 269 ; Solvay and
Slosse, Ibid, 35, 547), or by passing over
hot spongy platinum (Jahn, Ber. 22,

9«9)-

From carbonic acid (carbon dioxide
in water) by reduction with hydrogen-
palladium or by electrolytic reduction
(Bach, Comp. Rend. 126, 479), or by the
action of violet light in presence of
uranium acetate (Ibid. Arch. Soc. Phys.
Nat. Geneve [4] 5, 401 ; Ch. Centr.
1898, 2, 42).

From acetylene [l; A, &c.], the silver,
mercury, or cuprous compounds of
which, as well as the sulphuric acid so-
lution, all yield iodoform on treatment
with iodine and alkali (Le Comte, Journ.

Pharm. 16, 297). From iodoform, as
below under D.

[B.] Methane [l] and oxygen give
formic aldehyde by the action of the
silent electric discharge (Maquenne,
Bull. Soc. [2] 37, 298).

Or from methane and air by passing
over heated catalytic surfaces of copper,
asbestos, &c. (Glock, Germ. Pat. 1 09014
of 1898; Ch. Centr. 1900, 2, 304), or
by slow combustion at low temperatures
with oxygen (Bone and Wheeler, Proc.
Ch. Soc. 19, 191 ; Trans. 83, 1074).

[C] From methyl alcohol [l3] by in-
complete combustion in air (Hofmann,
Proc. Roy. Soc. 16, 156; Ber. 2, 152; 11,
1685; Ann. 145, 357; Volhard, Ann.
176, 128 ; Kablukoff, Journ. Russ. Soc.

14, 194; Tollens, Ber. 15, 1629; ^^y
917; 19, 2133; Loew, Journ. pr. Ch.
[2 33, 321 ; Ber. 20, 144; Klar and
Schulze, Germ. Pat. 106495 of 1898;
Ch. Centr. 1900, 1, 1082). From
methyl alcohol (trace only) by oxidation
with air in a solution containing col-
loidal platinum (Glaessner, Ch. Centr.
1902, 2, 731).

Also from methyl alcohol by electro-
lytic oxidation in sulphuric acid solution
(Elbs and Brunner, Zeit. Elektroch. 6,
604) or by pyrogenic decomposition
(Ipatieff, Ber. 34, 598 ; 35, 1055).

Or from methyl alcohol through
methyl ether (Dumas and Peligot, Ann.

15, 12; Kane, Ann. 19, 166; Ebelmen,
Ann. 57, 328 ; Erlenmeyer and Kriech-
baumer, Ber. 7, 699 ; Tellier, Jahresber.
1877, 1157). The latter gives formic
aldehyde by pyrogenic decomposition
(Tistschenko, Journ. Russ. Soc. 31,
784 ; Ch. Centr. 1900, 1, 586).

Or from methyl alcohol through
methylal by oxidation with sulphuric
acid and manganese dioxide (Kane,
Ann. 19, 175; Malaguti, Ann. 32, $^,
or by electrolysis of the alcohol in di-
lute sulphuric acid (Renard, Ann. Chim.
[5] 17, 291). Methylal gives formic
aldehyde when heated with sulphuric
acid, the aldehyde rapidly polymerising
(Wohl, Ber. 19, 1841).

iro

ALDEHYDES AND KETONES: FATTY GROUP [81 C-F.

Note: — Methylal can be obtained from methyl
alcohol by converting the alcohol into methyl
chloride and the latter into methylene chloride
by chlorination (Kegnault, Ann. Chim. [2] 70,
377 ; 'Ann. 33, 328). Methylene chloride inter-
acts with sodium methylate to form methylal
(Arnhold, Ann, 240, 190).

Methyl alcohol gives formic aldehyde
among the products of the action of
chlorine or bromine (Lobry de Bruyn,
Ber. 26;, 271; Brochet, Comp. Rend.
121, 130).

By the action of fuming sulphuric
acid on methyl alcohol there is formed
an ' oxymethanesulphonic acid/ the
sodium salt of which gives formic alde-
hyde on decomposition by water (Miil-
ler, Ber. 6, 1032).

Or from methyl alcohol and acetic
acid [Vol. II] through methyl acetate,
chlormethyl acetate by chlorination
(Henry, Ber. 6, 740), and the action of
water at 100° on the latter (Michael,
Am. Ch. Journ. 1, 419).

[D.] From (?%/ alcohol [14] by in-
complete combustion (Mulliken, Brown,
and French, Am. Ch. Journ. 25, 11 1), or
by the incomplete combustion of ethyl
nitrate (Pratesi, Gazz. 14, 221).

Or from ethyl ether, the vapour
giving a trace of formic aldehyde when
passed through a hot tube (Tis-
tschenko, Journ. Russ. Soc. 31, 7^4 i
Ch. Centr. 1900, 1, 586).

Or from ethyl alcohol through chloro-
form (see under methane [l ; D]), methyl-
ene chloride by reduction (Perkin, Ch.
News, 18, 106 ; Greene, Comp. Rend.
89, 1077 ; Jahresber. 1879, 49° ; Ch.
News, 60, 75 ; Journ. Am. Ch. Soc. 1,
522), and methylal as above under C.

Note : — The generators of chloroform referred
to under methane [1 ; M ; P ; R, &c.] thus be-
come, with methyl alcohol, generators of formic
aldehyde through methylal.

Or from ethyl alcohol through ethyl-
ene, the latter giving formic aldehyde
when heated to 400° with an insufficient
quantity of oxygen for complete com-
bustion (Schutzenberger, Bull. Soc. [2]
31, 482).

Note : — All generators of ethylene thus be-
come generators of formic aldehyde.

Or from ethyl alcohol through ethyl-
ene glycol [45] (see under isopropyl al-

cohol [16 j C]). The latter, on electro-
lysis in presence of dilute sulphuric
acid, gives ' trioxymethylene ' (Renard,
Ann. Chim. [5] 17, 303), a polymeride
of formic aldehyde which is resolved by
heat, by hot water, or by combination
with acid sodium sulphite into the mono-
molecular aldehyde (Hofmann, Ber. 2,
152 j Tollens and Mayer, Ber. 21, 157 1 ;
Kraut, Ann. 258, 105 ; Harries, Ber.
34, 6'3,^ : see also Kekule, Ber. 25,
2435). Or trioxymethylene gives formic
aldehyde when passed with air through
a hot tube (Wolkoff and Menschutkin,
Ber. 31, 3067).

Or from glycol through glycollic alde-
hyde (see under furfural [126 ; G]), and
then as below under O.

Or from ethyl alcohol through iodo-
form (see under methane [l; D]), me-
thylene iodide by heating the latter
with hydriodic acid and phosphorus, &c.
(Butleroif, Ann. Chim. [3] 53, 313 ;
Hofmann, Ann. 115, 267 ; Baeyer, Ber.
5,1095). Methylene iodide gives me-
thylene chloride by chlorination (But-
leroff, Ann. 107, no; 111, 251), and
this, with methyl alcohol, is a generator
of methylal and of formic aldehyde as
above under C.

Or iodoform and sodium ethylate give
acrylic acid (Butleroff, Ann. 114, 204).
From the latter through a-chlorlactic
and glyceric acid [54 ; l] or through
oxyacrylic(glycidic)acid [92; j]. The
latter gives glyceric acid in contact
with water (Melikoff, Ber. 13, 272).
Subsequent steps as below under M.

Or from iodoform through methylene
iodide and trioxymethylene by the action
of silver oxide (or oxalate) on the iodide
(Butleroff, Ann. Ill, 242).

[E.] From acetic aldehyde\_d2] through
iodoform by the action of iodine and
alkali [l ; I], and then as above under
D. Or from aldehyde through crotonic
aldehyde [102] and crotonic acid (see
under n-butyl alcohol [17 ; G] and
under benzyl alcohol [54 ; H]). From
crotonic acid through /3-methylglyceric
acid to formic aldehyde as below under J.

[F.] From acetone [106], formic alde-
hyde being among the products formed
by passing the vapour over a heated
platinum spiral (Trillat, Comp. Rend.

91 P J.]

FORMIC ALDEHYDE

171

132, 1495), or by incomplete combustion
(Mulliken, Brown, and French, Am. Ch.
Journ. 25, iii).

Or from acetone through diacetona-
mine (see under aldehyde [92 ; S]),
the latter giving- trioxy methylene
(among other products) when the sul-
phate is oxidised by chromic acid mix-
ture (Heintz, Ann. 198, 45).

Or from acetone through chloroform
by the action of bleaching powder (see
under methane [l; J]), and then, with
sodium methylate, through methylal as
above under D and C. Or from acetone
through iodoform (see under methane
[1 ; j]), and then as above under D.

[G.] From /ormic acid [Vol. II], the
aldehyde being among the products ob-
tained by the dry distillation of the
calcium salt (Mulder, Zeit. [2] 4, 26^ ;
Ann. 159, ^66 ; Linnemann, Ann. 157,
119; Lieben and Rossi, Ann. 158, 107).

[H.] From acetic acid [Vol. II] by
incomplete combustion (Mulliken,
Brown, and French, Am. Ch. Journ.
25, III). Or from acetic &nd ffl^collic
acid [Vol. II] ; formic aldehyde is
produced when an electric current is
passed through a solution of potassium
acetate (positive electrode) and potassium
gly collate (negative electrode) (v. Miller
and Hofer, Ber. 27, 467; 28, 2437).
Or by the electrolysis of sodium acetate
in presence of sodium perchlorate (Hofer
and Moest, Ann. 323, 284).

Also from acetic acid through acetyl
cyanide and pyroracemic acid (see under
benzyl alcohol [54 ; l]). The latter, on
heating with acetic anhydride and
sodium acetate at 160-180°, gives a-
crotonic acid (Homolka, Ber. 18, 987),
which can be converted into ^-methyl-
glyceric acid and formic aldehyde as
below under J.

Or from acetic acid and methyl alco-
Jiol [13] through methylglycollic acid
by tne action of chloracetic acid on
sodium methylate (Heintz, Jahresber.
1859, 358). The methylglycollic acid
gives formic aldehyde among the pro-
ducts of electrolysis of the sodium salt
(v. Miller and Hofer, Ber. 27, 469).

Calcium glycoUate on heating with
dilute sulphuric acid at 170-180°, or
the acid itself on heating to 220-240°,

gives ' trioxymethylene ■* (Heintz, Ann.
138, 43 ; Jahresber. 1861, 444), which
is related to formic aldehyde as under D.

Silver glycollate gives formic alde-
hyde when decomposed by iodine (Her-
zog and Leiser, Monats. 22, '^Sl)- C)r
glycollic ester interacts with hydrazine
to form a hydrazide, which by the
action of nitrous acid gives glycolazide
(CH2 [OH] CO . N3) (Curtius and Hei-
denreich, Journ. pr. Ch. [2] 52, 225).
The azide on heating with alcohol
gives glycolurethane, and this by the
action of mineral acid is resolved into
formic aldehyde and other products
(Curtius and Miiller, Ber. 34, 2795).

Or from acetic acid through mono-
chloracetic acid and ^ trioxymethylene/
the latter being among the products
formed by passing the vapour of the
chloro-aeid through a hot tube (Grassi-
Cristaldi, Gazz. 27, 502).

[I.] Lactic acid [Vol. II] gives iodo-
form by the action of iodine and alkali
(Lieben, Ann. Suppl. 7, 218 ; 377), and
this can be converted into methylene
iodide, chloride, methylal, &c., as under D.

Or from lactic acid through pyro-
racemic acid (see under benzyl alcohol
[54; P]), a-crotonic acid, &c., as above
under H, and then as below under J.

Potassium lactate gives crotonic alde-
hyde [102] on electrolysis, the positive
electrode being kept alkaline (v. Miller
and Hofer, Ber. 27, 468). Sarcolactic
acid [Vol. II] also yields crotonic alde-
hyde under these conditions [Ibid.).

[J.] From normal butyric acid [Vol. II]
through a-crotonic acid [54 ; K], a/3-
dibrombutyric acid by bromination
(Korner, Ann. 137, 234 ; Michael and
Norton, Am. Ch. Journ. 2, 12; Ber.
14, 1202 : see also Kolbe, Journ. pr. Ch.
[2] 25, 396), and ^-methylglyceric (a/3-
dihydroxybutyric = 2:3- butanediol-
carboxylic) acid by boiling the latter
with water (Kolbe, loc. cit, 390).
Formic aldehyde is among the products
of the electrolysis of potassium y3-
methylglycerate (Pisarjevsky, Journ.
Russ. Soe. 29, 289).

Crotonic acid also gives ^-methyl-
glyceric acid by oxidation in alkaline
solution with barium permanganate
(Fittig and Kochs, Ann. 268, 8).

173

ALDEHYDES AND KETONES: FATTY GROUP [91J-S.

Or crotonic acid combines with hypo-
bromous acid to form (with a-) some
)8-brom-a-hydroxybutyric acid^ which
on heating with water gives j3-methyl-
glycerie acid (MeUkoff, Ann. 266,, 435 ;
Jom-n. pr. Ch. [a] 61, 554).

Or crotonic acid combines with hypo-
chlorous acid to give a-chlor-^-hydroxy-
butyric acid (Erlenmeyer and Miiller,
Ber. 15, 49 j Melikoff, Ann. 2^4, 198),
which by the action of alcohoKc potash
is converted into /3-methylglycidic acid
(Melikoff, loc. cit. 304). The latter on
heating with water at 100° gives
/3-methylglyceric acid (Ibid. 308 ; and
Ber. 21, 3055), from which formic alde-
hyde can be obtained as above.

Or ;8-methylglycidic acid (potassium
salt) itself can be electrolysed (Pisar-
jevsky, loc. cit.).

[K.] From ^-hyclroxyhutyric acid
[Vol. II] through a-crotonic acid [54 ;
Ii], and then as under J. Crotonic
aldehyde is among the products of
electrolysis of /3-hydroxybutyric acid
(v. Miller and Hofer, Ber. 27, 469).

[L.] From acetoacetic ester [Vol. II]
through a-crotonic acid [54; I], and
then as above.

[M.] From glycerol [48] and hydrogen
cyanide [172] through allyl cyanide
[54 ; P], a^ - dibrombutyronitrile by
bromination, and the acid by hydro-
lysis (Palmer, Am. Ch. Journ. 11, 93).
Subsequent steps as above under J.

Or from glycerol through glyceric
acid and pyroracemie acid [54 ; F],
and then as under H and J. Formic
aldehyde is among the products of
electrolysis of potassium glycerate (v.
Miller and Hofer, Ber. 27, 469). Silver
glycerate gives formic aldehyde on
decomposition by iodine (Herzog and
Leiser, Monats. 22, 357).

Glycerol on electrolysis in dilute
sulphuric acid solution gives 'trioxy-
methylene'' among other products (Re-
nard, Ann. Chim. [5] 17, 331 : see
also Bartoli and Papasogli, Gazz. 13,
387), and then as under D.

Or from glycerol through trimethyl-
ene (see under n-propyl alcohol [15; E]),
which gives formic aldehyde when passed
with air through a red-hot tube (Wolkoff
and Menschutkin, Ber. 31, 3067).

Or from glycerol through allyl alcohol
(see under ethyl alcohol [14 ; G]), the
latter giving acrolein [lOl] and then
formic aldehyde by ^ contact ' oxidation
over heated platinum (Trillat, Comp.
Rend. 123, 833).

[N.] From p-opionic acid [Vol. II]
through pyroracemie acid [54 ; O], and
then as under H, &c.

Or from propionyl chloride and zinc
methyl through tertiary amyl alcohol
(see under aldehyde [92 ; E]). The
latter gives formic aldehyde among the
products formed by passing the vapour
mixed with air over a heated platinum
spiral (Trillat, Comp. Rend. 132, 1495).

[O.] From tartaric or racemic acid
[Vol. II] through pyroracemie acid
[54; N], and then as above. Formic
aldehyde is among the products of
electrolysis of potassium tartrate (v.
Miller and Hofer, Ber. 27, 468).

Or from tartaric acid through di-
hydroxymaleic acid and glycollic alde-
hyde (see under furfural [126 ; E]).
The oxime of the latter on treatment
with acetic anhydride and sodium
acetate gives the acetyl derivative of
the nitrile, and this, on treatment with
ammoniacal silver oxide and distillation
of the product with dilute sulphuric
acid, yields formic aldehyde (Fenton,
Proc. Ch. Soc, 16, 148).

[P.] From allyl isoihiocyanate [16 6]
through allyl cyanide [54 ; J], and
then through a/3-dibrombutyric acid,
&c., as under M.

[Q.] From malonic acid [Vol. II] by
electrolysis of a solution of the potassium
salt (Petersen, Zeit. physik. Ch. 33,

Or from malonic and acetic acids
[Vol. II], and aldehyde [92 : paralde-
hyde] through a-crotonic acid [54; G],
and then as under J.

[B.] From eryfhritol [50] smd formic
acid [Vol. II] through crotonic aldehyde
[102] (see under normal butyl alcohol
[17; I]), and crotonic acid (see also
under benzyl alcohol [54 ; H]), and then
as under J.

[S.] From mannitol [51], ^trioxy-
methylene' being among the products
of its electrolysis in dilute sulphuric
acid solution (Renard, Ann. Chim. [5]

91 S-PP.]

FORMIC ALDEHYDE

irs

17^ 321). Or from mannitol through
n-hexane (n-hexyl alcohol [23 ; B]), and
then as below under V.

Note : — Generators of n-hexane given under
n-liexyl alcohol thus become generators of
formic aldehyde.

[T.] From malic acid [Vol. II].
Crotonic aldehyde is among" the pro-
ducts of electrolysis of sodium malate
(v. Miller and Hofer, Ber. 27, 470),
and can be converted into crotonic acid^
&c., as under P and J.

[U.] Dextrose [154] gives 'trioxy-
methylene' among the products of its
electrolysis in presence of dilute sul-
phuric acid (Renardj Ann. Chim. [5]
17, 321), and this is resolved into
formic aldehyde as under D.

[v.] From n-ptopyl alcohol [15]
through propyl ether (Chancel, Ann.
151, 304 ; Linnemann, Ann. 161, 37 ;
Norton and Prescott, Am. Ch. Journ.
6, 343). The latter gives formic alde-
hyde (trace) by pyrogenic decomposi-
tion (Tistschenko, Journ. Russ. Soc.
31, 784; Ch. Centr. 19CO, 1, 586).

Or the alcohol gives formic aldehyde
(2' 7 2 per cent.) by incomplete com-
bustion (MuUiken, Brown, and French,
Am. Ch. Journ. 25, iii).

Or from n-propyl alcohol through
n-hexane (n-hexyl alcohol [23 ; A]).
The latter when mixed with air and
passed over heated platinum gives
formic aldehyde (v. Stepski, Monats.

23, in)-

Or from normal or isopropyl alcohol
[I6] through propylene, acrolein [lOl]
(see under benzyl alcohol [54; E]),
acrylic, a-chlorlactic, and glyceric acids,
&c., as above under M.

Note : — All generators of propylene thus
become generators of formic aldehyde (see
under isopropyl alcohol [16] and under glycerol
[48] for generators of propylene).

[W.] From acetal [93] through gly-
collic aldehyde (see under furfural
[126 ; P]), and then as above under O.

[X.] From isohuiyl alcohol [I8], being
among the products of slow combustion
of the vapour in contact with heated
platinum (v. Stepski, Monats. 23, 773).

Or from tertiary butyl alcohol [19] by
incomplete combustion (5-17 per cent. :

Mulliken, Brown, and French, Am. Ch.
Journ. 25, iii), or by passing the
vapour mixed with air over a heated
platinum spiral, acetone being simul-
taneously formed (Trillat, Comp. Rend.
132, 1495). _

Or from this last alcohol anidpofassinm
cyanide [172], the alcohol being con-
verted into tertiary butyl iodide and
cyanide, and the latter reduced to tri-
methylethylamine, the hydrochloride of
which gives tertiary amyl alcohol by
the action of silver nitrite (Tissier,
Ann. Chim. [6] 29, '3,'}^$ ; Freund and
Lenze, Ber. 24, 2150). From tertiary
amyl alcohol as above under N.

[Y.] From amyl alcohol [22] through
amylene (trimethylethylene) and tertiary
amyl alcohol (see under acetone [IO6 ;
E]), and then as above under N. Formic
aldehyde (a-oi per cent.) is also formed
by the incomplete combustion of amyl-
ene (Mulliken, Brown, and French,
loc. cit.).

[Z.] From choline [Vol. II] through
glycol [45] and glycollic aldehyde (as
under furfural [l26 ; H ; K]), and then
as above under O.

[AA.] From trimethylamine [Vol. II]
through methyl chloride (see under
methane [l; Z]). From the latter
through methylene chloride, methylal,
&c., as above under C.

[BB.] From acrolein [lOl] through
acrylic acid by oxidation, and from the
latter through a-chlorlactic, oxyacrylic
(glycidic),and glyceric acids to pyrorace-
mic, crotonic, and ^-methylglyceric acids
as above under D and M.

[CO.] From crotonic aldehyde [102]
through crotonic to /3-methylglyceric
acid as above under M, H, and J.

[DD.] From isobutyric and acetic
aldehydes [94 ; 92] through the aldol,
CgHjgOg, trimethylethylene-lactic acid,
and tertiary amyl alcohol (see under
acetone [IO6 ; DD]). From the latter
as above under N.

[EE.] From isobutyric acid [Vol. II]
and acetic aldehyde [92] through tri-
methylethylene-lactic acid (see under
acetone [IO6 ; Kj), and then through
tertiary amyl alcohol, &c., as above.

[PP.] Fentane gives fonnic aldehyde
(o-88 per cent.) among the products of

174 ALDEHYDES AND KETONES: FATTY GROUP [91 FF-92 A.

its incomplete combustion (Mulliken,
Brown, and French, Am. Ch. Journ.
25, III).

Note : — Generators of pentane as given under
n-amyl alcohol [20, B ; C ; D, &c.] are : acetic
acid ; acetone [106j, acetic acid and ethyl alcohol
[14] ; pyridine ; piperidino ; methyl and n-butyl
alcohols [13 ; 17T ; ethyl and n-propyl alcohols [14 ;
15].

Generators of hexane are also generators of
pentane (see under n-amyl alcohol [20 ; G ; H ;
I ; J]). For similar production fromisopentane
see V. Stepski, Monats. 23, 773.

[GrG.] From citric acid [Vol. II]
through acetonedicarboxylic, /i-oxyglu-
taric, vinylacetic, and crotonic acid (see
under n-propyl alcohol [15 ; W]). From
crotonic acid as above under J.

[HH.] Methylamine [Vol. II] gives
the oxime of formic aldehyde among
the products of its oxidation by mono-
persulphuric acid (Bamberger and Selig-
man, Ber. 35, 4299).

92. Acetic Aldehyde ; Acetalde-
hyde ; Ethanal.

CH3
H.C:0

Natural Sources.

A product of the anaerobic fermenta-
tion of sugar (Schutzenberger and
Destrem, Jahresber. 1879, 1007 : see
also Roeser, Ann. Inst. Past. 7, 41).
The production of aldehyde from
sugar by Mucor racemosus was first
observed by Fitz (Ber. 6, 48 : the
mould is erroneously named M. mucedo
in this paper) and by M. clrcellino'ides
by Gay on (Ann. Chim. [5] 14, 285 ;
Comp. Rend. 86, 52 ; Bull. Soe. [2] 31,

139)-

Among the products of the methane

fermentation of cellulose by bacteria
from intestine of oxen (see imder
methane [l]). A product of the al-
coholic fermentation of dextrose and
laevulose by O'idivm albicans (Linossier
and Roux, Comp. Rend. 110, "^SS) 868;
Bull. Soc. [3] 4, 704).

Aldehyde (trace) was found among
the products of fermentation of saccha-

rose by an ellipsoidal yeast (Claudon
and Morin, Comp. Rend. 104, 1109;
Bull. Soc. [2] 49, 178).

Aldehyde is a product of fermentation
by the mould-fungus, Eurotiopsis gayoni
(Duclaux, Journ. Fed. Inst. 6, 412).
This mould can produce aldehyde from
lactic acid when grown in a nutrient
solution containing the acid (Maze,
Comp. Rend. 134, 240 : see also Ann.
Inst. Past. 16, 433) and probably from
dextrose through alcohol {Ibid. Ann.
Inst. Past. 16, 346).

According to Bottinger, aldehyde is
invariably present in fermentation acetic
acid (Ch. Zeit. 24, 793).

Aldehyde is among the products of
fermentation of dextrose by Dunbar's
and other Vibrios (Gosio : quoted by
Emmerling, ' Die Zersetzung stickstoff-
freier organischer Substanzen durch
Bakterien/ pp. 47 and ^6), and of starch
by Bacillus siiaveolens (Sclavo and Gosio,
Bied. Centr. 20, 419; Journ. Ch. Soc.
60, abst. 1284).

Aldehyde occurs in certain brandies,
in the first runnings from the rectifica-
tion of crude spirit, and in certain fusel
oils (see, for instance, Pierre and Puchot,
Ann. 163, 253 ; Kramer and Pinner,
Ber. 2, 403; 4, 787; Kekule, Ber. 4,
718 ; Rabuteau, Comp. Rend. 87, 501 ;
Ordonneau, Comp. Rend. 102, 217;
Allen, Journ. Fed. Inst. 3, 38 and 43).
It is doubtful whether the aldehyde in
these cases is of biochemical origin or
due to secondary oxidation.

Acetic aldehyde occurs in American
oil of peppermint (Power and Kleber,
Pharm. Rund. 12, 157 ; Arch. Pharm.
232, 639 ; Zeit. anal. Ch. 33, 762) and
in the first (aqueous) distillates from
oil of camphor from Lanriis campliora
(Gildemeister and Hoffmann, p. 485},
and from oil of aniseed from PimpiHella
anisum [Ibid. 734).

Synthetical Processes.

[A.] From acetylene (see under
methane [l ; A]), by absorption of this
gas by 1-35 sp. gr. sulphuric acid,
and distillation of the product with
water (Lagermark and Eltekoff, Ber.
10, .637 : see also Zeisel, Ann. 191, 372 ;

92 A-C]

ACETIC ALDEHYDE

175

Erdmann and Kothncr, Zelt. anorg. Ch.
18, 48), or by the action of mercuric
bromide on acetylene and water (Kut-
scheroff, Ber. 14, 1540) ; also by com-
bining- acetylene with mercuric chloride
and decomposing the compound with
dilute hydrochloric acid {Ibid. V7, 13;
Kriiger and Piickert, Ch. Ind. 1895,
p. 454 : see also Travers and Plimpton,
Trans. Ch. Soc. 65, %6^).

Acetylene also combines with mer-
curic nitrate to form a compound which
readily gives aldehyde on decomposition
(Kothner, Inaug. Diss. Halle, 1896;
Erdmann and Kothner, loc. cit. ; Ber.
31, 3475 > ^- ^- Hofmann, Ber. 31,
2212; 2783). Acetylene forms a
compound with mercuric acetate which
decomposes on heating with acids
with the formation of aldehyde (Bur-
kard and Travers, Trans. Ch. Soc. 81,
1271).

Aldehyde is formed when acetylene
is passed through boiling phosphoric
acW (1-15 sp. gr.) or sulphuric acid (30
per cent.) containing mercuric oxide in
suspension (Erdmann and Kothner,
loc. cit.).

Aldehyde is among the products of
oxidation of acetylene by hydrogen
peroxide in presence of ferrous sulphate
(Cross, Bevan, and Heiberg, Ber. 33,
3015).

Acetylene combines with water to
form aldehj'de above 300° (Desgrez,
Ann. Chim. [7] 3, 216).

Or from ethylene by heating with
carbon dioxide at 400° (Schiitzenberger,
Bull. Soc. [2] 31, 482) ; or from ethyl-
ene dibromide and water at 150-160°
(Carius, Ann. 131, 172), or from the
dibromide through vinyl bromide and
the action of mercuric acetate on the
latter (Saytzeff, Zeit. [2] 3, 675 ; Linne-
mann, Ann. 143, 347).

Also from ethylene through glycol [45] .
The latter gives aldehyde when heated
with water to 210° (Nevole, Bull. Soc.
[2] 25, 289), or with zinc chloride
(Wurtz, Ann. 108, 915 : see also Lie-
ben, Monats. 23, 60).

Or ethylene can be combined with
hyi)ochlorous acid to form chlorethyl
alcohol = glycol chlorhydrin (Carius,
Ann. 126, 197), which on treatment with

potassium iodide gives glycol iodhydrin
(Butleroff and Ossokin, Ann. 144, 42).
The latter, on heating with lead hy-
droxide, gives aldehyde quantitatively
(Charon and Paix-Seailles, Comp. Rend.
130, 1407).

Glycol chlorhydrin gives aldehyde
among the products of decomposition
by heating in contact with lead or zinc
oxide. (Kaschirsky, Ber. 10, 1104), or
(in small quantity) by heating with
water (Krassusky, Journ. Russ. Soc. 34,
287). Or the chlorhydrin, on treatment
with potash, gives ethylene oxide
(Wurtz, Ann. Chim. [3] 69, 317 ; Ann.
110, 125; Demole, Ann. 173, 125).
The latter yields aldehyde more readily
than the glycol when heated with zinc
chloride (Krassusky, loc. cit. ^37)'

According to Berthelot, aldehyde is
formed by the oxidation of ethylene
with chromic acid (Comp. Rend. 68,

334)-

The ' ethylenic nitrate ' formed by the
combination of ethylene with nitric an-
hydride gives aldehyde on reduction
(Demjanoff, Ch. Centr. 1899, 1, 1064).

[B.] Methane [l] and carbon mon-
oxide give aldehyde under the influence
of the silent electric discharge (Lo-
sanitsch and Jovitschitsch, Ber. 30,

Ethmie and carbon monoxide also give
aldehyde by this method (De Hemp-
tinne. Bull. Acad. Roy. Belg. [3] 34,
269).

Or from ethane and air by passing
over hot copper or asbestos, &c. (Clock,
Germ. Pat. 109015 of 1899; Ch.
Centr. 1900, 2, 304).

Note : — All generators of ethane (see under
ethyl alcohol [14 ; A ; D, &c.]) thus become
genei'ators of aldehyde.

[C] From ethyl alcohol [l4] by oxida-
tion (Dobereiner, Gmelin's ' Handbuch
d. org. Ch.' IV, 55^ ; 585 ^ 61 1 ; Liebig,
Ann. 14, 133 ; W. and R. Rodgers,
Journ. pr. Ch. 40, 240 ; Stadeler, Ibid.
76, 54 : for conditions determining the
electrolytic oxidation of alcohol to alde-
hyde see Dony-Henault, Zeit. Elektrocli.

Or from ethyl alcohol through its

176

ALDEHYDES AND KETONES: FATTY GROUP [92 C-P.

ether, the latter giving acetaldehyde
among the products of its photochemical
oxidation (Bertbelot, Comp. Rend. 129,
627), or by passing through a hot tube
(Liebig, Ann. 14, 134; Tistschenko,
Journ. Russ. Soc. 31, 784; Ch. Centr.
1900, 1, 586).

From alcohol by chemical, aided by
electrolytic, oxidation (Dai*mstadter,
Germ. Pat. 109012 of 1897; Ch.
Centr. 1900, 2, 151); or by electrolysis
in presence of sulphuric acid (Elbs and
Brunner, Zeit. Elektroch. 6, 604).
Among the products of photo-oxidation
of alcohol by ferric chloride (De Coninck,
Comp. Rend. 131, 375), and among the
products of pyi'ogenic decomposition
(Ipatieff, Ber. 34, 598): the yield is in-
creased by the pyrogenic ' contact '
influence of certain metals, such as iron
or zinc, &c., or certain metallic oxides
{Ihld. 34, 3579 ; 35, 1047).

Ethyl alcohol is oxidised to aldehyde
by quinones, ketones, benzaldehyde, and
anisaldehyde in presence of light (Ciami-
cian and Silber, Ber. 34, 1530)'

Magnesium ethylate gives aldehyde
when acted upon by dry chlorine (Meu-
nier, Comp. Rend. 134, 472).

Ethyl hypochlorite decomposes spon-
taneously into aldehyde and hydrogen
chloride (Schmitt and Goldberg, Journ.
pr. Ch. [2] 19, 393 ; 24, 106).

[D.] From formic and acetic acids
[Vol. II] by distilling a mixture of the
dry calcium salts (Ritter, Ann. 97,

369)-

Or from acetic acid through acetyl

cyanide and pyroracemic acid (see under

benzyl alcohol [54; l]), and then as

below under E.

Formylacetic ethyl ester (see under
cymene [6 ; IX]), when boiled with di-
lute sulphuric acid, gives aldehyde
among other products (Wislicenus and
Bindemann, Ann. 316, 18).

[E.] From propionic acid [Vol. II],
being among the products of electrolysis
of sodium propionate in presence of
sodium perchlorate (Ilofer and Moest,
Ann. 323, 284).

Or from propionic acid through
ethane by photochemical decomposition
in presence of uranium salts, or through
ethylene by electrolysis (see under

ethyl alcohol [14; H]). Ethane yields
aldehyde as under B, and ethylene as
under A.

Or from propionic acid and methyl
alcohol [13] through tertiary amyl al-
cohol by the interaction of proj)ionyl
chloride and zinc methyl (Popoff, Ann.
145, 293 ; Jermolajeff, Zeit. [2] 7, 275 ;
Wischnegradsky, Ann. 190, 336), the
corresponding iodide, and amylene (tri-
methylethylene) by the action of alco-
holic potash on the latter. According to
Wagner (Ber. 21, 1235), acetic aldehyde
is among the products of oxidation of
this amylene.

Or from propionic acid through the
a-bromo-acid by bromination (Friedel
and Machuca, Comp. Rend. 53, 408 ;
Ann. 120, 286; Bischoff, Ann. 206,
319; Zelinsky, Ber. 20, 2026 ; Michael
and Graves, Ber. 34, 4044), the a-cyano-
acid by the action of potassium cyanide
[172], and hydrolysis of the latter to iso-
succinic (methylmalonic) acid (Wichel-
haus, Zeit. [2] 3, 247 ; Byk, Journ.
pr. Ch. [2] 1, T9; Cohn, Ann. 251,
'^'>iS'} Pusch, Arch. Pharm. 232, 188).
Acetic aldehyde (trace) is among the
products of electrolysis of the potassium
salt of this latter acid (Petersen, Ch.
Centr. 1897, 2, 519; Zeit. physik. Ch.
33, 702).

Or from propionic acid through pyro-
racemic acid (see under benzyl alcohol
[54; O]). The latter, on heating with
dilute sulphuric acid at 150°, gives
aldehyde (Beilstein and Wiegand, Ber.
17, 840). Pyroracemic acid also yields
aldehyde among the products of its
electrolytic oxidation (Rockwell, Journ.
Am. Ch. Soc. 24, 719).

Or a/3-dibrompropionic acid can be
converted into acrylic acid by treatment
with zinc and sulphuric acid (Caspary
and Tollens, Ann. 167, 241 ; Melikoff,
Journ. Russ. Soc. 13, 156), and the
latter into /3-chlorlactic acid by the
addition of hypochlorous acid (Melikoff
loc. cit. 157). ^-Chlorlactic acid gives
aldehyde on heating with water, or by
boiling a strong solution of the sodium
salt (Erlenmeyer, Ber. 13, 309 ; Reisse,
Ann. 257, S?>l)-

[F.] From malonic acid [Vol. II],
methyl and ethyl alcohols [13 ; 14],

82 P-J.]

ACETIC ALDEHYDE

177

through isosuccinic (methylmalonic)
acid by the action of methyl iodide on
sodiomalonie ester (Ziiblin, Ber. 12,
1 1 1 2), and then as above under E.

Or from malonic acid through ethyl-
ene by electrolysis (see under ethyl
alcohol [14 j W]), and then as above
under A.

[G.] From succinic acid [Vol. II]
through ethylene by electrolysis [14 ;
X], and then as under A.

Or through dibromsuccinic acid by
bromination (Kekule, Ann. 117, 1 23 ;
Suppl. 1, 131 : see also under methane
[1 ; T]), and the action of boiling water
on the dibromo-acid or its salts (Lossen
and Riebensahm, Ann.292,295; Lessen^
Ann. 300; I; Lossen and Reisch,

md. 5).

Aldehyde is among the products of
electrolysis of potassium succinate (Peter-
sen, Zeit. physik. Ch. 33, 711).

Or from succinic acid through acetyl-
enediearboxylic acid (see under methane
[1 j T]). The latter gives aldehyde (and
paraldehyde) on heating with water to
300° (DesgreZ; Ann. Chim. [7] 3,
219).

[H.] From lachc acid [Vol. II] by
oxidation with various oxidising com-
pounds (Liebig; Stadeler,Ann,69, 332),
or by heating with dilute sulphuric
acid at 130° (Erlenmeyer, Zeit. [2] 4,
343). Also by electrolysis of a strong
solution of the potassium salt (Kolbe,
Ann. 113, 244; Brester, Zeit. [2] 2,
680; V. Miller and Hofer, Ber. 27,
468), or by the action of iodine on the
silver salt (Herzog and Leiser, Monats.

22, 357)-

Also from lactic acid through pyro-
racemic acid (see under benzyl alcohol
[54; P]), and then as under E.

Or lactic ester can be converted into
lactic hydrazide by the action of hydra-
zine, and the hydrazide into the azide
by nitrous acid. The azide hydrolyses
to acetic aldehyde, &c. (Curtius and
Aufhauser, Ber. 34, 2796).

Sarcolactic acid [Vol. II] gives acetic
aldehyde under similar conditions to
those which give rise to this aldehyde
from ordinary lactic acid (for electro-
lysis see v. Miller and Hofer, loc. cit.).

[I.] From tartaric or raeemic acid

EVol. II] through pyroracemic acid
54 ; N], and then as under E.
Aldehyde is among the products of the
distillation of tartaric acid (Volckel,
Ann. 89, 57).

[J.] From glycerol [48] through
glyceric acid and pyroracemic acid
[54 ; F], and then as under E.

Or from glycerol and potassitim
cyanide [l72] through allyl cyanide
[54; F] and ^-methylglyceric acid
(see under formic aldehyde [91 ; M and
J]). Acetic aldehyde is among the
products of electrolysis of potassium
iS-methylglycerate (Pisarjevsky, Journ.
Buss. Soc. 29, 289).

Or glycerol may be converted into
acrolein [lOl] by dehydration (Redten-
bacher, Ann. 47, 1 20 ; Geuther and
Cartmell, Ann. 112, 2 ; Hiibner, Arm,
114, -3^^ ; Van Romburgh, Bull. Soc. [2]
36, 549 ; Wagner, Journ. Russ. Soc.
16, 317 ; Griner, Ann. Chim. [6] 26,
367; AronsteiUj Ann. Suppl. 3, 180;
Fischer, Ber. 20, 3388; Wohl and
Neuberg, Ber. 32, 1352 ; Wohlk, Journ.
pr. Ch. [2] 61, 2CO), acrylic acid by
oxidation of the latter (Redtenbacher,^oc.
cit. 125; Claus, Ann. Suppl. 2, 123),
and ^-chlorlactic acid by the addition
of hypochlorous acid to acrylic acid
(Melikoff, Journ. Russ. Soc. 13, 157).
^-Chlorlactic acid gives aldehyde as
above under E.

Or acrolein and etkyl alcohol [14] com-
bine under the influence of hydrogen
chloride to form /3-chlorpropionacetal
(Wohl, Ber. 21,61 8; 31,1796). The latter
is converted by the action of alkali into
the ^-hydroxy-acetal, and this by oxida-
tion with potassium permanganate gives
^-diethoxypropionic acid. The latter,
on heating with dilute sulphuric acid at
50°, yields the semi-aldehyde of malonic
acid, which is resolved above 50°
into carbon dioxide and acetic alde-
hyde (Wohl and Emmerich, Ber. 33,
2760).

Or from glycerol through glyceric
acid, a-chlorlactic acid by the action of
hydrochloric acid on the latter (Werigo
and Melikoff, Ber. 12, 178), oxyacrylie
(glycidic) acid by the action of alcoholic
potash (Melikoff, Ber. 13, 271 ; Journ.
Russ. Soc. 13, 211), /3-chlorlactic acid

178

ALDEHYDES AND KETONES: FATTY GROUP [92 J-L.

by addition of hydrogen chloride {Ibid.
Journ. Russ. Soe. 13^ I57); ^"^^ iheo. as
above.

Glycerol may also be converted into
a-chlorlactic acid through a/3-dichlor-
propyl alcohol by the action of chlorine
on allyl alcohol (Tollens, Ann, 156,
164; Hiibner and Miiller, Ann. 159,
168), by the addition of hypochlorous
acid to allyl chloride (v. Gegerfeldt,
Ann. 154, 247 ; Ber, 6, 720 ; Henry,
Ber, 3, ^^2 ; 7, 414), or by the direct
action of dry hydrogen chloride (Faucon-
nier and Sanson, Bull. Soc. [2] 48, 236).
The a^-dichlorpropyl alcohol gives a/3-
dichlorpropionic acid on oxidation
(Henry, Ber. 7, 414; Werigo and
Melikoff, Ber, 10, 1500), and the latter
yields a-chlorlactic acid by the action of
water (Melikoff, Ber, 12, 2227),

Or glyceric acid may be converted
into /3-iodopropionic acid by the action
of phosphorus iodide (Beilstein, Ann,
120, 226 ; 122, 366 ; Erlenmeyer, Ann.
191, 284; Meyer, Ber. 19, 3294; 21,
24). The iodo-acid gives acrylic acid
by the action of alcoholic potash, or by
heating with lead oxide (Schneider and
Erlenmeyer, Ber. 3, 339 ; Wislicenus,
Ann, 166, 2), and this can be converted
into ^-chlorlactic acid and aldehyde as
above.

Or from glycerol through a-epichlor-
hydrin by the action of phosphorus
pentaehloride, or by the action of hydro-
chloric acid or alkali on dichloi'hydrin
(Berthelot, Ann, Chim. [3] 41, 299 ;
Reboul, Ann, Suppl, 1, 221 ; Prevost,
Journ, pr. Ch. [2] 12, 160 ; Fauconnier,
Bull. Soc. [2] 50, 213). Epichlorhydrin
on oxidation with nitric acid gives
/3-chlorlactic acid (Richter, Journ. pr.
Ch. [2] 20, 193), from which aldehyde
can be obtained as above.

Acetic aldehyde is among the pro-
ducts of the dry distillation of the
calcium derivative of glycerol (Destrem,
Ann, Chim. [5] 27, 20).

[K.] From normal huti/ric acid [Vol, II]
through a-crotonic acid (see under benzyl
alcohol [54 ; K]), and /3-raethylglyceric
= a/3 -dihydroxy butyric acid (see under
formic aldehyde [91 ; J]), and then as
above under J.

Or a-crotonic acid gives aldehyde

directly by oxidation with chromic acid
mixture (Kekule, Ann, 162, 315).

Or from isohidyric acid [Vol. II]
through a-hydroxyisobutyric = 2-me-
thyl-2-propanolic acid by oxidation
with potassium permanganate (Meyer,
Ann, 219, 240), The acid gives alde-
hyde among other products by the
action of heat or dehydrating agents
(Scholtz, ^Der Einfluss der Raumerfiil-
lung der Atomgruppen auf den Verlauf
chemischer Reaktionen,' 1899, p. '>fi'i^',
Bischoff and Walden, Ann. 279, ill).

Or isobutyric acid can be brominated
(Markownikoff, Ann. 153, 229 ; Hell
and Waldbauer, Ber. 10, 448), the
a-bromo-acid converted into the hydroxy-
acid by treatment with barium hy-
droxide or sodium carbonate solution
(Markownikoff, loc. cit.; Fittig, Ann,
200, 70), and then as above.

Or isobutyric acid (or chloride) on
chlorination gives, with other products,
a-chlorisobutyric acid (Balbiano, Ber.
11, 1693 ; Michael and Garner, Ber. 34,
4054), and this yields the hydroxy-acid
on heating with water at 180° (Ostrop-
jatoff, Journ. Russ. Soc. 28, 51).

[L.] From acctoacetic ester [Vol. II]
through a-crotonic acid (see under
benzyl alcohol [54 ; l]), or through
/3-methylglyceric acid (see under formic
aldehyde [91 ', L and J]), and then as
above under J and K.

Or acctoacetic ester may be con-
verted into its methylpropyl-derivative
by the alternate introduction of methyl
and propyl by the action of the alkyl
iodides on sodio-acetoacetic ester (Lie-
bermann and Kleemann, Ber. 17, 918;
Jones, Ann. 226, 287). Methylpropyl-
acetoacetic ester on reduction with
sodium amalgam gives a-methylpropyl-
/3-hydroxybutyric (3-methyl-2-hexanol-
3-carboxylic) acid (Jones, loc. cit. 288),
and this on dry distillation breaks down
into acetic aldehyde and methylpropyl-
acetic acid.

Or instead of methyl and propyl two
other alkyls may be introduced into
acctoacetic ester, such as two ethyls,
giving rise to a-diethyl-,8-hydroxy-
butyric (3-ethyl-2-pentanol-3-carboxy-
lic) acid by reduction with sodium amal-
gam as above (Schnapp, Ann. 201, 6<).

92 L-S.]

ACETIC ALDEHYDE

179

This acid on dry distillation also breaks
down into acetaldehyde and diethyl-
acetic acid.

Note : — This synthesis of aldehyde from dial-
kyl-/3-hydroxybutyric acids is general what-
ever the alkyls may be (Reformatsky, Journ.
pr. Ch. [2] 54, 477).

Or from acetoaeetic ester through
' oxymesitenedicarbonic ' acid and its an-
hydride (lactone) which is formed by the
action of hydrochloric or sulphuric acid
on the ester (Duisberg-, Ann. 213, 177 j
Polonowska, Ber. 19, 2403 j Anschiitz,
Bendix, and Kerp, Ann. 259, 153).
The lactone on distillation with lime
gives mesityl oxide (Hantzsch, Ann.
222, 21), and this can be converted
into hydroxyisobutyric acid as below
under S, and aldehyde as above under K.

[M.] From ^-hyclroxylutyric acid
[Vol. II] through a-crotonic acid (see
under benzyl alcohol [54; L]), or
through /3-methylglyceric acid (see
under formic aldehyde [91 ; K]), and
then as under J and K.

[N.] From erythritol [50] a,ndfonnic
acid [Vol. II] through a-crotonic alde-
hyde [102] and acid, or through ^-methyl-
glyceric acid (see under formic aldehyde
[91 ; B]), and then as under J and K.

[O] From allyl isothiocyanate [166]
through ^-methylglyceric acid [91;
P], and then as under J.

[P.] From fumaric or maleic acids
[Vol. II] through acetylene (see under
methane [l ; U]), and then as above
under A.

Or from fumaric acid through di-
bromsuccinie acid by the addition of
bromine (Kekule, Ann. 117, 123;
Suppl. 1, 131 ; Baeyer, Ber. 18, 676),
and then as under G.

Or from maleic acid through iso-
dibromsuccinic acid by the addition of
bromine (Kekule, Ann. Suppl. 2, 89),
and decomposition of the isodibrom-
suceinafces by boiling with water (Lossen
and Reisch, Ann. 300, .5).

[Q.] From malic acid [Vol. II], being
formed in small quantity by the electro-
lysis of a strong solution of the potas-
sium or sodium salt (Bourgoin, Bull.
Soc. [2] 9, 427 ; v. Miller and Hofer,
Ber. 27, 470).

Also by boiling the aqueous solution
of the acid with manganese dioxide
(Liebig, Ann. 113, 14), by heating with
dilute sulphuric acid at 135° (Weith,
Ber. 10, 1744), or by oxidation with
potassium permanganate (Denig^s,
Comp. Rend. 130, 32).

[B.] Tiglic acid [Vol. II] gives alde-
hyde on oxidation with potassium
permanganate (Beilstein and Wiegand,
Ber. 17, 2262).

[S.] From acetone [IO6] through the
dibromide or diiodo-derivative (see under
glycerol [48 ; E]), acrolein [lOl], acrylic
acid, /3-chlorlactic acid, &c., as above
under J.

Or from acetone and hydrogen cyanide
[172], which condense in the presence
of hydrochloric acid to form hydroxy-
isobutyric acid (Staedeler, Ann. Ill,
320; Markownikoff, Ann. 146, 339).
The latter gives aldehyde as above
under K.

Or from acetone and chloroform[l; D],
which condense in the presence of caus-
tic alkali to form ' acetone-chloroform '
(see under tertiary butyl alcohol [19 ;
D]). The latter gives hydroxyiso-
butyric acid on heating with water or
dilute alkali (Willgerodt, Ber. 15, 2307 ;
Willgerodt and Schiff, Journ. pr. Ch.
[2] 41, 519).

Acetone by the action of sulphuric
acid, of lime, or of hydrogen chloride
followed by caustic alkali or water
gives mesityl oxide = 2-methyl-2-
pentenone-4 (Kane, Phil. Trans. 44,
475 ; Fittig, Ann. 110, 32 ; Kasanzeff,
Journ. Russ. Soc. 7, 173; Baeyer,
Ann. 140, 297 ; Claisen, Ann. 180, 4 j
Freer and Lachman, Am. Ch. Journ.
19, 887, note). Or mesityl oxide results
from the action of zinc methyl or ethyl
(Pawloff, Ber. 9, 1311; Ann. 188,
130), or of acetyl chloride on acetone
(Beilstein and Wiegand, Bull. Soc. [2]
38, 167). Mesityl oxide gives hydroxy-
isobutyric acid on oxidation with potas-
sium permanganate (Pinner, Ber. 15,

591)-

Acetone and ammonia condense in
the presence of acids to form diaceton-
amine (Heintz, Ann. 174, 154; 189,
214). The latter (or its salts) gives
mesityl oxide on dry distillation (Soko-

n2

180

ALDEHYDES AND KETONES : FATTY GROUP [92 S-CC.

loff and Latschinoff, Ber, 7, 1387;
1777; Heintz, Ann. 174, 156; 175,
252 ; 181, 70).

Diacetonamine salts also give mesityl
oxide (with diaeetone alcohol) on treat-
ment with potassium nitrite (Sokoloff
and Latschinoff, loc. cit. ; Heintz, Ann.
178, 342). Diaeetone alcohol also gives
mesityl oxide on treatment with strong
sulphuric acid (Heintz, Ann. 178, 351).

Or diacetonamine on oxidation with
chromic acid mixture gives a-aminoiso-
butyric acid (Heintz, Ann. 198, 46),
and this yields hydroxyisobutyric acid by
the action of nitrous acid (Tiemann and
Friedlander, Ber. 14, 1973), from which
aldehyde can be obtained as under K.

[T.] Dextrose [154] gives acetic alde-
hyde among other products on oxidation
with sulphuric acid and manganese
dioxide (Liebig, Ann. 113, 16).

'Invert sugar' (dextrose and Iffivu-
lose) gives this aldehyde on electrolysis
of the aqueous solution in presence of
sulphuric acid (H. T. Brown, Journ. Ch.
Soc. 25, 578).

[IT.] Ethylamhie [Vol. II] gives alde-
hyde among other products on oxidation
with chromic acid mixture (Wanklyn
and Chapman, Journ. Ch. Soc. 20,
328), and the oxime of the aldehyde
among the products of oxidation by
monopersulphuric acid (Bamberger, Ber.

35, 4293)-

[v.] Alanine [Vol. II] gives aldehyde
on boiling its aqueous solution with
lead peroxide, on heating ^jer se, or on
heating with strong phosphoric acid
solution at 220° (Drechsel, Ber. 25,

3503)-

[W.] Choline [Vol. II] on boiling in

concentrated aqueous solution gives

glycol [45] and trimethylamine. From

the former aldehyde can be obtained as

under A.

[X.] Furfural [126] on oxidation

gives pyromucie acid (Schwanert, Ann.

114, 63 ; 116, 257 ; Volhard, Ann. 261,

379), which on heating with bromine

at ]CO° yields 8-brompyromueic acid

(Hill and Sanger, Ann. 232, 46 ; Ber.

16, 1 130). The latter on heating with

bromine and water gives isodibrom-

succinic acid (H. and S. Ann, 232, ^"^y

which yields aldehyde as under P.

[Y.] Citral [l04] on boiling with
dilute alkali gives (with methylhepte-
none) acetaldehyde (Verley, Bull. Soc.
[3] 17, 175)-

[Z.] From citric acid [Vol. II]
through acetonedicarboxylic acid (see
under orcinol [75 ; C]). The latter by
the action of strong sulphuric acid
yields citracoumalic acid (Nieme and v.
Pechmann, Ann. 261, 199), and this
on heating at 200° gives the lactone
of mesitenecarbonic acid {llnd. 202),
from which mesityl oxide can be
obtained as under L, hydroxyisobutyric
acid as under S, and aldehyde as
under K.

Or from acetonedicarboxylic acid
through /3-oxyglutaric, vinylacetic, and
crotonic acid (see under n-propyl alco-
hol [15 ; W]), and then as above
under K.

[AA.] From amyl alcohol from fusel
oil [22] through amylene = trimethyl-
ethylene (Balard, Ann. Chim. [3] 12,
320 ; Frankland, Journ. Ch. Soc. 3,
^^ ; Wurtz, Bull. Soc. 5, 301), tri-
methylethylene bromide, and glycol (see
under acetone [1O6 ; E]). The latter
gives hydroxyisobutyric acid on oxida-
tion with nitric acid (Wurtz, Ann.
107, 197)- Subsequent treatment as
under K.

Aldehyde is among the products of
oxidation of this amylene by potassium
permanganate, the glycol being formed
as an intermediate product (Wagner,
Ber. 21, 1235).

Or from isoamyl alcohol through the
iodide, which gives secondary pentane
(4-methylbutane) on heating with zinc
and water (Frankland, Ann. 74, ^^).
The pentane gives hydroxyisobutyric
acid among the products of the action
of nitric acid (Poni, Ch. Centr. 1902,
2, 16).

[BB.] From oxalic acid [Vol. II] and
methyl alcohol [13] through hydroxyiso-
butyric acid (see under acetone [IO6 ;
O]), and then as above under K.

[CC] From methyl alcohol [l3],
acetic aldehyde being among the pro-
ducts obtained by heating aluminium
methylate (Tistschenko, Journ. Buss.
Soc. 31, 784; Ch. Centr. 1900, 1,
585).

92 CC-94.]

ACETIC ALDEHYDE

181

Or from methyl alcohol throug^h
ethane (see under ethyl alcohol [14 ; D]),
and then as above under B.

[DD.] Jsobutijlene glycol [47] on treat-
ment with hydrochloric acid gives a
chlorhydrin which, on oxidation with
nitric acid, yields a-chlorisobutyric acid
(Henry, Bull. Soc. [2] 26, 24). From
the latter through a-hydroxyisobutyric
acid as above under K.

[EE.] Methjl'isoeugenol [8O] gives
aldehyde among the products of oxida-
tion by potassium permanganate (Kolo-
koloff, Journ. Russ. Soc. 29, 23; Ch.
Centr. 1897, 1, 915).

[FP.] From uobutyl alcohol [18], or
tertiary butyl alcoJiol [l9], through iso-
butylene [18; A; 19; B] and acetic
acid [Vol. II]. Isobutylene and acetyl
chloride or acetic anhydride condense in
presence of zinc chloride to form mesityl
oxide (Kondakoff, Journ. Russ. Soc. 26,
12; 232). Subsequent treatment as
above under S, &c.

Note : — Generators of isobutylene are given
under isobutyl alcohol [18 ; B ; C] and under
butyric aldehyde below [94],

93. Acetal ; Ethylidenediethyl Ether.
CH3.CH(O.C2H,),

Natural Sources.

Occurs in raw spirit after filtration
through animal charcoal (Geuther, Ann.
126, 63) ; also in fusel oil of whisky
(Allen, Journ. Fed. Inst. 3, 38). Has
been found in forerunnings from spirit
rectification (Kramer and Pinner, Ber.
2, 402; 4, 788; Kekule, Ber. 4, 719).

It is doubtful whether the acetal is
a biochemical product or due to secon-
dary reactions.

Synthetical Processes.

[A.] From ethyl alcohol [14] by
oxidation (Dobereiner, Gmelin^s Handb.
d. org. Ch. IV, 805 ; Liebig, Ann. 5, 25 ;
14, 156; Stas, Ann. Chim. [3] 19,
146 ; Wurtz, Ibid. 48, 370 ; Ann. 108,
84). By electrolysis (Renard, Ber. 8,
132).

[B.] From aldehyde [92] and ethyl
alcohol [14] by passing hydrogen
chloride into a mixture, and acting on
the monochlorethyl ether (CH3 . CHCl .
OCgHg) thus formed with sodium ethyl-
ate (Wurtz and FrapoUi, Comp. Rend.
47, 418; Ann. 108, 223). Or by
passing hydrogen chloride into a mixture
of alcohol and aldehyde, and allowing
to interact at ordinary temperatures
(Fischer and Giebe, Ber. 30, 3053).

Also by converting aldehyde into
ethylidene dibromide by the action of
phosphorus pentabromide, and the
interaction of the dibromide with so-
dium ethylate (W. and F., loc. cit.).

Or from aldehyde by heating with
alcohol and acetic acid at 100° (Geuther,
Ann. 126, 60:,), or by passing hydrogen
phosphide into a cold mixture of alde-
hyde and absolute alcohol (Engel and
Girard, Comp, Rend. 91, 692 ; Jahres-
ber. 1880, 694).

Also from aldehyde through a-chlor-
ethyl acetate (Wurtz, Ann. 102, 94),
or by the action of acetyl chloride on
aldehyde (Simpson, Ann. 109, 156).
By the action of bromine at 100-103"
a-chlorethyl acetate gives bromethyl
bromacetate (Kessel, IBer. 10, 1994 ;
11, 1916), and the latter (CH.,Br. CO.
O . CHBr . CH.,), when heated with
alcohol, yields acetal among other pro-
ducts {Ibid. 11, 1 91 8).

Hydrogen chloride passed into a cooled
mixture of alcohol and hydrogen cyanide
[172] gives formimino-ethyl ether (Pin-
ner, Ber. 16, 354, 1644). The hydro-
chloride of the latter interacts with
acetic aldehyde to form acetal (Claisen,
Ber. 31, 1014).

Acetal is best prepared by acting on
aldehyde with a i per cent, solution of
hydrogen chloride in alcohol (Fischer
and Giebe, loc. cit.).

94. Butyric Aldehyde ; Butanal.
CgH^ . CHO

Natural Sources.

A butyric aldehyde is said to occur
in the oil of Eucalyptus globulus and in
oil of cajeput from Melaleuca lencaden-

182

ALDEHYDES AND KETONES: FATTY GROUP

[94-E

dron (Voiiy, Bull. Soc. [a] 40, io6 ;
50, io8 ; Comp. Rend. 106, 1419;
1538). A butyric aldehyde occurs in
rancid fat, probably a bacterial product
(Nagel, Am. Ch. Journ. 23, 173).

Synthetical Processes.

The constitution of the natural pro-
duct has not been determined, so the
synthetical methods for both normal
and iso-aldehydes are given : —

[A.] Butyric Sind formic acids [Vol.
II] give the n-aldehyde on distilling
a mixture of the dry calcium salts (Lie-
ben and Rossi, Ann. 158, 146; Linne-
mann, Ann. 161, 186 ; Lipp, Ann. 211,
355 i Kahn, Ber. 18, 3364).

Or n-butyric acid can be converted
into the chloride, and the latter reduced
in moist ethereal solution with sodium
amalgam (W. H. Perkin, junr., and
Sudborough, Proc. Ch. Soc. 10, 216).

[B.] Isohutyric acid [Vol. II] gives
the iso-aldehyde by distilling the cal-
cium salt jDf?/* se^ or with calcimn formate
[Vol. II] (Popoff, Ber. 6, ).i^^ ; Bar-
baglia and Gucci, Ber. 13, 1572 ; Linne-
mann and Zotta, Ann. 162, 7).

[C] Isobutyl alcohol [I8] gives the
iso-aldehyde on oxidation with chromic
acid mixture (Pfeiffer, Ber. 6, 699 ;
Michaelson, Ann. 133, 182; Pierre and
Puchot, Comp. Rend. 70, 434 ; Lipp,
Ann. 205, 2; Fossek, Monats. 2, 614;
W. H. Perkin, junr.. Trans. Ch. Soc.
43, 91). Also by pyrogenic decomposi-
tion (Ipatieff, Ber. 34, 598) ; especially
by the contact action of certain heated
metals {Ibid. 35, 1052), or by passing
the vapour mixed with air over heated
platinum (v. Stepski, Monats. 23, 773).

Isobutyl hypochlorite is decomposed
by hydrochloric acid with the formation
of isobutyric aldehyde (Tiesenhold :
Krassusky, Journ. Russ. Soc. 34, S5^)-

[D.] Tertiary butyl alcohol [l9] can
be converted into isobutylene by acting
on the iodide with alcoholic potash, or
on the alcohol with sulphuric acid or
zinc chloride (Wurtz, Ann. 93, 107;
De Luynes, Comp. Rend. 56, 1175;
ButlerofP, Ann. 144, 1 9 ; Zeit. [2] 6,
236 ; Konowaloff, Bull. Soc. [2] 34,
333; Nevole, Bull. Soc. [2] 24, i22j

Lermontoff, Ann. 196, 117; Puchot,
Ann. Chim. [5] 28, 508 ; Scheschukoff,
Bull. Soc. [2] 45, 181). Isobutylene
bromide, when heated with water at
160°, gives isobutyric aldehyde (Linne-
mann and Zotta, Ann. 162, '^6).

Or from isobutylene through the
chlorhydrin, which gives isobutyric
aldehyde on heating with water or by
passing over heated zinc oxide (Kras-
susky, Journ. Russ. Soc. 34, 287). Iso-
butylene oxide (from the chlorhydrin)
gives the aldehyde when heated with
zinc chloride {Ibid. 537).

Or isobutylene by chlorination gives
(with an isomeride) isobutenyl chloride =
2-methyl-3-chlorpropylene (Scheschu-
koff, Journ. Russ. Soc. 16, 495), which,
by potassium carbonate and water, is
converted into isopropenyl carbinol
= I -hydroxy- 2-methylpropylene {Ibid.
499). The latter, on heating with water
acidified with sulphuric acid, gives iso-
butyric aldehyde {Ibid. 502).

[E.] Isovaleric acid [Vol. II] gives
isobutylene among the products of the
electrolysis of a strong solution of the
potassium salt (Kolbe, Ann. 69, 259),
and this can be converted into isobutyric
aldehyde as above under D.

Or from isovaleric acid through ^-
dimethylacrylic acid and isobutylene
(see under isobutyl alcohol [I8 ; C]).

Or /3-dimethylacrylic ester on nitra-
tion gives an a-nitro-derivative (Bou-
veault and Wahl, Comp. Rend. 131, 687),
which, on reduction by sodium in moist
ether, or by heating with sodium hy-
droxide solution, yields nitroisobutylene
{Ibid. 1 211). The latter, on reduction
with aluminium amalgam or zinc dust
and acetic acid, gives the oxime of iso-
butyric aldehyde, from which the alde-
hyde can be obtained by hydrolysis
{Ibid. 134, 1 145).

Note : — Other generators of /3-dimethylacrylic
acid given under isobutyl alcohol are acetoyie
[106] and glycerol [48], or acetone, malonic acid,
and acetic anhydride.

Or isovaleric acid can be brominated
or chlorinated (Cahours, Ann. Suppl.
2, 78 j Borodin, Ann. 119, 121 ; Fittig
and Clark, Ann. 139, 199; Ley and
Popoff, Ann. 174, 6g ; Schmidt, Ann.

84E-95/B.]

BUTYRIC ALDEHYDE

183

193, 104; Schlebusch, Ann. 141, 322),
and the a-halo-acid converted into a-
hydroxy isovaleric acid = 2 - methyl - 3 -
butanolic-4-acid (Fittig and Clark,
Ann. 139, 206 ; Schmidt and Sacht-
leben, Ann. 193, 106; Schlebusch, ^oc.
ciL). The latter gives isobutyric alde-
hyde on heating with acids, or by oxida-
tion with chromic acid mixture (Ley
and PopofP, loc. cif. ; Ley, Journ. Euss.
Soc. 9, 131), or with lead peroxide and
phosphoric acid (v. Baeyer and H. v.
Liebig, Ber. 31, 21 10).

[F.] Le?tci?ie [Vol. II], on distillation
with water and lead peroxide, gives
butyric aldehyde (? normal : Liebig,
Ann. 70, 313).

[G.] From glycerol [48] and acetone
[loe] through dimethylallyl carbinol,
^-hydroxyiso valeric acid, ^-dimethyl-
acrylic acid, and isobutylene or nitro-
isobutylene (see under isobutyl alcohol
[18 ; D]), and then as above under D
or E.

[H.] From isoamyl alcohol [22]. Iso-
butylene is among the products formed
when the vapour of fusel oil is passed
through a hot tube (Wurtz, Ann. 104,
249 ; Butlerolf, Ann. 145, 277 ; Ipatieff,
Ber. 35, 1053).

Or from amyl alcohol through aniyl-
ene (isopropylethylene) (Eltekoff, Ber.
10, 1904; Wischnegradsky, Ann. 190,
358). Isobutyric aldehyde is among
the products of oxidation of this amyl-
ene by potassium permanganate (Wag-
ner, Ber, 21, 1233).

[I.] From oxalic acid [Vol. II], ethyl
alcohol [14], and isojjropyl alcohol [I6],
through a-hydroxyisovaleric acid by the
action of zinc on a mixture of oxalic
diethylester and isopropyl iodide, and
hydrolysis of the ester thus formed
(Markownikoff, Zeit. [2] 6, 517). Sub-
sequent steps as under E above.

[J.] From crotonic aldehyde [102],
n-butyric aldehyde being among the
products of reduction (Lieben and
Zeisel, Monats. 1, 825 ; Charon, Ann.
Chim. [7] 17, 223).

[K.] Isobutylene glycol [47] gives iso-
butyric aldehyde on heating with water
to 180-200° (Nevolcj Ber. 9, 448).

95. Valeric Aldehyde ; Valeral.
C4H9 . CHO

Natural Sources.

A valeric aldehyde is said to occur in
the oils of Eucalyptus globulus and of
cajeput from Melaleuca leucadendron
(Voiry : see under butyric aldehyde [94])
and (isovaleric aldehyde) in American
peppermint oil (Power and Kleber, Zeit.
anal. Ch. 33, 762; Pharm. Rund. 12,
157 j Arch. Pharm. 232, 639).

A valeric aldehyde probably occurs in
the Japanese ' kesso ' oil from the root
of Valeriana ojfici^ialis var. ayigustl^
folia (Bertram and Gildemeister, Arch.
Pharm. 228, 483).

The oil of Eucalyptus rostrata con-
tains a valeric aldehyde (Schimmel's
Ber. Oct. 1891).

Synthetical Processes.

I. Normal Valeric Aldehyde ; Pentanal.

CH3 . CHg . CHg . CHg . CHO

[A.] From normal valeric and /m«/c
acids [Vol, II] by distilling a mixture
of the calcium salts (Lieben and Rossi,
Ann, 159, 70 ; Zander, Ann. 224, 81).

[B.] Succinic acid [Vol. II] is con-
verted into thedibromo-acid by bromina-
tion (Kekule, Ann. 117, 123 ; Suppl. 1,
131 ; Bourgoin, Bull. Soc. [2] 19, 148;
Gorodetzky and Hell, Ber. 21, 1731 ;
Lassar-Cohn, Ann. 251, 346). The
dibromo-acid, on heating with alcoholic
potash, gives acetylenedicarboxylic acid
(Bandrowski, Ber. 10, 838; 12, 2212;
13, 2340 ; 15, 2694 ; Baeyer, Ber. 18,
677 ; 2269), and the latter (or its acid
potassium salt), on heating with
water, yields propiolic (propargylic =
propinic) acid (Bandrowski, Ber. 13,
2340), which, by oxidation with cupric
hydroxide, is converted into diacetylene-
dicarboxylic = hexanediinedicarboxylic
acid (Baeyer, /oc. ct7. 678; 2270). The
acid sodium salt of the latter acid on
heating in aqueous solution and sub-
sequent oxidation of the copper salt
with potassium ferricyanide, gives tetra-
acetylenedicarboxylic acid {Ibid. 2271),

184 ALDEHYDES AND KETONES: FATTY GROUP [95JB-/ZZB.

which, on reduction with zinc and
sulphuric acid and finally with sodium
amalgam, yields an acid apparently
identical with sebacic acid {Ibid. 2272).
Sebacic acid on heating with lime is
said to give, among other products, va-
leric aldehyde (Calvi, Ann. 91, 110;
Petersen, Ann. 103, 1 84 ; Dale and
Schorlemmer, Ann. 199, 149).

[C] Fnmaric acid [Vol. II] gives
dibromsuccinic acid on heating with
bromine and water (Kekule, Ann.
Suppl. 1, 131; Baeyer, Ber. 18, 676),
and this can be converted into sebacic
acid as above.

[D.] From adipic acid [Vol. II], which
gives sebacic acid (ester) on electrolysis
of a solution of the potassium salt of
the monoethyl ester (Crum Brown and
Walker, Ann. 261, 121).

[E.] Stearic acid [Vol. II] gives se-
bacic acid when heated with nitric acid
(Arppe, Zeit. [2] 1, 296).

[P.] Normal hexoic acid [Vol. II], on
bromination and boiling with sodium
carbonate solution, gives a-hydroxy-
hexoic = 2-hexanolic acid (Jelisafoff,
Journ. Russ. Soc. 12, 367), and this, on
oxidation with chromic acid mixture,
yields valeric aldehyde among other pro-
ducts (Ley, Ibid. 9, 139).

II. Isovaleric Aldehyde ; 'i-Methyl-
^-buianal.

CH3.CH(CH3).CH2. CHO

[A.] From isoamyl alcohol [22] by
oxidation (Dumas and Stas, Ann. Chim.
[2] 73, 145 ; Parkinson, Ann. 90, 114 ;
Kolbe and Guthrie, Ann. 109, 296;
Bouveault and Rousset, Bull. Soc. [3]
11,300).

An amylene from fusel oil (isopropyl-
ethylene : see above under butyric alde-
hyde [94; H]) gives isopropylethylene
glycol (Flawitzky, Ann. 179, 351 ;
Wagner, Ber. 21, 1232), and this on
heating with phosphorus pentoxide or
zinc chloride yields isovaleric aldehyde
(Flawitzky, Ber. 10, 2240 : see also
Michailenko, Journ. Russ. Soc. 27, 57).

Isoamyl alcohol gives 30-40 per cent,
isovaleric aldehyde by pyrogenic de-
composition (Ipatieff, Ber. 34, 598).

[B.] From isovaleric acid [Vol. II]
by the dry distillation of its salts or by
distilling the calcium salt with calcium
formate [Vol. II] (Chancel, Ann. 60,
318 ; Ebersbach, Ann. 106, 262 ;
Wurtz, Ann. 134, 302 ; Schmidt, Ber.
5, 600 j Limpricht, Ann. 97, 370;
Dilthey, Ber. 34, 2115). Or isovaleric
acid can be converted into isovaleryl
chloride, and the latter reduced in moist
ethereal solution with sodium amalgam
(W. H. Perkin, junr., and Sudborough,
Proc. Ch. Soc. 10, 216).

[C] Leucine [Vol. II] gives isovaleric
aldehyde when acted on by sulphur tri-
oxide (Schwanert, Ann. 102, 226).

[D.] Formic aldehyde [9l] and iso-
hutyric aldehyde [94] combine under the
influence of alcoho ic potash to form
' pentaglycol,' (CH3), : C(CH2 . OH)^
(Just, Monats. 17, 76). The latter by
the action of 5-20 per cent, sulphuric
acid gives, among other products, iso-
valeric aldehyde (Fischer and Winter,
Monats. 21, 301 : see also Lieben, Ibid.
23, 60).

///. Methyl ethylacetaldehyde ;
l-Methylbutanal.

CH3.CH2.CH(CH3).CHO

[A.] Tiglic aldehyde [103] gives this
valeric aldehyde on reduction with iron
and acetic acid (Herzig, Monats. 3, 1 23 j
Lieben and Zeisel, Ibid. 7, ^6).

[B.] Isoamyl alcohol [22] gives an
amylene which, on conversion into
bromide and treatment with alcoholic
potash, yields a monobromamylene. The
latter on further heating with strong
alcoholic potash gives (with valerylene)
a valeryl ethyl ether, which, on heating
with dilute sulphuric acid at 150°, yields
a valeric aldehyde probably having the
above constitution (Eltekoff, Ber. 10,
706). ^

Or isoamyl alcohol can be converted
into isoamyl iodide and amylene, and
the latter by the action of chlorine into a-
ethylallyl chloride [CH^ : ^i^^r^ . CH^
CI] (Kondakoff, Journ. Russ. Soc. 20,
149). This chloride on heating with
potassium carbonate solution gives the
corresponding a-ethylallyl alcohol, and

05 /// B-06 III B.]

VALERIC ALDEHYDE

185

the latter on heating- with very dilute
sulphuric acid yields the above valeric
aldehyde {Ibid. 154).

Note: — Forvaleral from methylethyl methyl-
carbinol (active amyl alcohol of fusel oil) see
Bemont, Comp. Rend. 133, 1222 ; also Etard and
Vila, I6i(i. 134, 122. For trimethacetaldehyde
= dimethylpropanal from trimethacetic and
formic acids see Tissier, Ann. Chim. [6] 29,
353-

96. Hexoic Aldehyde ; Caproic
Aldehyde.

CgHii . CHO

Natural Sources.

Hexoic aldehyde occurs in small
quantity in oil of TLucalyptus globulus
(Bouchardat and Oliviero, Bull. Soc.
[3] 9j 429). A caproic aldehyde occurs
in rancid fat, probably a bacterial pro-
duct (Nagel, Am. Ch. Journ. 23, 173).

Synthetical Processes.

/. Normal Caproic Aldehyde ; Hexafial.

CH3 . CH2 . CH2 . CH2 . CH2 . CHO

[A.] From normal caproic = hexoic
and formic acids [Vol. II] by distilling-
a mixture of the calcium salts (Lieben
and Janecek, Ann. 187, 130).

11. Isocaproic Aldehyde ; Isolutylacet-
aldehyde ; \-Methylpentanal.

CH3 . CH(CH3) . CH2 . CH2 . CHO

[A.] From isoLuty I acetic and formic
acids [Vol. II] by distilling a mixture
of the calcium salts (Rossi, Ann. 133,
178).

III. Methylpropylacetaldehyde ;
1 -Methylpen tanal.

CH3 . CH2 . CH2 . CH(CH3) . CHO

[A.] From normal propyl alcohol [15]
through the aldehyde (propanal) by
oxidation (Chancel, Ann. 151, 301 ;
Przybytek, Journ. Russ. Soc. 8, 0^^^ ;
Lieben and Zeisel, Monats. 4, 14). Pro-
panal on heating with sodium acetate
solution gives methylethylacrolem = 2-

methyl-2-pentenal (L. and Z., loc. cit.
16 ; Hoppe, Ibid. 9, 637), and this, on
standing in contact with iron and acetic
acid for four weeks in the cold, is con-
verted into the above hexoic aldehyde
(L. and Z., loc. cit. 23).

Or indirectly from propyl (or iso-
propyl) alcohol through propylene, the
bromide and cyanide, and hydrolysis of
the latter to pyro tartaric acid (Simpson,
Ann. 121, 161). Subsequent steps as
under I and C below.

Or through propylene chloride or
bromide and glycol, and then as below
under B. According to Michael (Journ.
pr. Ch. [2] 60, 417 : see also Beilstein
and Wiegand, Ber. 15, 1496) propanal
is among the products of the action
of water and silver oxide on propylene
bromide.

Or propylene chlorhydrin by the
action of potash gives propylene oxide,
and this yields propanal on heating with
zinc chloride more readily than the
glycol (Krassusky, Journ. Russ. Soc.

Note : — Generators of propylene (see under
glycerol [48 ; B to G, &c.) thus become
generators of the above hexoic aldehyde.

[B.] From glycerol [48] through ally!
alcohol (see under ethyl alcohol [l4 ;
G]). The latter gives methylethyl-
acrolem among other products when
heated with 10 per cent, hydrochloric
acid at 100° (Solonina, Journ. Russ.
Soc. 19, 306). Subsequent reduction as
above under A.

Or allyl chloride from allyl alcohol
gives a chlorhydrin which is decomposed
by heating with water with the forma-
tion of acetone and propanal (see under
acetone [106 ; F]).

Or from glycerol through glyceric
acid and pyrotartaric acid (see under
benzyl alcohol [54; P]), or through allyl
cyanide and pyrotartaric acid [Ibid.).
Pyrotartaric acid is converted into citi*a-
dibrompyrotartaric acid and then treated
as below under C. Or pyrotartaric acid
gives propanal among the products of
electrolysis of the potassium salt (Peter-
sen, Zeit. physik. Ch. 33, 704).

Or from glycerol through propylene
glycol by distilling with sodium hy-

186 ALDEHYDES AND KETONES: FATTY GROUP [9e/77B-F.

droxide (Belolioubek, Ber. 12, 1873;
Morley and Green, Trans. Ch. Soc. 47,
133) and the action of acidified water
on the glycol at 215° (Linnemann, Ann.
192, 61 : see also Lieben, Monats. 23,
60), or by heating with zinc chloride
(Flawitzky, Ber. 11, 1356 ; Journ. Russ.
Soc. 10, 348), by which propanal is
formed.

Or from glycerol through acrolein
[101], which, on treatment with/?o?^fl6-5mwi
cyanide [172] and acetic acid, gives the
nitrile of vinylglycollic = i : 3-butenolic
acid and the acid itself on hydrolysis.
The latter combines with bromine to
form 4:3: 2-dibrombutanolic acid, and
this is reduced by sodium amalgam to
a-hydroxybutyric acid (Van der Sleen,
Rec. Tr. Ch. 18, 303 ; 21, 209). Subse-
quent steps as below under N.

[C] From citric acid [Vol. II] through
citraconic acid (see under benzyl alcohol
[54 ; M]). The latter combines with
bromine to form citradibromjjyrotartaric
acid (Kekul^, Ann. Suppl. 2, 96 ; Fittig
and Krusemark, Ann. 206, 3), and this
on heating with alkali gives propanal
(Friedrich, Ann. 203, -3,^^ ; Fittig and
Krusemark, /oc. cit. 4; Ssemenoff, Journ,
Russ. Soc. 31, 396), which can be con-
verted into methylethylacrole'm, &c., as
under A.

Citraconic acid gives mesaconic acid
under the influence of acids, alkalis, or
water (Gottlieb, Ann. 77, 368 ; Kekule,
Ann. Suppl. 2, 94; Fittig, Ann. 188,
77,80; Delisle, Ann. 269, 83; Swarts,
Jahresber. 1873, 579), and this com-
bines with bromine to form mesadi-
brompyrotartaric acid (Kekule, loc. cit.
103), which also yields propanal among
the products of its decomposition by
alkalis (Fittig and Krusemark, /otf. ci?5. 4).

Or citric acid by distillation, or by
heating with dilute sulphuric acid, gives
itaconic acid (Baup, Ann. 19, 39 ;
Markownikoff and Purgold, Zeit. [2]
3, 364), which combines with hydrogen
chloride to form itachlorpyrotartaric
acid (Swarts, Zeit. [3] 2, 731 ; Michael,
Journ. pr. Ch. [3] 45, 60). The latter
on treatment with water or alkalis
yields itamalic (hydroxymethylsuccinic)
acid, which readily passes into its an-
hydride, paraconic acid (Swarts, Zeit.

[3] 3, 648 ; Beer, Ann. 216, 84), and
this gives citraconic anhydride on dis-
tillation.

Or from citric acid through acetone-
dicarboxylic, /3-oxyglutaric, vinylacetic,
and cro tonic acid (see under n-propyl
alcohol [15 ; W]). From crotonic acid
as under N below.

[D.] From lactic acid [Vol. II]
through citraconic acid by distillation
(Engelhardt, Ann. 70, 343 ; 346), and
then as above. Or through pyroracemic
acid and pyrotartaric acid (see under
benzyl alcohol [54 ; P and I]), and then
as below under I and above under C.

[E.] From acetoacetic acid (ester)
[Vol. II] and Jiydrogen cyanide [l72]
through hydroxypyrotartaric and citra-
conic acid (see under benzyl alcohol
[54 ; M, note]), and then as above
under C. Or from acetoacetic ester
and a-hrom propionic ester through /3-
methylacetosuccinic ester and pyrotar-
taric acid (see under benzyl alcohol
[54; I]). Or from chloracetic ester
and acetoacetic ester through aceto-
succinic ester, a-methylacetosuccinic
ester, and pyrotartaric acid {Ibid.). Or
from acetoacetic ester through isonitroso-
acetone, acetyl cyanide, pyroracemic and
pyrotartaric acid {Ilnd.),

Or from acetoacetic ester through
methylacetoacetic ester by the action
of methyl iodide on the sodium deriva-
tive of acetoacetic ester ; methylaceto-
acetic ester on successive treatment
with bromine and alcoholic potash gives
mesaconic ('oxytetric ') acid (Demar9ay,
Ann. Chim. [5] 20, 473 ; Gorboff,
Journ. Russ. Soc. 19, 605 ; Cloez,
Bull. Soc. [3] 3, 598 ; 603 : see also
under benzyl alcohol [54 ; I]), and this
can be converted into propanal, &c., as
under C.

Or from acetoacetic ester through
the y-bromo-derivative, succinylsuccinic
ester, and ethyl malonic acid (see under
n-propyl alcohol [15 ; A A ; Y ; O]).
From the latter as below under G.

Or from ethylacetoacetic ester through
I : i-dinitropropane and propanal as
under n-propyl alcohol [15 ; AA].

[P.] From isovaleric acid [Vol. II]
through hydroxypyrotartaric acid, citra-
conic acid, &c. [54; M].

86 /// G-L.]

HEXOIC ALDEHYDE

187

[G.] From malonic dindi propionic acids
[Vol. II] through propanetricarboxylic
ester, citraconic or mesaconic acid (see
under benzyl alcohol [54; M, note]),
and then as before.

Or from malonic and acelic acid
through propanetricarboxylic ester by
the interaction of sodio-methylmalonic
ester and chloracetic ester, and pyro-
tartaric acid by hydrolysis of the tri-
carboxylic ester (Bischoff and v. Kuhl-
berg, Ber. 23, 6'^^). Subsequent steps
as under I below and C above.

Or malonic acid can be converted
into ethylmalonic (a-isopyrotartaric)
ester by the action of ethi/l iodide on
sodio-malonic ester (Conrad, Ann. 204,
134 : see also Daimler, Ann. 249, 174),
chlorethylmalonic ester by chlorination
(Conrad, Ber. 14, 618 ; Conrad and
Guthzeit, Ann. 209, 232), or iodethyl-
malonic ester by the action of iodine
on sodio-ethylmalonic ester. The
chloro- or iodo-esters on hydrolysis
with baryta water give a-ethyltartronic
acid (Conrad and Guthzeit, loc. cit. 233 ;
Bischoff and Hausdorfer, Ann. 239,
127), and the latter on heating to 180°
yields a-hydroxybutyric acid (Guthzeit,
Ann. 209, 234 ; Conrad, Ber. 14, 618),
from which propanal can be obtained
as under TS, and the latter treated as
under A. Chlorethylmalonic ester also
gives a-hydroxybutyric acid on heating
with hydrochloric acid.

[H.] From acetic and propionic acids
[Vol. II], alcohol [14], and piotassium
cyanide [172] through a-methyl-^-
cyanosuccinic ester and citraconic acid
(see under benzyl alcohol [54; M, note]).
Or from acetic acid through acetyl cyan-
ide, pyroracemic acid, and pyrotartaric
acid (see under benzyl alcohol [54; l]).

[I.] From tartaric acid [Vol. II]
through pyrotartaric acid (see under
n-propyl alcohol [15 ; V]), citradi-
brompyrotartavic acid by the action of
bromine and phosphorus on the latter
Auwers and Imhauser, Ber. 24, 2237),
and then as above under C.

[J.] From propio7iic and oxalic acids
[Vol. II] and alcohol [l4] through
methyloxalacetic ester, ^-methylmalic
acid, and citraconic or mesaconic acid
(see under benzyl alcohol [54 ; M]).

Or from propionic acid through the
aa-dibromo-acid, the a^S-acid, glyceric
acid, and pyrotartaric acid ; or through
the aa-dibromo-acid, pyroracemic and
pyrotartaric acids ; or through propion-
amide, propionitrile, aa-dichlorpropionic
acid, pyroracemic and pyrotartaric acids
(see under benzyl alcohol [54 ; O]).

Or from propionic acid through
.propionyl chloride and cyanide (Claisen
and Moritz, Trans. Ch. Soc. 37, 692).
The latter on hydrolysis gives ethyl-
glyoxylic acid = propionylf ormic or 2-
butanonic acid {Ibid, and Ber. 13,
2121), which is reduced by sodium
amalgam to a-hydroxybutyric acid,
from which propanal can be obtained
as under N, and 2-methylpentanal as
under A.

Propanal is obtainable directly from
propionic acid by distilling the calcium
salt with calcium formate [Vol. II]
(Rossi, Comp. Rend. 70, 129).

[K.] From allyl isothiocyanate [16 6]
through allyl cyanide and pyrotartaric
acid (see under benzyl alcohol [54; F
and J]), and then as above under I
and C.

[L.] From ethyl alcohol [l4] through
iodoform, acrylic acid, a-chlorlactic acid,
glyceric acid (see under benzyl alcohol
[54; I]), and then through pyrotar-
taric acid as above under B.

Or from ethyl alcohol through ethyl
ether, dichlorether, chloracetaldehyde,
yS-chlorlactic acid, glyceric acid, and
pyrotartaric acid [54 ; l].

Or from ethyl alcohol through chlor-
acetal, chloracetaldehyde, j3-chlorlactic,
glyceric, and pyrotartaric acids [54; l].

Or through chloral, the cyanhydrin,
trichlorlactic acid, dichloracetaldehyde,
dichlorlactic acid, chloracetaldehyde,
/3-chIorlactic acid, &c. [54 ; l]. Or from
ethyl alcohol through ethylene, vinyl
chloride, chloracetaldehyde, ^-chlor-
lactic acid, &c., as before (see under
benzyl alcohol [54; A]).

Note : — By this last method generators of
ethylene thus become generators of a-methyl-
pentanal.

Ethyl alcohol might be converted
more directly into propanal through
ethyl cyanide and propionic acid, and

188 ALDEHYDES AND KETONES: FATTY GROUP [96///L-Q.

distillation of the calcium salt of the
latter with calcium formate.

Or from alcohol and formic acid
[Vol. II] through diethyl carbinol by
the action of zinc on ethyl iodide and
formic ester, and decomposition of the
product with water (Saytzeff and
Wagner, Ann. 175, 351). The car-
binyl iodide gives symmetrical methyl-
ethylethylene (= 3-pentene) on treat-
ment with alcoholic potash (S. and W.
loc. cit. 373 ; 179, 302), and the corre-
sponding 1 : 3-dibrompentane yields
symmetrical methylethylethylene glycol
(= a : 3-dihydroxypentane) on treat-
ment with silver acetate and hydrolysis
of the acetate (Ihid. 179, 308). The
glycol gives a-hydroxy butyric acid on
oxidation by dilute nitric acid. Sub-
sequent steps as below under N.

Notes : — The amylene fromziwc e^At/^and chloro-
form may be symmetrical methylethylethylene
(Beilstein and Rieth, Ann. 124, 245 ; Beilstein's
' Handbuch,' I, 116).

Diethyl oxalate interacts with zinc ethyl to form
diethoxalic ester [21 ; G]. The latter by the
action of phosphorus trichloride gives a-ethyl-
crotonic ester (Frankland and Duppa, Journ.
Ch. Soc. 18, 133 ; Fittig and Howe, Ann. 200,
22), and the free acid combines with hydrogen
bromide to form bromhydro-ethylcrotonic =
bromhexoic acid (F. and H. loc.cit. 23). The latter
acid is decomposed by cold sodium carbonate
solution with the formation of symmetrical
methylethylethylene {Ihid. 30).

Ethyl alcohol and acetic acid give ethylaceto-
acetic ester and, by the action of nitrous acid,
the latter yields an isonitroso-derivative which
is decomposed on heating with dilute sul-
phuric acid with the formation of acetyl-pro-
pionyl = 2 : 3-pentadione (v. Pechmann, Ber.
21, 141 2 ; 24, 3956). The diketone on reduction
with zinc and dilute sulphuric acid gives
methylethylketol (v. P. and Dahl, Ber. 23,
2425) and, on further reduction with sodium
amalgam, symmetrical methylethylethylene
glycol {Ihid. 2426).

Methylpropyl ketone [21 ; A] and diethyl ketone
[21 ; G ; H] give acetyl-propionyl on heating
with nitric acid (Fileti and Ponzio, Gazz. 25,
239 ; Journ. pr. Ch. [2] 55, 194).

[M.] From aconitic acid [Vol. II]
through itaconic acid by heatmg with
water at i8o° (Pebal, Ann. 98, 94), and
then as above under C.

[N.] From normal buti/ric acid [Vol.
II] through propanal by electrolysis of
the sodium salt (v. Miller and Hofer,
Ber. 27, 468 ; Hofer and Moest, Ann.
323, 284). Or through the a-chloro- or
a-bromo-acid and a-hydroxy-acid (Nau-

mann, Ann. 119, 115; Friedel and
Machuca, Ann. 120, 279; Markowni-
koff, Ann. 153, 242). The latter gives
propanal on oxidation (Ley, Journ.
Russ. Soc. 9, 131). Propanal can be
converted as under A above.

Note : — Since crotonic acid gives a- with
some )3-brombutyric acid on combination with
hydrogen bromide (Hemilian, Ann. 174, 325),
the generators of crotonic aldehyde and acid
referred to under normal butyl alcohol [17 ; G,
&c.] and benzyl alcohol [54 ; G ; H, &c.] thus
become generators of a-hydroxybutyric acid
and propanal. These generators are : — malonic
acid and acetaldehyde ; acetoacetic ester ; glycerol ;
allyl isothiocyanate ; p-hydroxyhutyric acid ; eiy-
thritol and formic acid ; n-butyric acid ; acetylene and
ethylene.

Crotonic acid on combination with hypo-
bromous acid gives also (with the a-) some
/3-brom-a-hydroxybutyric acid, which yields
propanal on heating the sodium salt with
water (Melikoff, Journ. pr, Ch. [2] 61, 556).

Or crotonic acid combines with chlorine to
form ojS-dichlorbutyric acid, the sodium salt of
which, on heating with water, gives propanal
among other products (Wislicenus, Ann. 248,
283 ; Michael and Browne, Am. Ch. Journ. 9,
282).

Or crotonic acid combines with hypochlorous
acid to form a-chlor-)8-hydroxybutyric acid
(Erlenmeyer and Miiller, Ber, 15, 49 ; Melikoff,
Ann. 234, 198), which, by the action of alco-
holic potash, gives yS-methylglycidic acid (Meli-
koff, loc. cit. 204). The latter combines with
hydrogen bromide to form /3-brom-a-hydroxy-
butyric acid, which is decomposed into propanal
as above (Melikoff, Journ, pr. Ch. [2] 61, 556).

Or from butyric acid through butyr-
one or methylpropyl or ethylpropyl
ketone, dinitropi'opane, and propanal
(see under n-propyl alcohol [l5 ; P ;

[O.] Manvitol [5l] on distillation
with lime gives, among other products,
' metacetone,^ which is a mixture con-
taining propanal (Favre, Ann. Chim.
[3] 11, 71 ; Fischer and Laycock, Ber.
22, loi). From propanal to 2-methyl-
pentanal as above under A.

[P.] From acetic aldehyde [92], the
oxime of which combines with acid
sodium sulphite to form a salt, which,
on heating with hydrochloric acid, gives
methylglyoxal (v. Pechmann, Ber, 20,
2543). The dioxime of the latter yields
propylene glycol by electrolytic reduc-
tion (Tafel and Pfeffermann, Ber. 35,
15 10). From the glycol through pro-
panal as above under B, &c.

[Q.] From acetol [43], which gives

06 /// Q-100.]

HEXOIC ALDEHYDE

189

propylene glycol on reduction with
sodium amalgam. From the glycol
through propanal, &c., as above
under A.

97. Heptoic Aldehyde ; (Euanthol ;
Heptanal.

CH3.CH2.CH2.CH2.CH2.CH2.CHO

Natural Sources.

(Enanthic aldehyde occurs in rancid
olive oil ; probably a bacterial product
derived from oleic acid (Scala, Ch.
Centr. 1898^ 1^ 439; from Staz. sper.
agrar. 30^ 613). This aldehyde occurs
also in rancid fat (Nagel, Am. Ch.
Journ. 23, 172).

alkali or sodium to form nitro-octanal,
which, on heating with zinc chloride,
gives nitro-octylene. The latter, by
reduction with zinc and acetic acid,
yields the oxime of octanal, from which
the aldehyde can be obtained by hydro-
lysis (Bouveault and Wahl, Comp.
Rend. 134, 1326).

[D.] From oclo'ic and formic acids
[Vol. II] by distilling a mixture of the
calcium salts (Schimmel & Co., Germ.
Pat. 126736 of 1900 ; Ch. Centr. 1901,
2. 1375)-

Note : — An octoic aldehyde is said to occur
among the products of distillation of castor-oil
soap (Limpricht, Ann. 93, 242 ; Bouis, Ann.
Chim. [3] 48, 99 ; Stadeler, Journ. pr. Ch. 72,
241 ; Dachauer, Ann. 108, 270 ; B6hal, Bull.
Soc. [2] 47, 33 ; 163).

The constitution of the natural aldehyde has
not been determined.

Synthetical Process.

[A.] Sebacic acid [Vol. II] gives
cenanthol, among other products, when
heated with lime (Calvi, Ann. 91, iio;
Petersen, Ann. 103, 184 : see also Dale
and Schorlemmer, Ann. 199, 149).

98. Octoic Aldehyde; Octanal.
C^Hjg.CHO

Natural Source.

This aldehyde possibly occurs in oil
of lemon (v. Soden and Rojahn, Ber.
34, 2809).

Synthetical Processes.

[A.] From 71-octyl alcohol [28] by
oxidation (SchimmePs Ber. April, 1 899 ;
Ch. Centr. 1899, 1, 1043).

[B.] From butyric aldeliyde [94]
through a-ethyl-/3-propy]acrolein = oc-
tenoic aldehyde, by the action of dilute
caustic alkali (Raupenstrauch, Monats.
8, 112). The acrolein reduces, by iron
and acetic acid, to a secondary octanal,
which is ethylbutylacetaldehyde {Ibid.

115).

[C] (Enanthol [97] and nitrometJiane
(see under hydrogen cyanide [172 ; J
and Y]) condense under the influence of

99. Enuoic or ITonoic Aldehyde ;
ITouanal.

CgHjY • CHO

Natural Sources.

Occurs in oil of lemon (v. Soden and
Eojahn, Ber. 34, 2809), in oil of
mandarin orange (SchimmeFs Ber. Oct.
1901 ; Ch. Centr. 1901,2, 1007), and
in Ceylon oil of cinnamon (SchimmeFs
Ber. April, 1902; Walbaum and
Hiithig, Journ. pr. Ch. [2] 66, 47).

Synthetical Process.

[A.] From nonoic and formic acids

[Vol. II] by distilling a mixture of the

calcium salts (Schimmel & Co., Germ.

Pat. 126736 of 19CO ; Ch. Centr. 1901,

2. 1375)-

Note : — The constitution of the natural alde-
hyde has not yet been determined.

100. Decoic Aldehyde ; Decanal.
CH3[CH2]8.CHO

Natural Sources.

According to Schimmel & Co.
(SchimmeFs Ber. Oct. 1900) the oil of
sweet orange contains n-decoie aldehyde

190

ALDEHYDES AND KETONES: FATTY GROUP [100-103.

to the extent of 8-5 per cent. (Stephan,
Journ. pr. Ch. [3] 62, ^2^).

The aldehyde has been found also in
oil of mandarin orang-e (Schimmel's
Ber. Oct. 1901 ; Ch. Centr. 1901, 2,
1007), and it may possibly occur in oil
of lemon (liul. Oct. 1902 ; Ch. Centr.
1902, 2, 1207).

Synthetical Process.

[A.] From n-decoic and formic acids
[Vol. II] by distilling a mixture of the
barium salts (Krafft^ Ber. 16, 17^7 j
Schimmel & Co., Germ. Pat. 126736
of 1900 ; Ch. Centr. 1901, 2, 1375).

101. Acrolein ; Acrylic Aldehyde ;
Fropenal.

CH2:CH.CH0

Natural Source.

Occurs in rancid fat ; probably a
bacterial product (Nagel, Am. Ch.
Journ. 23, 172).

Synthetical Processes.

[A.] From glycerol [48] by heating
with dehydrating agents (see under
mannitol [51; B]).

[B.] From acetone [IO6] through
the dibromide i^bid. C] ; also glycerol
[48; E]).

[C] From alcohol [14] and acetic
acid [Vol. II] through diiodacetone
(glycerol [48; K]).

[D.] From viannitol [5l] (glycerol
[48; O]). , , , .

[E.] From dextrose [154], bemg
among the products of oxidation by
chromic acid or by sulphuric acid and
manganese dioxide (Liebig, Ann.113, i).

[P.] From normal or isopropyl alcohol
[15 ; 16] through the compound of
propylene with mercuric sulphate (ben-
zyl alcohol [54; E]).

Note : — For generators of propylene see under
glycerol [48 ; B to G] ; also under isopropyl
alcohol [16].

102. Crotonic Aldehyde ;
2-Bateual.

CH3.CH:CH.CH0

. Natural Source.

Said to have been found in the first
runnings from spirit rectification
(Kramer and Pinner, Ber. 3, 76). Bio-
chemical origin doubtful.

Synthetical Processes.

Syntheses of crotonic aldehyde are
given under n-butyl alcohol [l7].

[A.] From acetic aldehyde [92] (n-
butyl alcohol [17 ; G]).

[B.] From erythritol [50] a-ud. formic
acid [Vol. II] (ibid. [17; Ij).

[C] From malic acid [Vol. II]
through coumalic acid or by electro-
lysis {Ibid. [17 ; O]).

[D.] From acetylene [l; A, &c.]
{Ibid. [17 ; I, note]).

[E.] From formic and acetic esters
[Vol. II] {Ibid. [17 ; J]).

[F.] From ethylene through vinyl
bromide {Ibid. [17; I, note]).

[G.] From lactic acid [Vol. II] {Ibid.
[17; I, note]).

[H.] From fi-hydroxybutyric acid
[Vol. II] {Ibid. [17 ; I, note]).

[I.] From tetramMhylenediamine [Vol.
II] through )S-butylene glycol [17; P].
Crotonic aldehyde is among the pro-
duets of oxidation of the glycol.

103. Tiglic Aldehyde ; Guaial ;
2-Methyl-2-Butenal.

CH3 . CH : C(CH3) . CHO

Natural Source.

The aldehyde does not occur in the
free state, but the complex exists in
some constituent of guaiacum resin
from the W. Indian Gnaiacum officinale.
The resin gives tiglic aldehyde on dry
distillation (Volckel, Ann, 89, 346 ;
Herzig, Monats. 3, 118; 822; 825).
The acid of guaiacum resin, guaiaretic
acid, does not appear to be the source

103-104 C]

TIGLIC ALDEHYDE

191

of the aldehyde (Herzig and Sehiff,
Monats. 18, 714).

Synthetical Process.

[A.] From acetic aldehyde [92] and
propionic aldehyde (see under hexoic
aldehyde [2-methylpentanal ; QQ, III ;
A, C, &c.]) by heating a mixture with
sodium acetate solution at 100° (Lieben
and Zeisel, Monats. 7, 54 : see also
Schmalzhofer, Monats. 21, 671).

104. Citral ; Geranial ;

Shodinal ; Licareal ;

2 : 6-Dimethyl-2 : 6-Octadieual-8.

CH3 . C :CH . CH2 . CH2 . C : CH . CHO
CH3 CH3

Natural Sources.

In oil of lemon-grass from Andro-
pogcn citrattis from India, Ceylon,
Singapore, and Jamaica (SchimmeFs
Ber. Oct. 1888; Dodge, Am. Ch. ,
Journ. 12, S53'> ^er. 24, 90; Ch.
Centr. 1891, 1, 88) ; in oils of lemon.
Citrus limonnm (Schimmel's Ber. Oct.
1888, p. 17); of C. medica {Ibid.
Oct. 1895; Burgess, 'Analyst,' 26,
260) ; of Eucalyptus staigeriana or
' lemon- scented iron-bark'' of Queens-
land (Schimmel's Ber. April, 1888);
of Backhousia citriodora, Queensland
{Ibid, and Oct. 1888); of Tetranthera
citrata, Java {Ibid. Oct. 1888); and of
Xanthoxylon piperitiim, Japan {Ibid. Oct.
1890).

Citral occurs also in oil of Lippia
{Aloysid) citriodora or Hemon-scented
verbena ' (Umney, Imperial Inst. Journ.
1896, p. 302; Journ. Soc. Ch. Ind. 15,
739 ; Pharm. Journ. 57, 2.57 ; Barbier,
Bull. Soc. [3] 21, ^'>,S)i i^ o^^ of man-
darin orange from Citrus ?iobilis or C.
madurensis (Semmler, Ber. 24, 202 ;
SchimmeFs Ber. April, 1897 ; Journ.
Soc. Ch. Ind. 16, 556 ; Flatau andLabbe,
Bull. Soc. [3] 19, 364), and in oil of
sassafras leaf from 8. officinalis (Power
and Kleber, Pharm. Rev. 14, 103 ; Ch.
Centr. 1897, 2, 42).

Citronella oil from Andropogon nardjis,

according to Flatau (Bull. Soc. [3] 21,
158), contains 2-5 per cent, citral. This
aldehyde is contained also in the oils of
Eucalyptus patenti^iervis and E. vitrea
(Smith, Proc. Roy. Soc, N. S. Wales,
1 900; 'Nature,' 62, 384; Schimmel's
Ber. Oct. 1901), in oil of sweet orange
(Semmler, Ber. 24, 202 ; Parry, ' Chemist
and Druggist,' &Q,462; 722; Fabris,
Journ. Soc. Ch. Ind. 19, 771), in oil of
W. Indian bay from Pimenta acris
(Power and Kleber, Pharm. Rund. 13,
60), in oil of Pimenta leaf from a
Trinidad sp. (Schimmel's Ber. Oct.
1896), and in German oil of rose (Wal-
baum and Stephan, Ber. 33, 2305).

Note :— Citral, according to Doebner (Ber. 31,
1888 ; also Tiemann, Ibid. 2313), is the chief
unsaturated open-chain aldehyde present in
lemon-grass oil. According to Stiehl (Journ.
pr. Ch. 58, 51 ; 59, 497 ; Ch. Zeit. 22, 1086)
two other aldehydes are present, but these
have not been found by Semmler (Ber. 31,
3001), by Doebner {Ibid. 3T95), nor by Tiemann
{Ibid. 3336; 32, 827). The citral from lemon-
grass oil and from ' verbena ' {Lippia citriodora)
consists of a mixture of two stereo-isomerides
(Tiemann, Ber. 33, 877 ; Kerschbaum, Ibid.

88.5)-

For bibliographical history of citral see Tie-
mann, Ber. 31, 3278 ; 32, 831, foot-note.

Synthetical Processes.

[A.] From acetic acid [Vol. II], alcohol
[14], and methylheptenone [ill]. Brom-
acetic ester (Perkin and Duppa, Ann.
108, 106 j Hell and Miihlhauser, Ber. 11,
241 ; 12, 735 ; Michael, Am. Ch. Journ.
5, 202) and methylheptenone are heated
with zinc, and the product (hydroxy-
dihydrogeranic ester) hydrolysed by
dilute alcoholic potash so as to give the
acid (hydroxydihydrogeranic = 2 : 6-di-
methyl-2-octene-6-olic-8-acid). The lat-
ter, on heating with acetic anhydride and
sodium acetate, gives geranic = 2:6-
dimethyl-2 : 6-octadiene-8-acid, and this,
on distilling the calcium salt with cal-
cium formate [Vol. II], yields citral
(Tiemann, Ber. 31, 827).

[B.] Geraniol [36] gives citral on
oxidation with chromic acid mixture
(Barbier, Bull. Soc. [3] 9, 803 ; Semm-
ler, Ber. 23, 2966; 24, 201 ; Tiemann,
Ber. 31, 3311).

[C] Linalool [37] gives citral on
oxidation as above (Tiemann and Semra-

193 ALDEHYDES AND KETONES : FATTY GROUP [104 C-106.

ler, Ber. 25, ii8o ; 26, 2711 ; Bertram
and Walbaum, Journ. pr. Ch. [a] 45
590).

105. Citronellal.
CH2 : C . [CH^ls . CH . CH2 . CHO

CH,

CHc

Natural Sources.

In citronella oil from the Indian
Androjjogon nardus (Dodge, Am. Ch.
Journ. 11, 460 ; 12, 553 ; Flatau, Bull.
Soc. [3] 21, 158: see also Gladstone,
Journ. Ch. Soc. 25, 7 ; Wright^ Ibid.
27, I ; Pharm. Journ. 5, 233) ; in oils
of Tlucalyptus maculata, E. citriodora,
K dealbata, and E. planchoniana (Schim-
meFs Ber. April, 1888; Oct. 1890;
April, 1 891; April, 1893; Oct. 1893;
Kremers, Am. Ch. Journ. 14, 203 : see
also Gildemeister and Hoffmann, p. 702);
probably in oil of balm from the S.
European Melissa officinalis (Semmler,
Ber. 24, 208 : see also Schimmers Ber.
Oct. 1 895) and in ' oleum citri ' (Doeb-
ner, Ber. 27, 2026),

The aldehyde occurs to a small extent
in lemon-grass oil (Tiemann and Schmidt,
Ber. 29, 918; Labbe, Bull. Soc. [3]
21, 77), in oil of mandarin orange
(SehimmeFs Ber. April, 1897; Ch.
Centr. 1 897, 1, 992), and of sweet orange
(Flatau and Labbe, Bull. Soc. [3] 19,
361). Citronellal is present in oil of
lemon (SchimmeFs Ber. Oct. 1902; Ch.
Centr. 1902, 2, 1207 : compare Burgess
and Child, ^Chemist and Druggist,'
60, 812).

The natural product is d-citronellal.
For quantities present in citronella oils
from Java and Ceylon see SchimmeFs
Ber. April, 19C0; Journ. Soc. Ch. Ind.
19, 556. A 1-citronellal has recently
been found in a citronella oil from Java
(Schimmers Ber. April, 1 903 ; Ch.
Centr. 1903, 1, 1086).

Note : — The 1-citronellol of oil of rose [38]
corresponds with an aldehyde (rhodinal : Bou-
veault, Bull. Soc. [3] 23, 458 ; 463^, which is
isomeric with the above citronellal and which
probably has the constitution :—(CH3)2 : C :
CH . €H, . CHa . CH(CH3) • CH» • CHO. An
aldehyde of this constitution has been synthe-

sised from menthone (Wallach, Ann. 278, 302 ;
296, 131 ; Harries and Schauwecker, Ber. 34,
2981).

Synthetical Process.

[A.] From acetic acid [Vol. II], alcohol
[14], and methylheptenone [ill] through
geranic acid (see under citral [l04 ; A]).
The latter on reduction with sodium in
boiling amyl alcohol gives citronellie
acid (Tiemann, Ber. 31, 2901), the cal-
cium salt of which on distillation with
calcmm formate [Vol. II] yields citro-
nellal {Ibid. 2902).

106. Acetone; Dimethyl Ketone;
2-Fropanone.

CH3 . CO . CH3

Natural Sources.

Acetone has been found in the dis-
tillate from the leaves of Erytliroxi/lon
coca ; also in oil of tea (SchimmeFs Ber.
April, 1898; Ch. Centr. 1898, 1, 991),
and (traces) in the ethereal oil (aqueous
distillate) from the wood of the Atlas
cedar, Cedrus atlantica, and of C. libani
(Grimal, Comp. Rend. 135, 582).

Phaseolunatin, a cyanogenetic gluco-
side found in .Fhaseolns lunatus, is the
dextrose ether of acetone-cyanhydrin
(Dunstan and Henry, Proc. Roy. Soc.
72, 291).

Acetone occurs in small quantity in
the urine of cattle, dogs, and cats ; in
human blood and urine, and in larger
quantity in cases of diabetes and aceto-
nuria. Traces occur in expired air and
in emanations from the skin of man
(Johannes Miiller, Arch. exp. Path. 40,
351 ; Ch. Centr. 1898, 1, 626 : for pro-
duction and origin of acetone in the
animal organism see Cotton in Journ.
Pharm. [6] 10, 193; Ch. Centr. 1899,
2, 722 ; Neuberg and Blumenthal, Beit,
ch. Physiol, u. Path. 2, 238).

Acetone has been found in the liquid
from a hydatid cyst of the liver (Malme-
jac, Journ. Pharm. [6] 13, 406). The
acetone in these cases probably results
from the decomposition of fat (Schu-
mann-Leclerq, Ch. Centr. 1901, 1,
1113).

106-B.]

ACETONE

193

Occurs among the products of fer-
mentation (putrefaction) of fish (Morner,
Zeit. physiol. Ch. 22^ 514)^ and among
the products of fermentation of milk
sugar by Bacterium lactis aerogenes of
Eseherich = Bad. aceticum of Baginsky
(Zeit. physiol. Ch. 12, 461)^ and of
dextrose by D unbares and other Vibrios
(Gosio : quoted by Emraerling in ' Die
Zersetzung, &c./ pp. 47 and 56).

Synthetical Puocesses.

[A.] From acetic acid [Vol. II] by
dry distillation of the calcium or barium
salt (Liebig, Ann. 1, 323 ; Dumas, Ann.
Chim. [2] 49, 208), or by passing the
vapour over heated pumice and barium
carbonate (Squibb^ Journ. Soc, Ch. Ind.
14:, 506; 15, 612 ; Conroy, Ibid, gl,

309)-

Or from acetic acid and methyl alcohol
[13] by the interaction of zinc methyl
and acetyl chloride (Chiozza_, Ann. 85,
332 ; Freund, Ann. 118, i) ; or by the
action of nascent zinc methyl on acetic
anhydride, or of zinc-sodium alloy on
methyl iodide and acetic anhydride (Sayt-
zeff, Zeit. [2] 7, 104).

Or zinc methyl and dichloracetyl
chloride give dimethylisopropyl carbinol
(see under tertiary butyl alcohol [l9 ;
a]), which yields acetone on oxidation
as under K below,

[B.] From normal or isopropyl alcohol
[15 ; 16] through propylene (see under
glycerol [48 ; Al), the chloride or brom-
ide, chlor- or brompropylene by the
action of alcoholic potash, and the action
of hypochlorous acid and mercuric oxide
on the halo-propylene. The chlor-
acetone thus formed gives acetone on
reduction.

Or from brompropylene by heating
with mercuric oxide and acetic acid at
100° or with water at 190°. Also from
propylene bromide by heating with
water at 180° (Linnemann, Ann. 138,
125; 161, 58; Bull. Soc. [2] 6, 216),
or with water and silver oxide (Michael,
Journ, pr. Ch. [2] 60, 418).

Also by dissolving 2-chlorpropylene
in strong sulphuric acid and distilling
the product with water (Oppenheim,
Ann. Suppl. 6, ofi'^). 2-(^)-Chlorpropyl-

ene is formed (with 3-(a)-chlorpropylene)
by the action of alcoholic potash on
propylene chloride (see under isopropyl
alcohol [16 ; B]),

Or from propylene bromide or chloride
through propylene glycol (Wurtz, Ann.
Chim. [3] 55, 438; Eltekoff, Journ.
Buss. Soc. 10, 210 ; Niederist, Ann.
196, 359)) aid the action of water at
180-190" on the latter, acetone and
propanal being simultaneously formed
(Eltekoff, loc. cit. 11, 409 : see also
Lieben, Monats. 23, 60),

Propylene gives acetone also by direct
oxidation with chromic acid (Berthelot,
Ann. 150, 373).

Or from propylene through acrolein
[101] and pyroracemic or pyrotartaric
acid (see under benzyl alcohol [54 ; E]),
and then as under P below.

Note : — Qenerators of propylene (see under
glycerol [48 ; B to I] and under isopropyl
alcohol [16]) thus become generators of acetone.

Isopropyl alcohol gives acetone di-
rectly by oxidation with chromic acid
(Linnemann, Ann. 140, 178 ; Berthelot,
Comp. Rend. 68, 334). Also by electro-
lysis in sulphuric acid solution (Elbs
and Brunner, Zeit. Elektroeh. 6, 604),
by passing over a heated platinum spiral
(Trillat, Comp. Rend. 132, 1495), or by
pyrogenic contact decomposition by
heated brass (Ipatieff, Ber. 35, 1057).

Propylene bromide may also be con-
verted into allylene (see under benzyl
alcohol [54 ; E]), the latter giving ace-
tone on treatment with a solution of
mercuric bromide or chloride (Kut-
scherofp, Ber. 14, 1541 ; 17, 15). Or
allylene, when dissolved in strong sul-
phuric acid and the product distilled
with water, gives (with mesitylene)
acetone (Schrohe, Ber. 8, 367). At 0°
sulphuric acid with allylene yields only
acetone (Michael and Leighton, Journ.
pr. Ch. [2] 60, 442).

Allylene is formed when the vapour
of propyl alcohol is passed over hot
magnesium and the product decomposed
by water (Keiser and Breed, Ch. News,
71, 118 J Am. Ch. Journ. 18, 328).

Note : — The generators of allylene referred
to under benzyl alcohol [54 ; P ; G ; H ; I,
&c.] thus become generators of acetone : —

194

ALDEHYDES AND KETONES : FATTY GROUP [106 B-E.

glycerol [48] ; malonic acid [Vol. II] and alde-
hyde [92] ; acetoacetic ester [Vol. II] ; allyl iso-
thiocyanate [166] ; P-hydroayiutyric acid ; normal
butyric acid ; citric add ; lactic acid ; isovaleric
acid ; malonic and propionic acids ; tartaric and
racemic acids; isobutyl and amyl alcohols [18; 22].

[C] Isobutyl alcohol [l8] gives ace-
tone among- other products on oxidation
with chromic acid (Kramer^ Ber. T, 352;
^c\\Ti\\dd>,lhkl. 1361). Or from isobutyl
alcohol through isobutylene (see under
tertiary butyl alcohol [19; B]). The
latter gives acetone among other pro-
ducts on oxidation with chromic acid or
potassium permanganate (F. and O.
Zeidler, Ann. 197, 351 ; Wagner, Ber.
21, 1232).

Or indirectly from isobutyl iodide
and potassium cyanide [172] through
the nitrile of isobutylformic acid and
the acid by hydrolysis (Erlenmeyer
and Hell, Ann. 166, 366 ; Schmidt
and Sachtleben, Ann. 193, 92). The
acid on oxidation with dilute alkaline
permanganate gives /3-hydroxyiso valeric
(2-methyl-2-butanolic-3)acid (v. ISIiller,
Ann. 200, 273), and this yields acetone
on oxidation with chromic acid mixture.

Isobutyl alcohol gives allylene when
the vapour is passed over hot magnesium
and the product decomposed by water
(Keiser and Breed, Ch. News. 71, 118 ;
Am. Ch. Journ. 18, 328). From allyl-
ene to acetone as under B.

[D.] From tertiary butyl alcohol [19]
through isobutylene (see under isobutyl
alcohol [is ; A]). Acetone is among
the products formed by passing the
vapour of this alcohol over a heated
platinum spiral (Trillat, Comp. Rend.
132, 1495).

Or from tertiary butyl alcohol and
hydrogen cyanide [172] through tertiary
amyl alcohol (see under formic aldehyde
[91 ; X]), and then as under E below.

Acetone is among the products of
oxidation of tertiary butyl alcohol by
chromic acid mixture (Butleroff, Zeit.

[2] 1, 485).

[E.] From amyl alcohol from fusel
oil [22]. Isobutylene is among the
products of decomposition by passing
through a hot tube (Wurtz, Ann. 104,
249 ; Butleroff, Ann. 145, 277 ; Ipatieff,
Ber. 35, 1053).

Or the amyl alcohol can be converted

into amylene by the usual methods
(Balard, Ann. Chim. [3] 12, 320 ;
Frankland, Ann. 74, 41 ; Wurtz, Ann.
128, 225; 316; Bauer, Journ. pr. Ch.
84, 257 ; Etard, Comp. Bend. 86, 488 ;
Eltekoff, Ber. 10, 1904; Wischne-
gradsky, Ann. 190, 332 : fusel oil
amylene prepared by the action of zinc
chloride contains, in addition to tri-
methylethylene, some isopropylethylene
and a trace of the symmetrical methyl-
ethylethylene, Kondakoff, Journ. Buss.
Soc. 24, 1 13). By the action of strong
sulphuric acid and subsequent hydro-
lysis this amylene is converted into
tertiary amyl alcohol = dimethylethyl
carbinol (Osipoff, Ber. 8, 1 240 ;
Wischnegradsky, loc. cit. 336 ; Konda-
koff, loc. cit. 25, 354), and the latter,
when chlorinated in the presence of
water, yields acetone among other pro-
ducts (Brochet, Ann. Chim. [7] 10,

Amyl alcohol also gives acetone
among the products of its oxidation, or
by passing the vapour over a heated
platinum spiral (Trillat, Comp. Rend.
132, 1495). .

Or fusel oil amylene (trimethylethyl-
ene) may be converted into the bromide
and trimethylethylene glycol (Wurtz,
Ann. Chim. [3] 55, 458 ; Wagner,
Ber. 21, 1235). The latter gives
acetone among the products of its
oxidation by chromic acid mixture
(Flawitzky, Ber. 10, 2240).

Trimethylethylene yields acetone by
oxidation with potassium permanganate,
the glycol being formed as an inter-
mediate product (Wagner, loc. cit.).
Trimethylethylene chlorhydrin from the
hydrocarbon and hypochlorous acid
gives methylisopropyl ketone on heat-
ing with water, or by passing over
heated zinc oxide (Krassusky, Journ.
Russ. Soc. 34, 287). Or the chlor-
hydrin, on treatment with potash, yields
trimethylethylene oxide (Eltekoff, Ibid.
14, 361). This oxide on heating with
lead chloride to 200° gives methyl-
isopropyl ketone (Krassusky, loc. cit.
537). The ketone yields acetone as
below.

Or trimethylethylene bromide on
heating with alcoholic potash gives

106 E-F.]

ACETONE

195

dimethylallylene (3-metliyl- 1 : 2-buta-
diene), which also yields acetone among
the products of its oxidation (Paworsky^
Journ. pr. Ch. [a] 37, 392).

Trimethylethylene bromide on heat-
ing- with water and lead oxide at 150°;
or with water alone, g-ives methyliso-
propyl ketone (Eltekoff, Journ. Russ.
Soc. 10, 215; Niederist, Ann. 196, 36Q;
Nageli, Ber. 16, 2983), and this yields
acetone among- the products of its oxida^
tion by chromic acid.

Trimethylethylene glycol also gives
o-hydroxyisobutyric = 2 -methyl- 2-pro-
panolic acid on oxidation with nitric
acid (Wurtz, Ann. 107, 197), and this
yields acetone as under O.

Or fusel oil amyl alcoliol by conver-
sion into the iodide, isopropylethylene
(Wischnegradsky, Ann. 180, 35^),
isopropylethylene bromide, and the
action of alcoholic potash on the latter
gives isopropylacetylene, which also
yields acetone among the products of
its oxidation (Eltekoff, loc. at. 9, 222 ;
224; Flawitzky and Kryloff, Ibid. IQ,
342). Isopropylethylene gives acetone,
among other products, on oxidation by
potassium permanganate (Wagner, Ber.
21, 1233).

Amyl alcohol gives allylene on pass-
ing the vapour over hot magnesium and
decomposing the product with water
(see above under C). Subsequent steps
as under B.

[P.] Yxoia. glycerol [48], acetone being
among the products formed by distilling
glycerol with lime (Tawilderoff, Ber. 12,
1487), or by oxidation with hydrogen
peroxide (Cotton, Journ. Pharm. 10,
194).

Or from glycerol through allyl iodide
(see under isobutyl alcohol [I8; D]),
propylene by the action of zinc and sul-
phuric acid or mercury and hydrochloric
acid (Berthelot and De Luca, Ann. 92,
306), or of acetic acid and zinc (Linne-
mann, Ann. 161, 54; Gladstone and
Tribe, Ber. 6, 1550; Niederist, Ann.
196, 358), and then as above under B.
Allyl iodide also gives propylene by
treatment with hydriodic acid (Butleroff,
Ann. 145, 271; Malbot, Comp. Rend.
107, 114; Bull. Soc. [2] 50, 449).

Or glycerol can be converted into

allyl alcohol (see under ethyl alcohol
[14 ; G]), and this gives propylene
(with ethylene) by heating with phos-
phorus pentoxide (Behal, Ann. Chim.
[6] 16, 3*^0). Or allyl chloride from
allyl alcohol gives a chlorhydrin by the
action of sulphuric acid (Oppenheim,
Ann. Suppl. 6, 367), and this yields
acetone (with propaldehyde) on heating
with water (Krassusky, Journ. B,uss.
Soc. 34, 287).

Glycerol gives propylene (with allyl
iodide) by the action of iodine and
phosphorus (Berthelot and De Luca,
loc. cit. ; Oppenheim, Ann. Suppl. 6,

354)-

Or from glycerol through allyleiie as
under benzyl alcohol [§4 ; F], and then
as above under B.

Or glycerol can be converted into
allyl bromide (Tollens, Ann. 156, 152 ;
Henry, Zeit. [2] 6, 575 ; Grosheintz,
Bull. Soc. [2] 30, 98), the latter into
tribromhydrin = 1 : 2 : 3-tribrompropane
(Tollens, Ann. 156, 168 : see also under
glycerol [48 ; 4-]), the latter into i : 2-
dibrompropylene by the action of solid
potash or sodium in ethereal solution
(Henry, Ann. 154, 371; Tollens, loc.
cit.), and the dibrompropylene into
'ailene' (CHgiCrCHJ by reduction
in alcoholic solution with zinc (Gustav-
son and Demjanoff, Journ. pr. Ch. 38,
?oi : compare Behal, Bull. Soc. [2] 48,
788). Allene dissolves in sulphuric aci 1,
and the product gives acetone on dis-
tillation with water (G. and D., loc. cit.).

Allyl bromide also gives propylene
by the action of zinc dust in alcoholic
solution (Wolkoff and Menschutkin,
Ber. 31, 3072), and this yields acetone
as above.

Glycerol gives propylene glycol
directly when the monosodiura com-
pound is distilled (Belohoubek, Ber.
12, 1873; Morley and Green, Trans.
Ch. Soc. 47, 132), and this yields acetone
as under B.

Propylene glycol may also be obtained
from glycerol by the action of sodium
amalgam on the monochlorhydrin (Lou-
ren^o, Ann. 120, 91), or by the action
of acetyl bromide on glycerol, and
reduction of the product (glycerol-aceto-
bromhydrin) with coppered zinc and

o 2

196

ALDEHYDES AND KETONES : FATTY GROUP [106 F-K.

hydrochloric acid (Hanriot, Ann. Chim.

[5] 17. 84).

Or from glycerol through crotonic
acid and tertiary heptyl alcohol (see
below under L).

Or from glycerol through glyceric
and pyroracemic acids (see under benzyl
alcohol [54 J F]), and then as under
P below.

[G.] Acetic aldehyde [92] gives acetone
when the vapour is passed over red-hot
lime (Schloemilch, Zeit. [2] 5, "i"^^)-
Or indirectly from aldehyde through
crotonic acid and tertiary heptyl alcohol
(see below under L). Or from aldehyde
through butyroehloral and allylene (see
under benzyl alcohol [54 j H]), and then
as above under B.

[H.] Isovaleric aldehyde [95] on treat-
ment with phosphorus pentachloride and
decomposition of the product with alco-
holic potash gives isopropylacetylene =
3-methyl-i-butine, and this yields ace-
tone among the products of its oxidation
by chromic acid mixture (Bruylants,

Ber. 8, 407 ; 413)-.

[I.] From propionic acid [Vol. II]
through tertiary amyl alcohol by the
interaction of propionyl chloride and
zinc methyl and decomposition of the
product with water (Popoff, Ann. 145,
293; Jermolajeft, Zeit. [2] 7, 275;
Wischnegradsky, Ann. 190, '>i^(>), and
then as above under E.

Or propionic acid may be brominated
(see under aldehyde [92 ; E]), and the
a-brompropionic aci I converted into
a-brompropionyl bromide, which, by
interaction with zinc methyl and de-
composition of the product with water,
gives dimethylisopropyl carbinol (Kas-
chirsky, Journ. Russ. Soc. 13, 82). The
latter yields acetone among other pro-
ducts on oxidation by potassium per-
manganate (see below under K).

Or from propionic acid through pyro-
racemic acid (see under benzyl alcohol
[54 ; O]), and then as under P below.

Or from propionic and acetic acids,
alcohol [14] and potaasium cyanide [l72]
through a-methyl-3-cyanosuccinic ester
and citraconic acid (see under benzyl
alcohol [54; M]), and then as under
Q below.

Or from propionic acid through pro-

pionamide and propionitrile (Dumas,
Malaguti, and Leblanc, Ann. 64, 334),
and then as below under S.

[J.] Acetoacetic acid [Vol. II] splits
up readily into acetone and carbon
dioxide on heating (Ceresole, Ber. 15,
1328).

Or indirectly from acetoacetic ester
through acetonedicarboxylic acid (see
under orcinol [75 ; D]), and then as
under Q below.

Or from acetoacetic ester and hydrogen
cyanide [172] through hydroxypyrotar-
taric acid and citraconic acid (see under
benzyl alcohol [54; M, note]), and then
as under Q below.

Or from acetoacetic ester through
methylacetoacetic ester and mesaconie
acid (see under benzyl alcohol [54; l]),
and then as under Q below.

Or from acetoacetic ester through
isonitrosoacetone and pyroracemic acid
[54 ; l], and then as under P below.

Or from acetoacetic ester and a-brom-
propionic ester through /3-methylaceto-
succinic ester and pyrotartaric acid as
under benzyl alcohol [54; l], and from
the latter through allylene \lbid. P ; M ;
and N], and as above under B.

Or from acetoacetic ester, chloracetie
ester, and methyl alcohol through aceto-
succinic ester, the a-methyl-derivative,
pyrotartaric acid, and allylene [54; I].

Or from acetoacetic ester through
the ^-chlorcrotonic acids, tetrolic acid
and allylene {Ibid.).

[K.] Isobutyric acid [Vol. II] gives
acetone when heated with chromic acid
solution at 140° (Popoff, Zeit. [2] 7, 4).

Or on oxidation with alkaline per-
manganate isobutyric acid gives a-
hydroxy isobutyric ( 2 -methyl- 2 -propan-
olic) acid, which yields acetone as below
under O.

Note : — Ketones which yield isobutyric acid
on oxidation are thus likely to give acetone,
e.g. diisopropyl ketone from calcium iaobutyrate
or the corresponding diisopropyl carbinol
(Popoff, Ber. 6, 1255 ; Munch, Ann. 180, 327 ;
333)-

Methylisopropyl ketone from iso-
butyryl chloride and zinc methyl
(Behal, Ann. Chim. [6] 15, 284) gives
j8-dichlorisopentane on treatment with
phosphorus pentoxide, and this by alco-

106 KtM.]

ACETONE

197

holic potash yields isopropylacetylene
{Tbid. 0,^6), which gives acetone on
oxidation (see under E).

Note :^Methylisopropyl ketone is obtained
also from aeetoacetic ester and isobutyryl
chloride through isobutyrylacetoacetic ester,
and the action of hydrochloric acid on the latter
at 140-150° (Bouveault, Comp. Rend. 131, 45).

Ethylisopropyl ketone from isobutyryl
chloride and zinc ethyl (Butleroff, Ann.
189, 44 ; Pawloffj Journ. Russ. Soc. 8,
243 ; Wagner, Ibid. 16, 697) gives
acetone among the products of its oxida-
tion by chromic acid.

Dimethylisopropyl carbinol from iso-
butyryl chloride and zinc methyl
(Prianischnikoff, Zeit. [2] 7, 275) gives
acetone among the products of its
oxidation by potassium permanganate
(Wagner, Journ. pr. Ch. [2] 44, 310).
Or dimethylisopropyl carbinol yields
tetramethylethylene and pinacone (see
under tertiary butyl alcohol [l9 ; E]).
The latter gives acetone on oxidation
with chromic acid mixture.

A mixture of calcium isobutyrate and
heptoate [Vol. II] gives isopropylhexyl
ketone on dry distillation, and this
yields acetone among the products of
its oxidation by chromic acid (Fuchs,
Journ. Russ. Soc. 7, 334)'

Isobutyric acid also gives the a-
bromo-acid on bromination (Markowni-
koff, Ann. 153, 229; Hell and Wal-
dauer, Ber. 10, 448 ; Michael and
Graves, Ber. 34, 4043), and the latter,
on heating with water or barium
hydroxide or sodium carbonate solution,
yields the a-hydroxy-acid (Markowni-
koff, loc. at. ; Fittig, Ann. 200, 70),
from which acetone can be produced as
below under O.

Or a-bromisobutyric ester and alde-
hyde [92] condense under the influence
of zinc to form trimethylethylenelactic
= 2 : 2-dimethyl - 3 - butanolic - 1 - acid
(ester) (Ephrussi and Reformatsky,
Journ. Russ. Soc. 28, 600). The acid
gives tertiary amyl alcohol (with tri-
methylacrylic acid) on distillation with
dilute sulphuric acid (Giljaroff, Jb\d.
508). The amyl alcohol yields acetone
as above under E.

[L.] From normal bnfyric acid [Vol.
JI] and methyl alcohol [13] through the

tertiary heptyl alcohol produced by the
interaction of a-brom-n-butyryl bromide
and zinc methyl and decomposition of
the product with water (Kaschirsky,
Journ. Russ. Soc. 13, 89). This heptyl
alcohol gives acetone among the pro-
ducts of its oxidation. Or n- butyric
acid may be converted into crotonic
acid (see under benzyl alcohol [54; K])
and allylene \Ibid. G], and then into
acetone as above under B.

Note : — Crotonic acid gives a- (with some iS-)
brombutyric acid on combination with hydro-
gen bromide (Hemilian, Ann. 174, 325). The
generators of crotonic acid referred to under
benzyl alcohol [54 ; G ; H, &c.] thus become,
with methyl alcohol, generators of acetone.

[M.] From isovaleric acid [Vol. II]
and ethyl alcohol [l4] through ethyl -
isobutyl ketone (2-methyl-4-hexanone),
which is obtained by passing carbon
monoxide over a mixture of sodium
isovalerate and ethylate at 160° (Loos,
Ann. 202, 327). The ketone gives
acetone among the products of its oxi-
dation by chromic acid mixture.

Ethylisobutyl ketone is also obtained
from the same materials by the inter-
action of isovaleryl chloride and zinc
ethyl (Wagner, Journ. pr. Ch. [2] 44,

^74). ...

Or isovaleric acid, by the action of
nitric acid, gives 2 : 2-( = /3) dinitropro-
pane, which on reduction by tin and
hydrochloric acid yields acetone (Bredt,
Ber. 15, 2322; Meyer and Locher, Ann.
180, 147).

Also from isovaleric acid and normal
propyl alcohol [l5] through propyliso-
butyl ketone (2-methyl-4-heptanone) by
the interaction of isovaleryl chloride and
zinc propyl (Wagner, Journ. Russ. Soc.
16, 668). This ketone also gives ace-
tone among the products of its oxida-
tion by chromic acid mixture.

Or from isovaleric acid through hy-
droxy pyrotartaric acid and citraconic
acid (see under benzyl alcohol [54 ; M,
note]), and then as under Q below.

Or from isovaleric acid and ethyl
alcohol through a-bromisovaleric ester,
/3-dimethylacrylic acid by heating the
latter with quinoline or diethylaniline
(see under isobutyl alcohol [18 ; C]),
and oxidation of the acid with potassium

198

ALDEHYDES AND KETONES : FATTY GROUP [106 M-R.

permanganate followed by potassium
dichromate and sulphuric acid (Crossley
and Le Sueur, Trans. Ch. Soe. 75, 164).

[N,] From lactic acid [Vol, II] and
meihyi alcohol [13] through a-brompro-
pionic acid by heating lactic acid with
saturated bromhydric acid (Kekule, Ann.
130, 16), and then dimethylisopropyl
carbinol by the interaction of a-brom-
propionyl bromide and zinc methyl, &c,,
as above under I and K.

Or from lactic acid through pyrora-
cemic acid (see under benzyl alcohol
[54 ; P]), and then as below under P.

Or from lactic acid through citra-
conic acid (see under benzyl alcohol
[54 ; M, note]) and /3-chlorcitramalic
acid as under Q below.

[O.] From oxalic acid [Vol. II] and
mt'thyl alcohol [13] through a-hydroxy-
isobutyric (3-methyl-2-propanolic) acid
by the interaction of zinc methyl and
dimethyl oxalate (Frankland arid Duppa,
Ann. 133, 80 ; 135, 25). The acid gives
acetone on oxidation with chromic acid
mixture, or on fusion with caustic alkali j
also on electrolysis of the potassium salt
(v. Miller and Hofer, Ber. 27, 468), on
decomposition of the silver salt by
iodine (Herzog and Leiser, Monats. 22,
357), or on heating with phosphorus
pentoxide (Bischoff and Walden, Ann.
279, III).

Or from oxalic and propionic acids
and alcohol through methyloxalacetic
ester, /3-methylmalic acid, and citra-
eonic acid (see under benzyl alcohol [54 ;
M, note]), and then as under Q below.

[P.] Tartaric acid [Vol. II] gives
acetone among the products of dry dis-
tillation (Volckel, Ann.-8&, 57), or of
oxidation by hydrogen peroxide (Cotton,
Journ. Pharm. 10, 195).

Or from tartaric (or racemic) acid
through pyroracemic acid (see under
benzyl alcohol [54 ; N]), the calcium
salt of which gives acetone on distilla-
tion (Hanriot, Bull. Soc. [2] 43, 417;
45, 81). A mixture of potassium pyro-
racemate and acetate yields acetone on
electrolysis (Hofer, Ber. 33, 654).

Or from tartaric acid through pyro-
tartaric acid and ally 1 en e, as under
benzyl alcohol [54 ; N], and then as
under B above.

[Q.] Citric acid [Vol. II] gives ace-
tone among other products when heated
with strong sulphuric acid (Wilde, Ann.
127, 170)^ on dry distillation with
glycerol (Clermont and ChautardjComj).
Rend. 105, 520), or on heating the
sodium salt with lime (Freydl, Monats.
4, T51). Citric acid yields acetone
among the products of dry distillation or
of oxidation by potassium permangan-
ate, by sulphuric acid and manganese
dioxide (Robiquet, Berz^ Jahresber. 18,
502; P^an de St. Gilles, Ann. Chim.
[3] 55, 374), or by hydrogen peroxide
(Cotton, Journ. Pharm. 10, 195)-

Acetone isformed by adding potassium
permanganate solution drop by drop to
a boiling solution of citric acid, or by
exposure of citric acid to air in presence
of iron or ferric chloride ; also from
Kammerer^s iron citrate under similar
conditions (Sabbatani, Atti Accad. Sci.
Torino, 35, 678 ; Journ. Ch. Soc. 78,
Abst. I, 536).

Or citric acid may be converted into
acetonedicarboxylic acid (see under or-
cinol [75 ; O]), and this gives acetone
on heating at 135° per se or by boiling
with water, acid, or alkaline solutions.

Or from citric acid through citraconic
acid (see under benzyl alcohol [54 ; M])
and /3-chlorcitramalic acid by the action
of hypochlorous acid or chlorine on the
latter (Gottlieb, Ann. 160, loi ; Carius,
Ann. 126, 204 ; Melikoff and Feldmann,
Ann. 253, 87). The chloro-acid gives
acetone on heating with water at iio-
120°.

Mesaconic acid^ the isomeride of
citraconic acid, also gives /3-chlorcitra-
malic acid when a solution of the sodium
salt is chlorinated (Morawski, Journ.
pr. Ch. [2] 18, 392).

Or from citraconic acid through allyl-
ene as under benzyl alcohol [54 ; M],
and then as above under B.

[R.] From malonic and propionic acids
[Vol. II] through propanetricarboxylic
ester, citraconic, and mesaconic acid
(see under benzyl alcohol [54 ; M, note]),
and then as above under Q.

Or from malonic acid and acetic alde-
hyde [92] through crotonic acid and
allylene (see under benzyl alcohol [54;
G]), and then as above under B.

106 R-AA-]

ACETONE

199

Or malonic ester, by the action of
sodium at 70-90°, g-ives acetonetriear-
boxylic ester, and this yields acetone on
heating" with strong acids (Willstatter,
Ber, 32, 1274).

[S.] From methyl and ethyl alcohoU [13 ;
14] and hydrogen cyanide [172] through
propionitrile (Pelouze, Ann. 10, 249 ',
Williamson, Phil. Mag. [4] 6, 205 ;
Buckton and Hofmann, Journ. Ch. Soc.
9, 250 ; Rossi, Ann. 159, 79). The
latter, on treatment with sodium in
ethereal solution, gives a product which
by interaction with methyl iodide fol-
lowed by aqueous hydrogen chloride
yields ' trimethylpyrolone ' (C^Hj^NO).
The latter, on heating with strong
aqueous hydrogen chloride at 140-150°,
gives ethylisopropyl ketone, from which
acetone is obtained by oxidation as under
K (E. V. Meyer, Journ. pr. Ch. [2] 38,
336 ; Hanriot and Bouveault, Com p.
Rend. 108, 1171 ; Bull. Soc. [3] 1, 549).

Or from ethyl and methyl alcohols
through chloral and dimethylisopropyl
carbinol (see under tertiary butyl alcohol
[19 ; G]), and then as above under K.

Or from methyl alcohol and hydrogen
cyanide through methyl cyanide (ace-
tonitrile). The latter interacts with
magnesium methobromide to form an
intermediate compound, which is de-
composed by acids with the formation
of acetone (general method of Blaise :
Comp. Rend. 132, 38).

Or from ethyl alcohol through iodo-
form, acrylic acid, a-chlorlactic acid, and
glyceric acid (see under benzyl alcohol
[54 ; l]). From the latter through
pyrotartaric acid and allylene as under
benzyl alcohol [54; F and E], and above
under B; or through pyroracemic acid as
under benzyl alcohol [54; E], and above
under F and P. Allylene is formed
when the vapour of ethyl alcohol is
passed over heated magnesium and the
product decomposed by water (Keiser
and Breed, Ch. News, 71, 118; Keiser,
Am. Ch. Journ. 18, 328).

Or from ethyl alcohol through pro-
pionitrile as above, and from the latter
through aa -dichlorpropionic acid and
pyroracemic acid as under benzyl alcohol
[54 ; l], and then as above under P.

Or from ethyl alcohol and hydrogen

cyanide through ethylene, vinyl chloride,
chloracetaldehyde,/3-chlorlactic acid, and
glyceric acid (see under benzyl alcohol
[54 j A]). From the latter, as above,
through pyrotartaric acid and allylene,
or through pyroracemic acid.

Note : — Other methods of passing from ethyl
alcohol through chloracetaldehyde to glyceric
acid are given under benzyl alcohol [54 ; I].

Generators of ethylene thus become (with
hydrogen cyanide) generators of acetone
through glyceric acid.

[T.] From ji-Jiydroxybulyric ac'.d [Vol.
II] through cro tonic acid and allylene
(benzyl alcohol [54; L]), and then as
above under B.

[U.] From erythritol [50] dsnA. formic
acid [Vol. II] through crotonic aldehyde
[102], crotonic acid and allylene (see
under n-butyl alcohol [17; I], and benzyl
alcohol [54; G]), and then as above
under B.

[v.] Mtthylhepfenone [ill] gives ace-
tone among the products of its oxida-
tion with chromic and sulphuric acids
(Tiemann and Semmler, Ber. 28, 2128).

[W.] Bimethylheptenol [35] gives ace-
tone among the products of its oxidation
by chromic acid mixture (Barbier, Comp.
Rend. 126, 1424).

[X.] Ethane [14; D] and carbon
monoxide give an acetone (C3HgO) when
submitted to the action of the silent
electric discharge in a cooled apparatus
(De Hemptinne, Bull. Acad. Roy. Belg.
[3] 34, 275). The product has not
been identified specifically as 2-pro-
panone.

[Y.] Citronellal [105] and citronellol
[38] give acetone (with ^-methyladipic
acid) on oxidation with potassium per-
manganate, followed by potassium di-
chromate and sulphuric acid (Tiemann
and Schmidt, Ber. 29, 908; Barbier and
Bouveault, Comp. Rend. 122, 673 : see
also Harries and Schauwecker, Ber. 34,
2981).

[Z.] Pulegone [128] gives acetone
among the products of its decomposition
by heating with formic acid (Wallach,
Ann. 289, 338), or by oxidation with
potassium permanganate.

[AA.] Dextrose [l54] gives acetone
among the products of dry distillation
(Tollens, ' Handbuch d. Kohlenhydrate,^

200 ALDEHYDES AND KETONES : FATTY GROUP [lO0 AA-107 A.

I, 46), and among the products o£ oxida-
tion by hydrogen peroxide(Cotton, Journ.
Pharm. 10, 195), or of dry distillation
with lime (Pereire and Guignard, Fr.
Pat. 316060 of 1901; Journ. Soc. Ch.
Ind. 21, 1096).

[BB.] From aconitic acid [Vol. II]
through itaconic acid (Pebal, Ann. 98,
94), allylene (see under benzyl alcohol
[54; M]), and then as above under B.

[CO.] From mann'itol [5l] through
acrolein [lOl] and acrylic acid (see under
benzyl alcohol [54; B and AA]), and
then as above under S.

Acetone is among the products of
fusion of mannitol with alkali (Gott-
lieb, Ann. 52, 132), and of oxidation by
hydrogen peroxide (Cotton, Journ.
Pharm. 10, 195).

[DD.] Isohutyric aldehyde [94], on
treatment with caustic potash, forms a
trimeric polymeride (Pfeiffer, Ber. 5,
700 ; Urech, Ber. 12, 191 ; W. H.
Perkin, junr.. Trans. Ch. Soc. 43, 91),
which, on bromination (in CS2) and by
the action of heat on the polymeride, gives
a-bromisobutyric aldehyde = 3-methyl-
3-brompropanal. The oxime of the
latter, on heating with acetic anhydride,
yields a nitrile which is decomposed by
sodium carbonate solution with the for-
mation of acetone (Franke, Monats.
21, 205 ; 210).

Or isohutyric and acetic aldehydes con-
dense to form an aldol (CgH^gOg), which,
on oxidation with potassium permangan-
ate, gives trimethylethylene lactic acid
(Lilienfeld and Tauss, Monats. 19, 81).
From the latter^ through tertiary amyl
alcohol, &c., as above under K and E.

Or isohutyric and formic aldehydes
condense to form a glycol, which gives
methylisopropyl ketone among the pro-
ducts of decomposition by heating with
water (Lieben, Monats. 23, 60). From
the ketone as under K above.

Or isohutyric aldehyde condenses in
contact with alkali with the formation
of diisopropylglycol = 2:2: 4-trimethyl-
pentanediol, and this gives diisopropyl
ketone on oxidation with potassium per-
manganate (Fossek, Monats. 4, 664 ;
Brauchbar, Ihid. 17, 641 ; Franke, Ibid.
673). The ketone yields acetone on
further oxidation as under K above.

[E£.] Phloroglucinol [86] gives ace-
tone among other products on heating
with 25 per cent, caustic potash solu-
tion at 160° (Combes, Bull. Soc. [3] 11,

[PF.] Chelidonic acid [Vol. II] gives
acetone (and oxalic acid) on heating
with aqueous alkali (Lieben and Haitin-
ger, Ber. 16, 1259).

[GG.] Menthone [129] gives an oxime
and the latter a nitrile, which can be
converted into an aldehyde isomeric
with citronellal. The aldehyde, on oxida-
tion, yields first menthonic acid and
finally (^-methyladipic acid and) ace-
tone (Wallach, Ann. 278, 302; 296,

131)-

[HH.] Acetyl carhinol [43] gives ace-
tone when reduced in acid solution in
the cold (Kling, Comp. Rend. 135,

970).

107. Methyl-n- amyl Ketone ;
2-Heptanone.

CH3.CO.[CH2]4.CH3

Natural Sources.

Occurs in small quantity in oil of
cloves (SchimmePs Ber. April, 1897,
and April, 1902 ; Ch. Centr. 1902, 1,
1058 : see also Erdmann^ Journ. pr. Ch.

■f

[2] 56, 155 ; Gerber, Mon. Sci. [4]
11, 880), and in Ceylon oil of cinnamon
(SchimmeFs Ber. April, 1902 ; Wal-
baum and Hiithig, Journ. pr. Ch. [2]
66, 47).

Synthetical Processes.

[A.] Normal hejytane [2], on chlorina-
tion, gives (with n-heptyl chloride) 2-
chlorheptane (Pelouze and Cahours, Jah-
resber. 1863, 528; Schorlemmer, Ann.
136, 266 ; Morgan, Ann. 177, 307),
from which the secondary alcohol (2-
heptanbl) can be obtained by the usual
methods (Schorlemmer, Ann. 127, 315 ;
161, 278; Journ. Ch. Soc. 26, 319);
Morgan, loc. cit.). The alcohol gives
the ketone on oxidation (Schorlemmer,
Ann. 161, 279).

Or n-heptane may be nitrated and the
2-nitroheptane reduced to methjlamyl

107 A-109.]

METHYL-N-AMYL KETONE

201

ketone (Konowaloff, Journ. Russ. Soc.
25,487; Bar. 26, Ref. 881).

[B.] Heptoic aldehyde or oenant/wl
[97] by the action of phosphorus penta-
chloride gives i : i -dichlorheptane =
cenanthylidene chloride (Limpricht,Anni
103, 81), which by the extreme action
of alcoholic potash is converted into
6-(a)-heptine = cenanthine or cenanthyl-
idene {Ibid. 84 ; Rubien, Ann. 142, 294 ;
Welt, Ber. 30, 1496). The latter, on
dissolving- in sulphuric acid and dis-
tillation with water, yields 2-heptanone
(B^hal, Ann. Chim. [6] 15, 270).

The ketone is formed also by heating
the heptine with acetic acid to 280°
and decomposing the product with water
(Behal and Desgrez, Comp. Rend. 114,
1074 : see also Desgrez^ Ann. Chim.
[7] 3, 228, and Moureu and Delange,
Comp. Rend. 131, 710; 800).

Or the sodium derivative of heptine
interacts with chlorocarbonic ester (from
carbon oxy chloride and the alcohol) to
form amylpropiolic ester, the free acid
of which, on heating with alcoholic
potash, gives hexoylacetic acid. The
latter decomposes readily at 60° into
carbon dioxide and methyl-n-amyl ke-
tone (Moureu and Delange, loc. cit.
132, 1121).

Or the free acid on esterification with
hydrogen chloride and an alcohol gives
amyl-/3-chloracrylie ester, and this also
yields methyl-n-amyl ketone on treat-
ment with alcoholic potash (Ibid.).

Or the sodium derivative of heptine
interacts with ethjlformate to form amyl-
propiolic aldehyde, CH3[CH2]4 . C :
C. CHO, and this gives methyl-n-amyl
ketone among the products of its de-
composition by boiling aqueous alkali
{Ibid. 133, 96).

[C] From n-heptyl alcohol [26] and
palmitic acid [Vol. II]. Heptyl palmi-
tate gives n-heptylene on heating to
350° in an atmosphere of carbon dioxide,
and the heptylene combines with brom-
ine to form a dibromide (i : 2-dibrom-
heptane), which, by the action of alco-
holic potash^ yields heptine = n-amyl-
acetylene (Welt, loc. dit. 1493). From
heptine as above under B.

108. Methyl-n-heptyl Ketone;
2-19'onanoue.

CH3.CO.[CH,]3.CH3

Natural Soueces.

Occurs to the eitent of about 5 per
cent, in oil of rue from Unta graveoleus
(Thoms, Ch. Centr. 1901, 1, 524; Ber.
deut. pharm. Gesell. 11, 3; Houben,
Ber. 35, 3587). This ketone is the
chief constituent of Algerian oil of rue
(v. Soden and Henle, Pharm. Zeit.
46, 277; 1026; Pharm. Journ. 67,
1619; Ch. Drug. 60, 304; Power
and Lees^ Trans. Ch. Soc. 81, 1588).
Has been found also in oil of cloves
(SchimmeFs Ber. April, 1903; Ch.
Centr. 1903, 1, 1086).

Synthetical Processes.

[A.] Prom acetic and n-octoic acids
[Vol. II] by distilling a mixture of the
barium salts (Thoms, loc. cit.).

[B.] From n-heptyl [26] and n-propyl
alcohol [15], a mixture of which on heat-
ing with sodium to 230° gives a decanol
= 8-methyl-9-nonanol. The latter, on
fusion with alkali, yields a decoic acid,
CH3 . [CHJe . CH(CH3) . COOH,
which on oxidation with chromic acid
gives the above ketone among other
products (Guerbet, Comp. Rend. 135,
172; Ann. Chim. [7] 27, 67).

109. Methyl-n-nonyl Ketone;
2-Undecanone.

CH3.CO.[CH,]3.CH3

Natural Sources.

Occurs as the principal constituent
of oil of rue from Ruta graveolens (Gre-
ville Williams, Phil. Trans. 1858, 1, 99 ;
Hallwachs, Ann. 113, 109; Harbordt,
Ann. 123, 293 ; Giesecke, Zeit. [2] 6,
429 ; Carette, Journ. Pharm. [6] 10,
255 ; Thoms, Ch. Centr. 1901, 1, 524;
Houben, Ber. 36, 3590) ; in Algerian
oil of rue (v. Soden and Henle, Ch.
Centr. 1901, 1, 1006; Pharm. Zeit. 46,

302

ALDEHYDES AND KETONES: FATTY GROUP [109-111 A.

377; J036; Ch. Drug. 60, 304;
Power and Lees, Trans. Ch. Soc. 81,
1588).

The ketone occurs also in the essen-
tial oil of lime leaves from Citrus llmetta
(Watts, Trans. Ch. Soc. 49, 316).

Synthetical Processes.

[a.] From octyl alcohol [28] and
acetoacetic acid {ester) [Vol. II]. The
alcohol is converted into n-octyl iodide
(Zincke, Ann. 152, 2 ; Moslinger, Ann.
185, 55), and the latter by interaction
with sodio-acetoacetic ester gives octyl-
acetoacetic ester (Guthzeit, Ann. 204,
2), which, on decomposition with alco-
holic potash, yields the ketone {Rirl. 4).

[B.] From acetic and decoic acids
[Vol. II] by the dry distillation of
a mixture of the calcium salts (Gorup-
Besanez and Grimm, Ann. 157, 275;
Ber. 3, 518).

110» Methyl-n-decyl Ketone ;
2-Dodecanoue.

CH3.CO.[CHJg.CH3

Natural Source.

Possibly in oil of rue with the pre-
ceding ketone (references as under
undecanone [l09] above).

Synthetical Processes.

[A.] From acetic and lauric acids
[Vol. II] through methylundecyl ketone
(2-tridecanone) by distilling a mixture
of the barium salts (Krafft, Ber. 12,
1 667). This ketone on oxidation gives
(with acetic acid) undecanoic acid {Ibid.),
the barium salt of which, on distillation
with barium acetate, yields 2-dodecanone
{Ibid. 15, 1708).

Note : — The identity of the natural with the
artificial product requires confirmation.

111. Methylheptenone ;
2-]M[etliyl-2-heptene- 6-one.

(CH3)2 : C : CH . CH2 . CH^ . CO . CH3

Note : — For constitution see Tiemann and
Semmler, Ber. 26, 2721; 28, 2128; Harries,
Ber. S5, 1 179.

Natural Sources.

In lemon-grass oil (Barbier and
Bouveault, Comp. Rend. 118, 983 j
Bertram and Tiemann, Ber. 32, 834),
in oil of Mexican 4ignaloe^ (SchimmeFs
Ber. April, 1892; Oct. 1894; Barbier
and Bouveault, loc. cit. 121, 168), and
in citronella oil (Schimmel's Ber. Api-il,
] 895). In oil of lemon {Ibid. Oct. 1 902 ;
Ch. Centr. 1902, 2, 1207).

The ketone is probably present in
other essential oils containing geraniol,
linalool, and citral (see Tiemann, Ber.
31, 3286).

Synthetical Processes.

[A.] From methyl and ethyl alcohols
[13 ; 14], acetic and propionic acids
[Vol. II], and acetone [IO6]. Di-
methylethyl carbinol is prepared by
the interaction of zinc methyl and
propionyl chloride (Popoff, Ann. 145,
292 ; Jermolajeff, Zeit. [2] 7, 275 ;
Wischnegradsky, Ann. 190, 336). On
bromination this alcohol gives as chief
product the amylene bromide, (0113)2:
CBr . CHBr . CH3 ^ 2 : 3-dibrom-3-
methylbutane, which by the extreme
action of alcoholic potash is converted
into dimethylallylene = 3-methyl- 1 : 2-
butadiene (see under acetone [IO6 ; E],
and Ipatieff, Ber. 29, Ref. 91). The
latter, on combination with hydrogen
bromide, gives the amylene bromide,
(CHs)^ : CBr . CHg . CH.Br = ^-di-
methyltrimethylene bromide = i^ : ^^-
dibrom-3-methylbutane (Ipatieff, loc. cit.
92). The latter reacts with sodio-
acetylacetone to form a diketone,
(CHg)^ : C : CH . CH2 . CH(CO . CI^^,
which, on decomposition with strong
caustic soda solution, yields (with acetic
acid) a small quantity of methyl-
heptenone (Barbier and Bouveault,
Comp. Rend. 122, 1423).

Note : — Acetylacetone is obtained by the
action of sodium on a mixture of acetone and
ethyl acetate (Claisen and Ehrhardt, Ber. 22,
101 1 ; also Germ. Pat. 49542 of 1S99 : see also
under n-primary amyl alcohol [20 ; B and C]).

The dimethylethyl carbinol may also
be prepared from the amyl alcohol of
fusel oil [22] through the correspond-

Ill A-113.J

METHYLHEPTENONE

203

ing amylenc (see under acetone [106 ;
E]). Or the fusel oil amylene (tri-
methylethylene) may be combined
directly with bromine to form 2:3-
dibrom-3-methylbutane (Wurtz, Ann*
Chim. [3] 55, 458 ; Bauer, Bull Soc.
2, 149), and the latter treated as above.
Or fusel oil arayl alcohol may be
converted into isopropylacetylene (as
under acetone [IO6; E]), and the latter
into dimethylallylene by heating with
alcoholic potash to 150° (Faworsky,
Jouvn. pr. Ch, [2] 37, 392). Subsequent
steps as above.

Or from ethyl alcohol and acetic acid
through acefoacetic ester [Vol. Il] and
the above dimethyltrimethylene brom-
ide. The latter interacts with sodio-
acetoacetic ester and sodium ethoxide
to form dimethylallylacetoacetic ester,
which, on heating with barium hydrox-
ide solution or dilute alcoholic potash,
gives methylheptenone (Ipatieff, Ber.
34, 594).

Or from ethyl alcohol, acetic acid,
and acetone through acetopropyl alco-
hol by the action of sodium ethylate
on acetoacetic ester and ethylene brom-
ide, and decomposition of the product
(bromethylacetoacetic ester) by boiling
with dilute hydrochloric acid (W< H.
Perkin, junr., and Freer, Trans. Ch.
Soc. 51, 833; Lipp, Ber. 22, 1197).
Acetopropyl alcohol is converted by the
action of fuming hydriodic acid into
the corresponding iodide, CH3.CO.
[CH^Ja . CHgl ; the latter, by the action
of zinc and acetone and the decom-
position of the intermediate product
with water, into the tertiary alcohol,
CH3 . CO . [CHaJa . C(CH3)2 . OH ; the
tertiary alcohol into the oxide by dry
distillation, and then into the iodide,
CH3.CO.[CH2]3.C(CH3),.I, by the
addition of hydrogen iodide. The
tertiary iodide gives methylheptenone
by the action of caustic alkali in dilute
solution (Verley, Bull. Soc. [3] 17, 122).

[B.] hovaleric aldehyde [95] and
acetone [106] condense in the presence
of alkali to foi-m methylheptenone
(Leser, Bull. Soc. [3] 17, 108 : accord-
ing to Tiemann, Ber. 31, 817, note 5,
this productis not a pure ketone : seealso
Tiemann and Kriiger, Ber. 28, 2115).

[C] Cineole [40] on oxidation with
potassium permanganate gives cineolic
acid, C.pHjj.Pg (Wallach and Gilde^
meister, Ann. 246, 268), the anhydride
of which on dry distillation yields
methylheptenone (Wallach, Ann. 258,
325). The latter is identical with the
natural product (Tiemann and Semmler,
Ber. 28, 2126, note i ; also SchimmeFs
Ber. Oct. 1 894).

[D.] B'methylheptenol [35] gives me-
thylheptenone among the products of
its oxidation by chromic acid mixture
(Barbier, Comp. Rend. 126, 1424: see
also SchimmeFs Ber. Oct. 1898, and
Tiemann, Ber. 31, 2991).

[E.] Cltral [104] gives methyl-
heptenone (with acetic aldehyde) on
boiling with sodium carbonate solution
(Verley, Bull. Soc. [3] 17, 175).

[F.] Geraniol [36], on heating with
strong alcoholic potash at 150°, gives
methylheptenol, and this yields methyl-
heptenone on oxidation (Tiemann, Ber.
31, 2989 ; 32, III).

112. Fhorone ;
2 ; 6-Dinietliyl-2 : 5-heptadieuone-4<

(CHa)^ : C : CH . CO . CH : C{C}1.^\

A phorone (CgHj^O) is said to have
been obtained from glycerol by bacterial
fermentation (hay bacilli : Schulze, Ber.
15, 64). This has been regarded as
possibly identical with the phorone
obtained from acetone [IO6] by heating
with lime or with hydrochloric acid
followed by alcoholic potash (Fittig,
Ann. 110, 32; Baeyer, Ann. 140, 301 :
also 61; B,p. 126). The phorone obtained
byFittig^s method is isophorone (Bredt
and Riibel, Ann. 289, 10; 299, 160).

The identity of the biochemical with
the synthetical product has net been
fully established.

113. Diacetyl; Dimethyldiketone ;
Diketobutane ; Butadiene.

CH3.CO.CO.CH3

Natural Soukces,

This diketone has been found in
aqueous distillates from oil of caraway
(Schimmel's Ber. Oct. 1899; Ch. Centr.

204

ALDEHYDES AND KETONES: FATTY GROUP [113-0.

1899, 2, 880), from vetiver oil from
Andropogon muricatus, E. and W. Indies,
Brazil, &c. {Ibid. April, 19C0 ; Ch<
Centr. 1900, 1, 907), and from oil of
bay (Ibid. April, 1901), Occurs also
in the lower boiling-point fraction of
oil of savin from Juniperus sabina {Ibid.
Oct. 1900; Ch. Centr. T900, 2, 970),
in the cohobation water of the same
oil, and in the distillation water of
W. Indian sandal-wood oil {IbkL April,
1903; Ch. Centr. 1903, 1, 1086).

Note :— It has not yet been proved that
diacetyl pre-exists ready formed in these oils.

Synthetical J*rocesses.

[A.] From methyl alcohol [13] and
acetoacetic ester [Vol. II] through
isonitrosomethylethyl ketone, &c., or
through acetosuccinic ester, &c., as
under quinol [71; O]. Or through
y-brom-methylacetoacetic ester and
tetrinic acid, or through Isevulic acid
{Ibid.). Or through pyroracemic acid,
&c. {Ibid. DD).

Or from methyl alcohol and aceto-
acetic ester through methylethyl ketone
(methylacetyl carbinol [44 ; B]). The
ketone is converted into the isonitroso-
derivative by the action of amyl nitrite
in presence of sodium ethylate or
hydrogen chloride according to the
method of Claisen and Manasse (Ber.
20, 6^6 \ 2194; 22, 526; Kalischer,
Ber. 28, 151 8; Diels and Jost, Ber.
35, 3290). From the isonitroso-ketone
= diacetylmonoxime as under quinol
[71; o].

Note : — All generators of methylethyl ketone
given under methylacetyl carbinol [44] thus
become generators of diacetyl.

[B.] From oxalic and acetic acids
[Vol. II] and alcohol [14] through
ketipic acid, &c. [71 ; S].

[C.] From dextrose [154], I^evulose
[155], or mannose [l56] through laevulic
acid (see under erythritol [50; H; I ; J]
and quinol [71 ; O]).

[D.] From glycerol [48] and acetic or
malonic acid [Vol. II] through Isevulic
acid (erythritol [50 ; P ; G]). Or

from glycerol through glyceric and
pyroracemic acids (quinol [71 ; X]) ; or
from glycerol and acetoacetic esier
through allylacetone and Isevulic acid
(erythritol [50 ; G]).

[E.] From hydrogen cyanide [172] and
acetic acid [Vol. II] through pyro-
racemic acid (quinol [71 ; DD]). Or
from hydrogen cyanide and ethyl alcohol
[14] through pyroracemic acid (Ibid.
CC).

[P.] From isohexoic and [Vol. II]
through Isevulic acid (erythritol [50 ;
E]).

[G.] From acetic aldehyde [92]
through Isevulic acid (erythritol [50 ;
N]). Or from aldehyde and zinc ethyl
through secondary butyl alcohol = 2-
butauol (secondary butyl mustard oil
[165; D]). The secondary alcohol gives
diacetyl when oxidised by nitric acid
(Ponzio, Gazz. 31, 401).

Note : — The generators of secondary butyl
alcohol given under secondary butyl mustard
oil thus become generators of diacetyl. These

are : — methyl [13] ; ethyl [14] ; normal and isobutyl
alcohols [17 ; 18] ; erythritol [50] ; formic acid ;
isovaleric acid ; acetoacetic ester ; and all generators
of methylethyl ketone.

[H.] From n-propyl [15] or isopropyl
alcohol [le] through propylene and
pyroracemic acid (quinol [71 ; HH]).

Note : — All generators of propylene thus
become, through pyroracemic acid, generators
of diacetyl.

[I.] From acetone [l06] and ethyl
acetate through acetylacetone and Isevu-
lic acid (erythritol [50 ; G]).

[J.] From methylheptenone [ill]
through Isevulic acid (erythritol [50 ;

[K.] From dimethylheptenol [35]
through Isevulic acid {Ibid. N).

[L.] From propionic acid [Vol, II]
through pyroracemic acid (quinol [71 ;
PF]).

[M.] From lactic acid [Vol. II]
through pyroracemic acid {Ibid. GG).

[N.] From tartaric or racemic acid
[Vol. II] through pyroracemic acid
{Ibid. BB).

[O.] From citric acid [Vol. II]
through pyroracemic acid {Ibid. EE).

114 -A.]

BENZOIC ALDEHYDE

205

AROMATIC ALDEHYDES AND KETONES.

114. Benzoic Aldehyde ;
Benzaldehyde ; Fhenal.

CHO

Natural Sources.

The complex exists in the glueoside
amygdalin, first discovered in the bitter
almond^ Amygdalus communis, var. amara
(Robiquet and Boudron, Ann. Chim.
[3] 44, 352 ; Henry and Boudron,
Journ. Pharm. 22, 118).

Amygdahn, either alone or in associa-
tion with its amorphous form, lauro-
cerasin, exists also in seeds of Prunus
domestica, P. spinosa, P. armenica,
P. avium, P. cerasus, P. cerasus-aus-
tera, P. chameecerasus, P. laurocerasus,
P. padus, P. mahaleb, Persica vulgaris,
Amygdalus nana, Pyrus malus, Cydonia
vulgaris, Sorbus aueuparia, Cotoneaster
vulgaris, Cratce-gus oxyacantha, Mesjtilus
japonica (Van Rijn, ' Die Glykoside,'
p. 232).

Amygdalin occurs also in leaves of
Gymnema latifoUum, and in the bark
of species of Pygium (Greshoff, Ber. 23,
354H).

Note : — For full references see Van Rijn as
above ; for occurrence of amygdalin in Dru-
paceous and Pomaceous plants see Lehmann,
Jahresber. 1885, 1799; for recent confirmation
of occurrence in seeds of Pomaceae, viz. Malus
communis, Cydonia vulgaris. C. japonica, Sorbus
aria, and S, aucuparia, see Lutz, E6p- d. Pharm.
1897, 312.

Benzaldehyde occurs in niauli oil
from the fresh leaves of Melaleuca
viridijiora. New Caledonia (Bertrand,
Bull. Soc. [3] 9, 433) ; in cajeput oil
from the leaves and stems of Melaleuca
leucadendron (Voiry, Comp. Rend. 106,
1538; Bull. Soc. [2] 50, 108); in oil
of cinnamon from Cinnamomum zeylani-
cum (Weber, Arch. Pharm. 230, 728 :
for occurrence in oil of Ceylon cinnamon

see SchimmeFs Ber. April, 1902 ; Wal-
baum and Hiithig, Journ. pr. Ch. [2]
66, 47)-

The aldehyde occurs in oil from the
leaves of Indigo f era galego'ides (Schim-
meFs Ber. Oct. 1894, and April, 1896).

Oroxylin from the bark of Orooaylon
indicum may contain the benzoic alde-
hyde complex (Naylor and Dyer, Trans.
Ch. Soc. 79, 954). The aldehyde is
contained in rassamala resin from the
Javan Attingia excelsa (Tschirch and
Van Itallie, Arch. Pharm. 239, 541).

A condensation product of benzalde-
hyde and methyl-n-nonyl ketone occurs
in oil of rue (Thoms ; Schimmel's Ber.
Oct. 1901).

Synthetical Processes.

[A.] All generators of benzene and
iolneyce (see under cymene [6] and under
benzyl alcohol [54]) become generators
of benzoic aldehyde through the follow-
ing processes : —

Benzyl chloride by oxidation with
dilute nitric acid or lead nitrate (Ber-
tagnini, Ann. 85, 183; Lauth and
Grimaux, Bull. Soc. [2] 7, 106).

Or toluene can be chlorinated up to
the stage of benzylidene = benzal
chloride (Beilstein, Ann. 116, '>f'^'^;
146, 322; Schramm, Ber. 18, 608).
The latter gives benzoic aldehyde on
heating with water, alkalis, or alkaline
carbonates in aqueous solution (Cahours,
Comp. Rend. 56, 222; Meunier, Bull.
Soc. [2] 38, 159; Limpricht, Ann.
139, 319)^ or with milk of lime (techni-
cal process : Espenschied, Germ. Pat.
47187 of 1880), or with water at 95°
in presence of iron or iron salts
(Schultze, Germ. Pats. 82927 of 1894
and 85493 of 1895 ; Ber. 28, Ref. 879 ;
29, Ref. 314). Benzal bromide yields
the aldehyde on contact with water
at ordinary temperatures (Curtius and
Quedenfeldt, Journ. pr. Ch. [2] 58,

390)-

A mixture of benzyl and benzal

chlorides gives benzaldehyde on oxida-

206

AROMATIC ALDEHYDES AND KETONES

[114 A.

tion with manganese dioxide suspended
in water (Schmidt, Germ. Pat. 20909
of 1882; Ber. 16, 448).

Benzal chloride gives benzoic alde-
hyde on heating with acetic acid in
presence of zinc chloride, &c. ( Jacobsen,
Ber. 13, 2013; 14, 1425; Germ. Pat.
11494 of 1879, and suppl. Pat. 13127
of 1880; Ch. Ind. 3, 384; 4, 202);
or with strong sulphuric acid and subse-
quent treatment with water (Oppen-
heim, Ber. 2, 215) ; or with anhydrous
oxalic acid (Anschiitz, Ann. 226, 18).

Or benzylamine (from benzyl chloride
and ammonia ; see under benzyl mustard
oil [169 ; H]) gives the oxime of benzoic
aldehyde among the products of oxida-
tion by monopersulphuric acid (Bam-
berger and Scheutz, Ber. 34, 2262).
Benzylamine gives the aldehyde by
oxidation with sulphuric acid and a di-
chromate (De Coninck and Combe,
Comp. Rend, 127^ 1222).

Or benzylaniline (from benzyl chlor-
ide and aniline) gives benzaldehyde on
oxidation with dichromate and sulphuric
aci 1, &c. (Meister, Lucius, and Briining,
Eng. Pat. 10689 of 1896); the sul-
phonic acid of benzylaniline also gives
benzaldehyde when oxidised in alkaline
or neutral solution {Ibid. Ch Centr.
1897, 2, 1063). Benzylidene deriva-
tives are formed as the first products,
and the aldehyde results from their
hydrolyi-is in these processes. Di-
benzylaniline can be similarly con-
verted into benzaldehyde by oxidation
(//>?>/. Ch. Centr. 1900, 2, 460: for
further list of patents by this firm
relating to the production of aldehydes
from benzylidene compounds see under
p-hydroxybenzaldehyde [119 ; E]).
Benzylidencaniline gives benzoic alde-
hyde by the action of acii chlorides
(Garzarolli-Thuralackh, Ber. 32, 2277).

Toluene on treatment with chromium
oxychloride and decomposition of the
product with water gives benzoic alde-
hyde (Etard, Ann. Chim. [5] 22, 225).
The aldehyde is also among the pro-
ducts of the electrolysis of a mixture
of toluene, alcohol, and dilute sulphuric
acid (Renard, Jahresber. 1881, 352 ;
also Merzbacher and Smith, Journ. Am.
Ch. Soc. 22, 723; Puis, Ch. Zeit. 25,

263), and among the products of oxida-
tion of toluene by potassium persulphate
(Moritz and Wolffenstein, Ber. 32, 433),
by manganese peroxide in presence of
sulphuric acid (Soc. Chim. d. Usines du
Rhone, Germ. Pat. IQ1221 of 1897;
Ch. Centr. 1899, 1, 959; 107722 of
1898; Ch. Centr. 1900, 1, 1113;
Weiler, Ber. 33, 464), or by nickel or
cobalt oxides (Bad. An. Sod. Fab.
Germ. Pat. 127388 of 1900; Ch.
Centr. 1902, 1^ 150).

Benzene gives benzoic aldehyde when
carbon monoxide and hydrogen chloride
are passed through the hydrocarbon in
the presence of aluminium chloride and
cuprous chloride (Parb. vorm. F. Bayer
& Co., Germ. Pat, 98706 of 1897 ;
Ch. Centr, 1898, 2, 951 : see also
Reformatsky, Journ, Russ. Soc. 33,
154). According to Kiichler and Buff
(Germ. Pat. 1 26421 of 1899; Ch.
Centr. 1901, 2, 1372) this process does
not work with aluminium chlox'ide, but
gives good results with the bromide or
iodide.

Benzene and chloroform give a small
quantity of benzaldehyde among other
products by the action of ferric chloride
(Meissel, Ber, 32, 2422).

Or from benzene and hydrogen cyanide
[172] by passing the latter gas with
hydrogen chloride through the hydro-
carbon in presence of aluminium chloride,
and decomposing the product with acid
(Farb. vorm. F. Bayer & Co., Eng. Pat.
19204, Aug. 1897; Journ. Soc. Ch.
Ind. 17, 838).

From benzene, acetic acid, and hydro-
0671 cyanide [l72] through iminobenzoyl-
methyl cyanide (benzaeetodinitrile) by
the action of sodium on a mixture of
benzonitrile and acetonitrile in dry ether
(Holzwart, Journ. pr, Ch. [2] 39, 242),
i^-cyanacetophenone by the action of
hydrochloric acid on the imino-cyanide
(Meyer, Rid. 243), benzoylacetimino-
ethyl ether by the action of alcoholic
hydrochloric acid on the cyanoketone
(Haller, Bull. Soc. [2 J 48, 24), benzoyl-
acetic ester by the action of dilute
alcohol on benzoylacetiminoethyl ether
{I/Ad. 25), and then as below under C.

Notes : — Acetonitrile is obtained from am-
monium acetate [Vol. II] through acetamide and

114 A.]

BENZOIC ALDEHYDE

207

the dehydration of the latter by heat or phos-
phorus pentoxide, &c. (Dumas, Comp. Rend.
35, 383 ; Buckton and Hofmann, Journ. Ch.
Soc. 9, 242 ; Henry, Ann. 152, 149 ; Wallach,
Ann. 184, 21 ; Demar^ay, Bull. Soc. [2] 33,
456). Also from methyl alcohol [13] by distil-
ling methyl sulphates with potassium cyanide or
ferrocyamde[172'] (Dumas, Malaguti, and Leblanc,
Comp. Rend. 25, 474 ; Frankland and Kolbe,
Mem. Ch. Soc. 3, 386; Ann. 65, 288). Hydro-
gen cyanide [172] and diazomethane combine to
form acetonitrile (v. Pechmann, Ber. 28, 857).
Ethylamine [Vol. II] gives acetonitrile among
the products of oxidation by monopersulphuric
acid (Bamberger, Ber. 35, 4293).

Benzonitrilo can be obtained from benzene
by the action of cyanogen chloride [172] in
presence of aluminium chloride (Friodel and
Crafts, Ann. Chim. [6] 1, 528) ; by the action
of aluminium chloride on a mixture of benzene
vapour and cyanogen [172] (Desgrez, Bull. Soc.
[3] 13, 735) ; by distilling benzenesulphonates
with potassium cyanide (Merz, Zeit. [2] 4, 33)
or (practically) by the diazo-method through
nitrobenzene, aniline, &c, (Sandmeyer, Ber. 17,
2653).

Also from benzene and formic or oxalic acid
[Vol. II], aniline and oxalic acid giving benzo-
nitrile on distillation (Hofmann, Ann. 142, 125)
and formanilide giving the nitrile on distilla-
tion over zinc dust (Gasiorowski and Merz,
Ber. 17, 73 ; 18, looi).

Also from aniline and acetic acid [VoL II] by
the action of sodium hydroxide on aniline
dichloracetate (Cech and Schwebel, Ch. Centr.
1877, 134) ; from chlor- or brombenzene and
potassium ferrocyanide [172] at 400° (Merz and
Weith, Ber. 8, 918 ; 10, 749) ; from iodobenzene
and silver cyanide (Merz and Schelnberger, Bor.
8, 1630) ; from benzene and cyanogen [172] by
pyrogenic synthesis {Ibid. ; Merz and Weith,
Ber. 10, 753) ; from aniline and methyl alcohol
[13] through dimethylaniline and the action
of heat on the latter (Nietzki, Ber. 10, 474) ;
or from aniline through phenyl isoeyanide and
isomeric transformation at 220° (Weith, Ber.
6, 213) and from aniline and carbon dieidiihide
[160] through phenyl thiocarbimide and the
action of copper on the latter (Ibid, and 7,725) ;
from magnesium nitride and benzoic anhydride
(Emmerling, Ber. 29, 1635) ; from benzoic acid
and ethylene cyanide (Mathews, Journ. Am. Ch.
Soc. 20, 650) ; fr')mbemoyl chloride and methylamine
through benzenylmethylimido-chloride (v.
Pechmann, Ber. 33, 611).

From benzene and acetic acid throug-h
aeetophenone, by the action of acetyl
chloride on benzene in presence of
aluminium or ferric chloride (Friedel
and Crafts, Ann. Chim. [6] 1, 507 ;
14 455 ; Nencki and Stoeber, Ber. 30,
1768 ; Boeseken, Bee. Tr. Ch. 20, 102),
and then as under G- and C below.

From benzene and e/h/l alcohol [14].
The latter, on treatment with nitric acid
in presence of mercury, gives mercury
fulminate (Howard, Phil. Trans. iHoo;
Liebig, Ann. 95, 284 ; Steiner, Ber. 9,

787; Lobry de Bruyn, Ber. 19, 1370).
The fulminate interacts with benzene
in presence of a mixture of aluminium
chloride and hydroxide, giving benzalde-
hyde (with its oxime, benzonitrile and
benzamide)(Scholl,Ber.32,349a; 36, 10),

Or from benzene and methyl alcohol
[13] through nitromethane by the
interaction of methyl iodide and silver
nitrite (see under glycerol [48 ; L]).
Sodium-nitromethane on treatment with
mercuric chloride solution gives a com-
pound which yields mercury fulminate on
treatment with hydrochloric acid (Jones,
Am. Ch. Journ. 20, 33 ; also Nef, Ann.
280, 276). Subsequent steps as above.

Or from benzene and ethyl alcohol
[14] through ethylbenzene and styrene
bromide (see under styrene [7 ; A] and
under phlorol [64 ; A]). The latter
can be converted into styrene g'lycol
or into phenyl-/3-lactic acid, and either
of these into benzaldehyde as below
under B. Or ethylbenzene can be con-
verted into acetophenone by oxidation
with chromic and acetic acids, or by
decomposing its chromoxychloride with
water (Friedel and Balsohn, Bull. Soc.
[2] 32, 616; V. Miller and Rohde, Ber.

23, 1078), and the ketone treated as
under G. (See also Fournier, Comp.
Rend. 133, 634).

Or from benzene and normal or isopro-
pyl alcohol [15 ; 16] through isopropyl-
benzene by the interaction of the alkyl
bromide and benzene in presence of
aluminium bromide, or of the alkyl
chloride and benzene in presence of
aluminium chloride (see under cymene
[6; a]), or of brombenzene and the
iso-alkyl iodide by sodium (Jacobsen,
Ber. 8, 1260). Isopropylbenzene gives
acetophenone (with hydratropic alde-
hyde) on oxidation with chromium
oxychloride (v. Miller and Rohde, Ber.

24, I35«)-

Trimethylene bromide [15 ; E] from
glycerol [43] and benzene condense under
the influence of aluminium chloride with
the formation of diphenylpropane and
propyl and isopropylbenzene. Propylene
bromide produces the same hydrocarbons
(Bodroux, Comp. Rend. 132, 155).

Note : — Generators of isopropylbenzene are
also given under cymene [6 ; A, note].

208

AROMATIC ALDEHYDES AND KETONES [114 A C.

Or from benzene and oxalic acid
[Vol. II] by the action of ethyloxalyl
chloride = chlorethaualic ester, CICO .
CO^ . CgHg, on the hydrocarbon in the
presence of aluminium chloride. Phenyl-
glyoxylic ester is synthesised by this
method, and the acid gives benzalde-
hyde as below under O (Bouveault,
Bull. Soc. [3] 15, 1017; 17, 363: see
also Roser, JBer. 14, 940).

Or from benzene and acetic aldehyde
[92] through aniline and phenylhydr-
azine and acetaldehydephenylhydrazone.
The latter gives acetophenone when
oxidised by air in alcoholic potash solu-
tion (Biltz and Wienands, Ann. 308,
16 : see also v. Pechmann, Ber. 31,
3125).

[B.] Sti/reiie [7] on heating with
nitric acid, or by the action of ' nitrous '
gas, gives phenylnitroethylene, CgHj .
CH : CH.NO2 (Simon, Ann. 31, 269;
Blyth and Hofmann, Ann. 53, 297 ;
Priebs, Ann. 225, 328). The latter
yields benzoic aldehyde on heating with
water, aqueous alkali, or dilute sulphuric
acid (Priebs, loc. cit.). Or phenylnitro-
ethylene, on heating with strong hydro-
chloric acid, gives phenylchloracetic acid
(Priebs, loc. cit. 337), and this yields
mandelic acid on boiling with aqueous
alkali (Spiegel, Ber. 14, 239). The
latter acid gives benzoic aldehyde on dry
distillation, on oxidation (Liebig, Ann.
18, 321), or on electrolysis of a solution
of the potassium salt (v. Miller and
Hofer, Ber. 27, 469).

Or styrene can be converted into the
bromide by bromination (Blyth and
Hofmann, Ann. 53, 306 ; Glaser, Ann.
154, 154; Zincke, Ann. 216, 288), the
corresponding phenylglycol by boiling
with aqueous potassium carbonate
(Zincke, loc. cit. 293), and into benzoic
aldehyde by oxidising the glycol with
chromic acid mixture. Or on oxidation
with nitric acid the glycol gives phenyl-
gl yoxylic acid (Zincke and Hunaus, Ber.
10, 1488), from which benzoic aldehyde
can be obtained as below under C.

Or styrene bromide on heating with
strong alcoholic potash gives phenyl-
acetylene (Glaser, Ann. 154, 155 ; Frie-
del and Balsohn, Bull. Soc. [2] 35, ^^ ;
Holleman, Ber. 20, 3081), which can

be converted into acetophenone as under
E, and the latter treated as under G.

Or styrene bromide on heating with
water, alcoholic potash, or potassium
acetate gives i^-bromstyrene (Radzis-
zewski, Ber. 6, 493 ; Glaser, Ann. 154,
168; Zincke, Ann. 216, 290 : according
to Nef, Ann. 303, 273, i^-(a))-bromsty-
rene is also formed by these methods),
and this, by the action of sodium and
carbon dioxide, yields phenylpropiolic
acid (Erlenmeyer, Ber. 16, 152), the
ester of which, when dissolved in strong
sulphuric acid and the solution poured
on to ice, gives benzoylacetic ester
(Baeyer, Ber. 15, 2705}. The latter can
be reduced to phenyl-^S-lactic acid, and
the acid converted into benzaldehyde
as below under C. Or phenylpropiolic
ester can be converted into benzoylacetic
ester by the action of dilute caustic
alkali (Baeyer and W. H. Perkin, junr.,
Ber. 16, 2128 ; W. H. P., junr., Trans.
Ch. Soc. 45, 174).

Or i^-bromstyrene on heating with
water at 180° gives acetophenone (Frie-
del and Balsohn, Bull. Soc. [2] 32, 614),
which can be treated as below under G-.
Or phenylpropiolic acid can be con-
verted into phenylacetylene and aceto-
phenone as below under E.

[C] From benzoic and formic acids
[Vol. II] by distilling a mixture of the
calcium salts (Piria, Ann. 100, 104) ;
by reduction of benzoic acid with sodium
amalgam in dilute acid solution (Kolbe,
Ann. 118, 122), or with stannous com-
pounds (Dusart, Comp. Rend. 55, 448) ;
or by electrolytic reduction (Nithack,
Germ. Pat. 123554 of 1899 ; Ch. Centr.
1901,2,715); orby heating with zincdust
(Baeyer, Ann. 140, 296). Also through
benzoyl chloride and benzoyl cyanide
and the action of zinc and hydrochloric
acid on the latter (Kolbe, Ann. 98, 344).
Or from benzoyl chloride and copper
hydride (Chiozza, Ann. 85, 232).

Benzoyl cyanide by the action of
hydrochloric acid in the cold gives
phenylglyoxylic = benzoylformic acid
(Claisen, Ber. 10,430; 845; Hiibner
and Buchka, Ibid. 479). The latter
yields benzoic aldehyde among other
products on distillation (Claisen, loc.
cit. J 666). Or phenylglyoxylic acid

114 C-E.]

BENZOIC ALDEHYDE

209

may be heated with aniline^ and the
anilide hydrolysed by heating with acid
(Fab. Prod. Chim. Thann & Mul-
house^ Germ. Pat. 94018 of 1896; Ch.
Centr. 1897, 2, 1166: see also Bou-
veault^ Bull. Soc. [3] 17, ^6^).

Or from benzoic acid and ethyl alcohol
and acetic acid through henzoylacetic
ester [Vol. II] by the action of sodium
ethylate on a mixture of ethyl benzoate
and acetic ester (Claisen and Lowman,
Ber. 20, 653), and reduction of the
benzoylacetic ester to phenyl-^-lactie
acid by sodium amalgam (W. H. Perkin,
junr., Trans. Ch. Soc. 47, 254). The
latter acid gives benzoic aldehyde on
electrolysis of a dilute solution of the
potassium salt (v. Miller, Hofer, and
Moog, Ber. 27, 469).

From benzoic acid and acetoacetic ester
[Vol. II] through benzoylacetoacetic
ester (Bonne, Ann. 187, i ; Fischer and
Biilow, Ber. 18, 2131 ; Nef, Ann. 266,
99), the sodium derivative of which is
decomposed by aqueous ammonia with
the formation of benzoylacetic ester
(Claisen, Ann. 291, 71). From the ester
through phenyl-/3-lactic acid as above.

Benzoic acid is converted into benzo-
nitrile by dehydrating the ammonium
salt by heat or dehydrating agents
(Fehling, Ann. 49, 91 ; Laurent and
Gerhardt, Jahresber. 1849, 327 ; Hof-
mann and Buckton, Ann. 100, 155 ;
Henke, Ann. 106, 276 ; Wohler, Ann.
192, 362 ; Anschiitz and Schultz, Ann.
196, 48; Henry, Ber. 2, 307). Benzo-
nitrile and acetonitrile givebenzaldehyde
through iminobenzoylmethyl cyanide,
I ^-cyanacetophenone, benzoy lacetimino-
ethyl ether, benzoylacetic ester (see
under A), and then through phenyl-/3-
lactic acid as above.

Note : — For further references to the pro-
duction of benzonitrile from benzoic acid see
under benzyl mustard oil [169 ; A]. For
syntheses of benzonitrile from benzene see the
note under A above.

Or benzonitrile and etht/l alcohol com-
bine in presence of hydrogen chloride
to form benzimidoethyl ether (Pinner,
Ber. 16, "^j-^ : general synthesis). The
ether on reduction with sodium amalgam
in acid solution gives benzoic aldehyde
(Henle, Ber. 35, 3041).

Or from benzoic acid and methyl
alcohol by the interaction of benzoyl
chloride and zinc methyl (Popoff, Ber.
4, 720), and treatment of the aceto-
phenone so produced as under G.

Benzoic acid and hydrazine interact
with the formation of benzhydrazide,
and this in presence of alkali condenses
to benzalbenzoylhydrazine. The latter
is decomposed by dilute acids into ben-
zoic acid and aldehyde and hydrazine
(Curtius, Ber. 33, 2559).

[D.] Phent/lacetic acid [Vol. II] gives
a trace of benzoic aldehyde on electroly-
sis of an acidified solution of the potas-
sium salt (Petersen, Bull, Acad. Roy.
Dane. 1897 ; Ch. Centr. 1897, 2, 520).
Benzoic aldehyde is also among the pro-
ducts of oxidation of phenylacetic acid
by dilute sulphuric acid and manganese
dioxide.

Phenylacetic acid gives dibenzyl ke-
tone on distillation of its calcium salt
(Popoff, Ber. 6, 560 ; Young, Trans.
Ch. Soc. 59, 623). Benzoic aldehyde is
among the products of the photochemical
oxidation of the ketone (Emily Fortey,
Trans. Ch. Soc. 75, 871).

[E.] From cinnamic acid [Vol, II]
through phenyl-a-chlor-/3-lactic acid by
combination with hypochlorous acid
(Glaser, Ann. 147, 79), phenyl-,d-lactic
acid by reducing the chloro-acid with
sodium amalgam {l/jid. 86), and then as
above under C.

Or the chloro-acid, on treatment with
alcoholic potash, gives ;8-phenyloxyacry-
lic = phenylglycidic acid (Glaser, Ann.
147, 98), and this yields phenyl-y3-lactic
acid on reduction with sodium amalgam
(Plochl, Ber. 16, 2823).

Or cinnamic acid can be combined
with hydrogen bromide to form i^-brom-
hydrocinnamic = phenyl - /3 - brompro-
pionic acid (Fittig and Binder, Ann.
195, 132; Anschiitz and Kinnicutt,
Ber. 11, 1 22 1 ). The latter gives pheny 1-
^-lactic acid on boiling with water (F.
and B. loc. cit. 138).

Or cinnamic ester can be brominated
so as to give phenyl-a/5-dibrompropionic
= a/3-dibromhydrocinnamic ester, and
this, by the action of alcoholic potash,
gives pheny Ipropiolic acid(W. H.Perkin,
junr., Trans. Ch. Soc. 45, 172 ; Lieber-

210

AROMATIC ALDEHYDES AND KETONES [114 E-G.

mann and Sachse^ Ber. 24, 41 13, note).
The latter yields benzoylacetic acid,
plienyl-^-laetic acid, and benzaldehyde
as above under B and C Or the phenyl
dibrompropionic ester by the limited
action of alcoholic potash gives a mixture
of two bromcinnamie esters, of which
the a-cster (i ^-bromcinnamie ester)
yields benzoylacetic ester when treated
successively with strong sulphuric acid
and water (Michael and Browne, Ber.

19. 1393)-.

Cinnamic acid can also be brominated
(Michael, Journ. pr. Ch. [2] 52, 292),
and the dibromo-acid debrominated in
two stages by successive treatment with
alkali {Ibid. Ber. 34, 3648). The final
product is phenylpropiolic acid, which
can be treated as above.

Or the dibromo-acid on heating with
10 per cent, sodium carbonate solution at
100° gives i^-(a))-bromstyrene, and this
on heating with strong alcoholic potash
at 130-135° yields phenylacetylene (Nef,
Ann. 308, 267). The latter gives aceto-
phenone as below (Friedel and Balsohn,
Bull. Soc. [2] 35, ^^), and benzaldehyde
as under G. Or the dibromo-ester by
the action of sodium ethylate gives
/3-ethoxycinnamic acid (Leighton, Am.
Ch. Journ. 20, i^^6), and this on heating
with alcoholic hydrochloric acid yields
benzoylacetic acid [Ibid. 13 7).

The /3-iodo- cinnamic acid obtained
by iodising the acid in presence of
pyridine gives benzoylacetic acid and
acetophenone on treatment with sodium
hydroxide solution (Ortoleva, Gazz. 29,

503)-

Or phenylpropiolic acid can be con-
verted into phenylacetylene by heating
with water or phenol (Glaser, Ann.
154, 155; Holleman, Ber. 20, 3081).
Phenylacetylene on treatment with sul-
phuric acid and water gives acetophe-
none (Friedel and Balsohn, as above),
which can be treated as below under G.

Or from cinnamic acid through
phenylnitroethylene by distilling the
acid with sodium nitrite in steam (Erd-
mann, Ber. 24, 2773), and then as
above under B. Or by the direct oxi-
dation of cinnamic acid with potassium
permanganate phenylglyceric acid is
obtained (Fittig and Riir, Ann. 268,

27) ; benzaldehyde is among the pro-
duets of the electrolysis of the potassium
salt of this acid in strong aqueous
solution (v. Miller and Hofer, Ber. 27,
470).

NoTK : — Phenylglyceric acid is also obtained
from cinnamic acid through phenyI-a-chlor-j3-
lactic acid (see above), and tlie action of
aqueous alkali on the latter (Lipp, Ber, 16,
1286).

[P.] Vnlpic acid [Vol. II] can be
converted into pulvic anhydride by
heating, and the latter into pulvic acid
by the action of caustic potash solution ;
or vulpic acid is directly convertible
into pulvic acid by boiling with milk of
lime (Spiegel, Ann. 219, 6). Pulvic
acid on oxidation with alkaline per-
manganate gives phenylglyoxylic acid
[Ibid. Ber. 14, 1689), and this yields
benzaldehyde as above under C.

[G.] From acetic and benzoic acids
[Vol. II] through acetophenone (Friedel,
Ann. 108, 122), phenylglyoxylic acid
by oxidation with alkaline permanganate
(Gliicksmann, Monats. 11, 248), and
then as above under C.

Or acetophenone can be converted
into i^ : i^-dibromacetophenone by
bromination (Hunnius, Ber. 10, 2010),
and this on heating with dilute caustic
potash solution gives mandelic acid
(Engler and Wohrle, Ber. 20, 2202),
from which benzaldehyde can be ob-
tained as above under B.

Or acetophenone can be converted
into the i^-nitroso-derivative by the
action of amyl nitrite and sodium
(Claisen, Ber. 20, 656). The sodium
bisulphite compound of the nitroso-ke-
tone gives benzoylformaldehyde (phen-
ethylal = pheny Iglyoxal) on heating with
dilute sulphuric acid (v. Pechmann, Ber.
20, 2904; Miiller and v. Pechmann,
Ber. 22, 2557), and the aldehyde yields
mandelic acid on heating with aqueous
alkali (v. Pechmann, Ber. 20, 2905).

Or the nitroso-ketone gives benzoyl
cyanide on heating with acetyl chloride
or acetic anhydride (Claisen and Ma-
nasse, Ber. 20, 2196). The cyanide
yields benzaldehyde as above under C

From acetophenone through benzoyl-
acetic acid by the action of diethyl

114 G-115 A.]

BENZOIC ALDEHYDE

211

carbonate and sodium ethylate on the
ketone (Claisen, Bar. 20, 656), or by
the action of carbon dioxide on the
sodium compound of acetophenone sus-
pended in dry ether (Beckmann and
Paulj Ann. 266, 17). Benzoylacetic
ester can be converted into phenyl-/3-
lactic acid, and the latter into benzoic
aldehyde as above under C.

Acetophenone, formic acid [Vol. II],
and ethyl alcohol [l4] give benzoyl-
acetaldehyde by the action of sodium
ethylate on a mixture of the ketone and
formic ester (Claisen and Fischer, Ber.
20, 2192; 21, 1 1 35). The oxime of
this aldehyde gives i^-cyanaeetophenone
by dehydration (Claisen and Stock, Ber.
24, 133), and this yields benzoylacet-
iminoethyl ether (see above under A),
benzoylacetic ester, phenyl-j8-lactic acid,
and benzoic aldehyde as under C. Or
benzoylacetaldoxime by the action of
acetyl chloride gives phenylisoxazole,
and this yields i^-cyanacetophenone by
the action of sodium ethylate {Ibid.

134)-

Or acetophenone, oxalic acid [Vol. II],
and ethi/l alcohol [14] give benzoylpyro-
racemic acid by the action of sodium
ethylate (Beyer and Claisen, Ber. 20,
2184; Claisen and Bromme, Ber. 21,
1 132), the oxime of which, treated with
acetyl chloride, gives phenylisoxazole-
carboxylic acid (Salvatori, Gazz. 21, II,
286). The latter yields i^-cyanaceto-
phenone on heating {Ibid. 287).

[H.] From phenol [6O] through tri-
phenyl phosphate by the action of phos-
phorus pentachloride or oxychloride
(Williamson and Scrugham, Journ. Ch.
Soc. 7, 240; Heim, Ber. 16, 1765),
benzonitrile by distilling the phosphate
with. potass iztm ci/anide[n2] (Scrugham,
Ann. 92, 318; Heim, loc. ciL 1771),
and then (with acetonitrile) through
iminobenzoylmethyl cyanide, &c., as
above under A and C.

[I.] Hippuric acid [Vol. II] gives
benzonitrile on heating per se or with
zinc chloride (Limpricht and Uslar, Ann.
88, 133; Gossmann, Ann. 100, 74).
Subsequent steps as above.

[J.] From naphthalene [l2] (see under
hydrojuglone [OO]), through phthalic
acid (benzyl alcohol [54; R]), and

phthalimide by the action of ammonia
on phthalic anhydride (Laurent, Ann.
41, no; Lansberg, Ann. 215, 181).
The imide gives benzonitrile on dis-
tillation with lime (Laurent, Jahresber.
1868, 549; Reese, Ann. 242, 5). Sub-
sequent steps as above.

[K.] From cymene [e] through cumic
aldehyde [II6] and cumic acid by oxi-
dation (Gerhardt and Cahours, Ann.
38, 74; Beilstein and Kupfer, Ann.
170, 302 ; R. Meyer, Ann. 219, 244),
isopropylbenzene (cumene) by distilling
the acid with lime or baryta (G. and C.
loc. cit. 88 ; Ann. Chim. [3] 1, 87 ; 372 ;
14, 107), acetophenone, &c., as above
under A, G, and C.

[L.] Benzyl alcohol [54] gives ben-
zoic aldehyde on oxidation with dilute
nitric acid, &c. Or by pyrogenic con-
tact decomposition by heated copper
(IpatiefP, Ber. 35, 1055).

[M.] From racemic or tartaric acid
[Vol. II] and n-propyl alcohol [15]
through pyroracemic acid, ethyliso-
phthalic acid, and ethylbenzene (see
under phlorol [64 ; J]), and then as
above under A.

Or from pyroracemic acid and isohu-
tyric aldehyde [94] through isopropyl-
benzene (see under cymene [6; A, note]),
and then as above under A.

115. Hydrocinnamic Aldehyde;
Fhenylpropiouic Aldehyde ;
Phenepropylal.

CeH5.CH2.CH2.CHO

Natural Source.

May possibly occur in Ceylon oil of
cinnamon (SchimmeFs Ber. April, 1902;
Walbaum and Hiithig, Journ. pr. Ch.
[2] 66, 52).

Synthetical Processes.

[A.] From n-propyl alcohol [15] and
benzene [6; I, &c.] through propylben-
zene by the condensation of propyl
bromide and brombenzene by the action
of sodium (Fittig, Schaffer, and Konig,
Ann. 149, 324), or of aluminium chloride
(Heise, Ber. 24, 768). Projiylbenzene

p2

212

AROMATIC ALDEHYDES AND KETONES [lis A-116.

forms a compound with chromium oxy-
chloride which gives the above aldehyde
on decomposition by water (Etard, Ann.
Chim. [5] 22, 254 : according to later
experiments by v. Miller and Rohde,
Ber. 23, 1070, this process gives benzoic
and not hydrocinnamic aldehyde).

Note : — Propyl chloride and benzene give
also isopropylbenzene = cumene by the action
of aluminium chloride unless the temperature
is kept below 0° (Konowaloff, Journ. Kuss. Soc.

27, 457).

[B.] From benzoic aldehyde [114] and
ethyl alcohol [14] through ethylphenyl
carbinol by the interaction of the alde-
hyde and magnesium ethiodide, the
chloride by the action of phosphorus
pentachloride on the alcohol, and pro-
penylbenzene by heating the chloride
with pyridine. Propenylbenzene gives
propylbenzene on reduction with sodium
in alcoholic solution (Klages, Ber. 36,
621 : see also Wagner, Journ. Buss. Soc.
16, 324).

Note : — Generators of propenylbenzene are :
bronihydroxyphenylcrotonic acid (Perkin,
Journ. Ch. Soc. 32, 660) ; a-methyl-)3-phenyl-
hydroxypropionic acid (W. H. Perkin, junr.,
and Stenhouse, Trans. Ch. Soc. 59, 1010) ;
methylbenzyl ketone or ethylphenyl ketone or
the chlorides from the corresponding secon-
dary alcohols (Errera, Grazz. 14, 504; 16, 318) ;
phenopropyltrimethylammonium hydroxide
(Senfter and Tafel, Ber. 27, 2312"); brompro-
piophenone from brompropionic acid and ben-
zene through a-ehlor-;8-brompropenylbenzene
(Kunkell and Dettmar, Ber. 36, 771 : compare
with respect to this process Klages, Ber. 36,
2572).

[C] From glycerol [48] through allyl
bromide (see under n-propyl alcohol
[15 ; E]) and henzene, a mixture of the
bromide and hydrocarbon giving propyl-
benzene among other products when
heated with zinc dust (Shukowski,
Journ. Buss. Soc. 27, 297).

[D.] 'Pvoviiquinoli7ie [Vol. II], propyl-
benzene being among the products of
reduction by hydriodic acid and phos-
phorus at 300-310° (Bamberger and
Williamson, Ber. 27, 1477)-

[E.] From cinnamic aldehyde [l23].
The hydrochloride of a formimino-ether
(prepared by the interaction of hydrogen
cyanide [172] and an alcohol in presence
of hydrogen chloride ; Pinner, * Die

Imidoaether,' 1892) condenses with the
aldehyde to form an acetal (Claisen,
Ber. 31, 1016). The latter, after reduc-
tion by sodium in alcohol, is decomposed
into hydrocinnamic aldehyde on heating
with dilute sulphuric acid (Fischer and
Hoffa, Ber. 31, 1991). The dimethyl
acetal is also formed from cinnamic
aldehyde and methyl alcohol by the
condensing action of hydrogen chloride
(F. and H. loc. cit. 1990).

[P.] From hydrocinnamic and formic
acids [Vol. II] by distilling a mixture
of the calcium salts (v. Miller, Bohde,
and Gerdeissen, Ber. 23, 1080 : see also
DoUfuss, Ber. 26, 197 1).

116. Cnmic Aldehyde; Cumiuol;

Para-isopropylphenal ; Cuminal ;

4-MetIioethylplienemetliylal.

CHO

CHCOHj),

Natural Sources.

Occurs (with cymene) in Roman oil
of cumin from Cuminum cyminum (Ger-
hardt and Cahours, Ann. 38, 70 ; Ann.
Chim. [3] 1, 60 ; Bertagnini, Ann. 85,
275 ; Kraut, Ann. 92, 66), and in oil
of water-hemlock from Cicuta virosa
(Trapp, Journ. pr. Ch. 74, 428 ; Arch.
Pharm. 231, 212; Ann. 108, ^>^6).

Said to occur also in oil of thyme
from Thymus vulgaris and T. serpyllum,
in oil of true bishop^s weed from
Ptychotis ajowan, in oil of pepperwort
from Satureia hortensis, and in oils of
Eucalyptus globulus, ginger, nutmeg,
sage, and citron (Sawer's ' Odoro-
graphia,' Vol. II, p. 140 : authorities
not given).

Cuminal is contained in the oils of
Eucalyptus hcemastoma (SchimmeFs Ber.
April, 1888), E. odorata {Ibid. April,
1889), E. oleosa (Gildemeister and
Hoffmann, p. 695), E. populifera
(Schimmers Ber. April, 1893), (■) ^-

116-117 E.]

CUMIC ALDEHYDE

213

viridis {Ihid. Oct. 1901), and E. liemi-
phloia [Ibid. April, 1892).

Note : — According to H. G. Smith (Proc.
Roy. See. N. S. Wales, 34) the aldehyde of
Eucalyptus oils is not curaic aldehyde, but a new
aldehyde, ' aromadendral.'

Cuminal is contained in Ceylon oil
of cinnamon (Schimmel's Ber. April,
1902 ; Walbaum and Hiithig, Journ.
pr. Ch. [2] 66, S5)-

Synthetical Peocess.

[A.] Cymene [e] on chlorination at
its boiling point gives i^-chlorcymene
= cymyl chloride (Errera, Gazz. 14,
377). The latter yields cuminal on
boiling with lead nitrate and water
(Ibid. 278). A small quantity of the
aldehyde is obtained by the oxidation
of cymene with sulphuric acid and
manganese dioxide (Fournier, Comp.
Rend. 133, 634).

117. Salicylic Aldehyde ;

Orthohydroxybenzaldehyde ;

Orthohydroxyphenal ;

2 -Fhenolmethylal,

CHO
,0H

Natural Sources.

The complex is contained in some
compound present in the flowers and
herb (but not in the root) of Sjnrfea
lihnaria (Pagenstecher, Berz. Jahresber.
18, '3,'3,6 ; Lowig, Ihid. 20, 'ifSS > I'og'8"-
Ann. 36, 383; Dumas, Ann. 29, 306;
Ettling, Ibid. 309 ; 35, 247) ; in the
herbs of Spiraa digifata, S. lobata, and
S.Jilipendula', in the flowers of S. aruncus
(Wicke, Ann. 83, 175), and in the root
and stem of hawk^s-beard, Crepisfoetida
(Wicke, Ann. 91, 374). The glucoside,
spirffiin, contained in the old roots of
Spircea Jcamschatica is a glucoside of
salicylic aldehyde (Beyerinck, Centr.
Bakter. II, 6, 425 ; Ch. Centr. 1H99,
2, 259).

Mould fungi [Aspergillus oryzce) split
off saligenin from salicin [157], and then
oxidise the alcohol to the aldehyde
(Brunstein ; Abst. in Journ. Fed. Inst.
7, ?>^1 ; 8, 507). _

The aldehyde is said to have been
obtained from the larva and imago of
the beetle, Chrysomela populi (Jahresber.
1850, 583 ; Enz, Ibid. 1859, 312).

Synthetical Processes.

[A.] From phenol [60] (with p-
hydroxybenzaldehyde) by heating with
chloroform [l; D] in presence of sodium
hydroxide solution(Tiemann and Reimer,
Ber. 9, 423 ; 824).

Or from phenol and eihyl alcohol [l4]
through coumarone (see under phlorol
[64 ; C]). The latter on nitration
gives a nitrocoumarone, which yields
salicylic aldehyde among the products
of its decomposition by sodium ethylate
(Stoermer and Richter, Ber. 30, 2094 ;
Stoermer and Kahlert, Ber. 35, 1640).

[B.] Saligenin [55] gives salicylic
aldehyde on oxidation (Piria, Ann. 30,

[C.} Salicin [157] gives salicylic
aldehyde on oxidation with sulphuric
acid and potassium dichromate, &c.
(Piria, loc. cii.; Schiff, Ann. 150, 193;
210, 115).

[D.] Acetophenone (see under benzoic
aldehyde [114 ; A ; G, &c.]) on nitra-
tion at a low temperature gives (with
m-nitro-) o-nitroacetophenone (Engler,
Ber. 18, 2238 ; Camps, Arch. Pharm.
240, 6), and this on reduction yields
o-aminoacetophenone (Gevekoht, Ann.
221, 326 ; Camps, loc. cit. 15). By
the diazo-method the latter is converted
into o-/iydroxyacetophenone [130] (Fried-
lander and Neudorfer, Ber. 30, 1080 ;
Dunstan and Henry, Trans. Ch. Soc. 75,
71). The hydroxy-ketone by acetyla-
tion and bromi nation gives acetyl- o-
hydroxy-co-acetophenone bromide, which,
on boiling with water and chalk, yields
ketocotimaran = coumaranone [132] (F.
and N. loc. cit. 1081). The latter on
heating in alkaline solution gives sali-
cylic aldehyde [Ibid.).

[E.] From cinnamic acid [Vol. II]
through o-nitrocinnamic acid and ester

214

AROMATIC ALDEHYDES AND KETONES [117 E- J.

by nitration (Beilstein and Kuhlberg,
Ann. 163, 125; Morgan, Ch. News,
36, 369 ; Baeyer, Ber. 13, 2258 ;
Miiller, Ann. 212, 142 ; Drewsen,
Ibid. 151; Fischer and Kiizel, Ann.
221, 265), o-nitroplienylpropiolic acid
by bromination of o-nitrocinnamic acid
and the action of excess of caustic soda
on the product (Baeyer, loc. cit.), and
o-nitrophenylacetylene by heating 0-
nitrophenylpropiolic acid with water
{Ibid. 2259}. o-Nitrophenylacetylene
on reduction with zinc dust and am-
monia gives o-aminophenylacetylene
(Baeyer and Landsberg, Ber. 15, 60 ;
JBaeyer and Bloem, Ber. 17, 964). The
latter, on treatment with sulphuric
acid and water, yields o-aminoaceto-
phenone (B. and B. Ber. 15, 2154),
which can be converted into o-hydroxy-
acetophenone, ketocoumaran, and sali-
cylic aldehyde as above under D.

Or from cinnamic acid through
phenylpropiolic acid, phenyl acetylene,
and acetophenone (see under benzoic
aldehyde [114; E]), and then as above
under D.

Or from cinnamic acid through
coumarone (see under phlorol [64 ; P]),
and then as under A above.

[F.] From benzoic acid and aceto-
acetic ester [Vol. II]. Benzoic acid on
nitration gives (with m- and p-nitro-)
some o-nitro-acid (Griess, Ann. 166,
129 ; Ber. 10, 1871 ; Ernst, Jahresber.
1860, 299; Holleman, Zeit, physik.
Ch. 31, 79). o-Nitrobenzoyl chloride
and sodio-acetoacetic ester give o-
nitrobenzoylacetoacetic ester (Gevekoht,
Ann. 221, 323), which on hydrolysis
with dilute sulphuric acid yields o-nitro-
acetophenone {Ibid. 325). Subsequent
steps as above under D.

Or from benzoic and acetic acids
through acetophenone (see under benzoic
aldehyde [114; G]), and then as above
under D.

Or from benzoic acid (benzoyl chlor-
ide) and zinc methyl through aceto-
phenone [114 ; C], and then as under D.
[G.] From salicylic acid [Vol. II]
through the ethyl ester of the methyl
ether (Cahours, Ann. 92, 315 ; Graebe,
Ann. 139, 137), and condensation of the
latter with acetic ester [Vol. II] to form

2-methoxybenzoylacetic ester (Tahara,
Ber. 25, 1306). The latter on hydro-
lysis with dilute sulphuric acid gives
o-methoxyacetophenone, which can be
demethylated by heating with hydro-
chloric acid at 130° {Ibid. 1309). The
o-hydroxyacetophenone can be treated
as above under D (see also Besthorn,
Banzhaf, and Jaegle, Ber. 27, 3035).

[H.] Coumarin [Vol. II] on combina-
tion with bromine forms a dibromide,
which on treatment with alcoholic
potash gives o-coumarilic acid (Perkin,
Journ. Ch. Soc. 24, 45 ; Fittig and
Ebert, Ann. 216, 163). The ethyl
ether of the coumarilic acid on heating
with dilute hydrochloric acid yields,
among other products, o-ethoxyaceto-
phenone (Fittig and Claus, Ann. 269,
10), which might be de-alkylated and
treated as above under G. Or from
coumarin through coumarone (see under
phlorol [64; D]), and then as above
under A.

[I.] Orthocoumaric acid [Vol. II] on
ethylation gives the /3-ethyl ether of
the acid (Fittig and Ebert, Ann. 216,
146), and this on combination with
bromine yields the ethyl ether of di-
brom-melilotic acid {Ibid. 158). The
latter, by the action of alcoholic potash,
gives the ethyl ether of o-coumarilic
acid (Fittig and CJaus, Ann. 269, 6),
which can be treated as above under H.

[J.] From toluene [54 ; A and D to
end] through o-nitrotoluene (see under
o-cresol [61 ; A]) and o-nitrobenzoic
acid by oxidation of the latter (Wid-
mann, Ann. 193, 225; Noyes, Ber. 16,
53 ; Monnet, Reverdin, and Noelting,
Ber. 12,443). Subsequent steps through
o-nitrobenzoylacetoacetic ester as above
under P.

Or from o-nitrotoluene through o-
nitrobenzaldehyde (see under saligenin
[55 ; C]), which condenses with malonic
acid [Vol. II] in presence of aniline to
form o-nitrocinnamic acid (Knoevenagel
and Baebenroth, Ber. 31, 2609). From
the latter through o-nitrophenylpropiolic
acid, &c., as above under E.

Or from benzene [6 ; I, &c.] through
nitrobenzene, aniline, o-nitraniline
(Nietzki and Benckiser, Ber. 18, 295 ;
Lellmann, Ann. 221, 6; Turner, Ber.

117 J-119 A.]

SALICYLIC ALDEHYDE

215

25, 986), and o-nitrobenzonitrile (Sand-
meyer, Ber. 18, 1492). The latter can
be hydrolysed to o-nitrobenzoic acid,
and then treated as before.

Or from benzene through aceto-
phenone by direct synthesis, or via
ethylbenzene or isopropylbenzene or
aeetaldehydephenylhydrazone (see under
benzoic aldehyde [114; A]) and aceto-
phenone, and then as above under D.

Acetanilide (from aniline and acetic
acid) on heating- with acetic and phos-
phoric acids and subsequent hydrolysis
of the acetyl-derivatives gives a mixture
of 0- and p-aminoacetophenone (Kohler,
Germ. Pat. 56971 of 1889; Ber. 24,
Ref. 685). From the o-aminoketone as
under D above.

[K.] "From sUjrene [7] through aceto-
phenone (see under benzoic aldehyde
[114 ; B]), and then as above under D.

[L.] From cymene [6] through cumic
aldehyde [II6] and acid and acetophenone
(see under benzoic aldehyde [114; K]),
and then as above under D.

118. Metahydroxybenzoic Aldehyde;

Metahydroxyphenal ;

3-Fhenolmethylal.

CHO

OH

Natural Source.

The glucoslde, salinigrin, occurs in
the bark of Salix discolor ( Jowett, Trans.
Ch, Soc. 77, 707 ; Jowett and Potter,
Pharm. Journ. [4] 15, 157).

Synthetical Processes.

[A.] From benzoic aldehyde [114]
through the m-nitro-aldehyde by nitra-
tion, the m-amino-aldehyde by reduc-
tion, and decomposition of the diazo-
stannichloride by boiling with water
(Tiemann and Ludwig, Ber. 15, 2045 :
see also under vanillin [121; C]).

[B.] From leaizolc acid [Vol. II]
through the m-l]ydroxy-acid (see under

phenol [60 ; E]). The latter gives the
m-hydroxy-aldehyde on reduction with
sodium amalgam in presence of dilute
acid (Sandmann, Ber. 14, 969).

Note : — Other generators of m-hydroxyben-
zoic acid are m-cresol [62], cinnamic acid [Vol. II],
and naphthalene [12]. For references see under
phenol [60 ; F ; I ; J].

119. Farahydrozybeuzoic Aldehyde ;

Farahydrozyphenal ;

4i-Fhenolmetliylal.

CHO

HO

Natural Sources.

Occurs in yellow Botany Bay or
acaroid resin from Xanthonhcea hastills
(L. Bamberger, Monats. 14, 339) ; also
in red Xanthorrhcea resin (Tschirch and
Hildebrand, Arch. Pharm. 234, 698 ;
Ch, Centr. 1897, 1, 422).

The complex (p-hydroxymandeloni-
trile) is contained in a cyanogenetic
glucoside (dhurrin) occurring in the
young plants of Sorghum vulgar e, the
great millet (Dunstan and Henry, Proc.
Roy. Soc. 70, 153).

Synthetical Processes.

[A.] ¥rom phenol [60] (with salicylic
aldehyde) by the action of chloroform
[1 ; D] in presence of sodium hydroxide
solution (Tiemann and Reimer, Ber. 9,
8 24 ; Tiemann and Herzfeld, Ber. 10,

Or from phenol and hydrogen cyanide
[172] by combining the two compounds
in benzene solution in presence of alu-
minium chloride and hydrogen chloride,
and decomposing the product with
dilute acid (Gattermann and Berchel-
mann, Ber. 31, 1766; also Eng. Pat.
13453 of 1898, Bayer & Co.). Zinc
chloride may be used as a condensing
agent instead of aluminium chloride
(Gattermann and Kobner, Bei\ 32, 278).

Or from phenol, ethyl alcohol [14],

216

AROMATIC ALDEHYDES AND KETONES [119 A-E.

and oxalic acid [Vol. II] through the
following stages : — Picric acid (from
phenol) is converted into picrylphenol
by the action of picryl chloride on
potassium phenate. Oxalic acid is con-
verted into ethyl oxalate, and the latter
into ethyloxalyl chloride [l20 ; B],
which combines with picrylphenol in
the presence of aluminium chloride to
form picryl-p-hydroxyphenylglyoxylic
ester : —

(NOJgCeH^.O.CeH,. CO. CO.CJI,.

The latter on hydrolysis with alcoholic
potash gives p-hydroxyphenylglyoxylic
acid, and this on distillation in vacuo,
or on heating with dimethylaniline,
yields (with p-hydroxybenzoic acid) p-
hydroxybenzoic aldehyde (Bouveault,
Bull. Soc. [3] 17, 947).

Note : — For technical production from
phenol by condensation with/ormic aldehyde [91]
and p-toluylhydroxylamine-m-sulphonic acid
(from p-nitrotoluene-m-sulphonic acid), and
decomposition of the condensation product by
heating with dilute acids or alkalis, see Geigy's
Germ. Pats, 103578 of 1898 ; Ch. Centr. 1899,
1, 926 ; 105103 of 1898 ; Ch. Centr. 1900, 1,
239 ; 105798 of 1898 ; Ibid. 523.

[B:] Cinnamic acid [Vol. II] or its
ester on nitration gives (with ortho-)
paranitrocinnamic acid or ester (Mit-
scherlich, Journ. pr. Ch. 22, 192; Ann.
Chim. [3] 4, 73; Kopp, Comp. Rend.
53, 634 ; Beilstein and Kuhlberg, Ann.
163, 1 26 ; Tiemann and Opermann,
Ber. 13, 2059; Miiller, Ann. 212, 124;
Drewsen, Ibid. 150). The p-nitro-acid
(or ester) on oxidation gives p-nitro-
benzoic aldehyde (Baeyer, Ber. 14, 2317 :
see also Basler, Ber. 16, 2714), which
combines with hydroxylamine to form
an oxime (Gabriel and Herzberg, Ber.
16, 3coo),and this reduces to the oxime
of p-aminobenzoic aldehyde [Ibid. 2001),
which, by the action of acids, yields the
p-amino-aldehyde [Ibid. 2002). The
latter gives the hydroxy-aldehyde by
the diazo-method (Walther and Bret-
schneider, Journ. pr. Ch. [2] 57, 53H).

Or cinnamic acid can be combined
with bromine or with hypobromous acid,
and the product converted into w-brom-
styrene by heating with water (Glaser,
Ann. 154, 168). The bromstyrene on
nitration gives (with another isomeride

and p-nitrobenzoic acid) a-p-n itropheny 1-
iQ-bromnitroethylene, NOg . CgH^ . CH :
CBrNOg, and this, on boiling with
water, yields p-nitrobenzoic aldehyde
among other products (Fliirscheim,
Journ. pr. Ch. [2] 66, 16).

[C] Styrene [7] by the action of
nitric or nitrous acid gives i^-nitrosty-
rene = phenylnitroethylene (Simon,
Ann. 31, 269; Blyth and Hofmann,
Ann. 53, 297 ; Priebs, Ann. 225, 328),
which, by further nitration, yields 4 : 1^-
dinitrostyrene (Priebs, loc. cit. 348).
The latter, on heating with strong sul-
phuric acid at 110°, gives p-nitrobenzoic
aldehyde (Friedlander and Mahly, Ann.
229, 213). Subsequent steps as above.

[D.] From benzoic aldehyde [114] and
methyl alcohol [13] by the action of
nitromethane on the aldehyde at 160°
in presence of zinc chloride (Priebs,
Ann. 225, 321), which gives i^-nitro-
styrene. Subsequent steps through
dinitrostyrene, p-nitrobenzoic aldehyde,
&c., as above.

Note : — Nitromethane is prepared from
methyl iodide and silver nitrite (Bewad, Journ.
Russ. Soc. 24, 126 ; Meyer, Ann. 171, 32).
Formed also from potassium chloracetate and
potassium nitrite (Kolbe, Journ. pr, Ch, [2] 5,
427; Preibisch, Ibid. 8, 310: see also under
glycerol [48 ; K ; L], and hydrogen cyanide
[172; J; Y]).

Or from benzoic aldehyde and succinic
acid [Vol. II] through phenylisocro tonic
acid by heating the aldehyde with suc-
cinic anhydride and sodium succinate
(Perkin, Journ. Ch. Soc. 31, 394), or
with sodium succinate and acetic anhy-
dride (Jayne, Ann, 216, 100; Leoni,
Ann, 256, 64). Phenylisocrotonic acid
by the action of fuming nitric acid
gives i^-nitrostyrene (Erdmann, Ber. 17,
412), which can be treated as above.

[E.] From benzene [6 ; I, &c.] or
toluene [54] by various processes : —

From benzene and formic aldehyde
[91] through phenylhydroxylamine
(Bamberger, Ber. 27, 1347; 1548;
Wohl, Ibid. 1432), which condenses
with the aldehyde to form a polymeric
anhydro-derivative of p-hydroxylamine-
benzyl alcohol. The diazo-derivative
of the latter, on heating with water,
gives p-hydroxybenzoic aldehyde (Kalle

119 E.]

PARAHYDROXYBENZOIC ALDEHYDE

217

& Co., Germ. Pat. 8797a of 1895;
Ber. 29, Ref. 747 : see also Germ. Pat.
89601 of T896; Ber. 29, Ref. 1195).
The same polymeric anhydro-derivative
is obtained by the electrolysis of nitro-
benzene in the presence of hydrochloric
acid and formic aldehyde (Lob, Zeit.
Elektroch. 1898, 4, 428).

From benzene through p-phenylene-
diamine (see under quinol [71 ; T]).
The latter combines with alloxan [Vol.
II] to form a product which, on heating
with sulphuric acid, gives p-aminoben-
zoic aldehyde, which can be treated as
above under B (Pellizari, Gazz. 17, 41 a ;
Bohringer & Sohne, Germ. Pat. 108026
of 1898; Ch. Centr. 19CO, 1, 11 14).

From toluene through p-nitrotoluene
and p-nitrobenzyl chloride (Wachen-
dorff, Ann. 186, 271), or through
benzyl chloride and nitration of the
latter (Beilstein and Geitner, Ann. 139,
337 ; Strakosch, Ber. 6, 1056). The
nitrobenzyl chloride on oxidation with
lead nitrate and dilute nitric acid gives
p-nitrobenzoic aldehyde (Fischer and
Greiff, Ber. 13, 670), which can be
treated as above under B.

Or p-nitrotoluene can be oxidised by
a mixture of sulphuric and chromic
acids in presence of acetic acid and
anhydride, when p-nitrobenzaldehyde
diacetate is formed, and this gives the
aldehyde on hydrolysis (Farbenfab. vorm.
F. Bayer & Co., Germ. Pat. 121788 of
1899; Ch. Centr. 1901, 2, 70).

Or p-nitrobenzyl chloride can be
combined with aniline or its sulphonic
acid (Strakosch, Ber. 6, 1056 ; Paal
and Sprenger, Ber. 30, 69), and the
p-nitrobenzyl compounds oxidised to
benzylidene-compounds by acid and
dichromate, or with alkaline or neutral
oxidising mixtures (Meister, Lucius,
and Briining, Germ. Pats. 91503 of
1896; Ch. Centr. 1897, 1, 1007 '•> 92084
of 1896; Ch. Centr. 1897, 2, 456;
93539 of 1897; Ch. Centr. 1897, 2,
1063; 97847 of 1896; Ch. Centr.
1898, 2, 696; 97948 of 1897; Ch.
Centr. 1898, 2, 742; 103859 of 1898;
Ch. Centr. 1899, 2, 949 ; 109608 of
1897; Ch. Centr. 1900, 2, 408; and
110173 of 1898; Ch. Centr. 1900, 2,
460). The p-nitrobenzylideneaniline or

sulphonic acid obtained by this process
gives p-nitrobenzoic aldehyde (with the
base or its sulphonic acid) on hydrolysis
with dilute mineral acid (see also under
benzoic aldehyde [114 ; A]).

Or p-nitrobenzylideneaniline or its
sulphonic acid can be reduced to the
p-aminobenzylidene compound by alka-
line sulphides : the latter on hydrolysis
gives p-aminobenzoic aldehyde, which
can be converted into the hydroxy-alde-
hyde by the diazo-method as above under
B (Meister, Lucius, and Briining, Germ.
Pat. 99542 of 1897; Ch. Centr. 1899,
1, 238; Germ. Pat. 100968 of 1897;
Ibid. 958 : also Journ. Soc. Ch. Ind. 17,
658; 18, 363 and 488 for Eng.
Patents).

Or p-nitrobenzyl chloride can be con-
verted into p-nitrobenzyl alcohol (or its
phenolsulphonic ether), which gives p-
aminobenzoic aldehyde on heating with
alkaline sulphides (Meister, Lucius, .and
Briining, Germ. Pat. J 06509 of 1898;
Ch. Centr. 1900, 1, 1084).

p-Nitrobenzyl chloride on combina-
tion with hydroxylamine gives ^-<^-
nitrobenzylhydroxylamine, which forms
a nitroso-derivative by the action of
nitrous acid. The nitroso-compound
decomposes on solution in acetic (with
nitric) acid with the formation of bis-
nitrosyl-p-nitrobenzyl, (NOg . C,jHg)2
(N0)2 (Behrend and Konig, Ann. 263,
216). Or the bisnitrosyl-compound can
be obtained by the action of bromine
water on p-nitrobenzylhydroxylamine
hydrochloride (Kjellin and Kuylen-
stjenia, Ber. 30, 1897). The bis-
nitrosyl-compound is decomposed by
caustic potash solution with the forma-
tion of p-nitrobenzaldoxime (a and /3)
(Behrend and Konig, loc. cit. 347).
Nitrobenzaldoxime is also formed from
nitrobenzylhydroxylamine as one pro-
duct of the action of bromine (Kjellin
and Kuylenstjerna, loc. cit.). The
nitrobenzaldoxime can be converted into
the amino-oxime, the amino-aldehyde,
and the hydroxy-aldehyde as above
under B. (For convertibility of a- and
/3-oximes see Behrend, Ber. 24, 3088.)

According to Geigy & Co. (Germ.
Pat. 86874 of 1895 ; Ber. 29, Ref. 530)
p-nitrotoluene gives p-aminobenzoic

218

AROMATIC ALDEHYDES AND KETONES [ll9 E-120 C.

aldehyde on reduction with alkahne
sulphide in dilute alcohol, or with sul-
phur in hot fuming sulphuric acid.

p-Nitrotoluene and oxalic ester com-
bine in the presence of sodium ethoxide
to form p-nitrophenylpyroracemic acid,
which gives p-nitrobenzoic aldehyde on
oxidation with chromic acid mixture
(Reissert, Ber. 30, 1049). p-Nitro-
toluene by the action of amyl nitrite in
presence of sodium ethoxide gives p-
nitrobenzaldoxime(Angeli and Angelico,
Atti Real. Accad. [5] 8, II, 28 ; Ch.
Centr. 1899, 2, 371 ; Meister, Lucius,
and Briining, Germ. Pat. 107095 of
1898; Ch. Centr. 1900,1, 886; Lap-
worth, Trans. Ch. Soc. 79, 1^74).

[F.] Paracresol [63], on oxidation
with sulphuric and chromic acids in
presence of acetic anhydride, gives p-
hydroxybenzaldehyde triacetate (Thiele
and Winter, Ann. 311, 357). The
triacetate is decomposed with the forma-
tion of the aldehyde on heating with
dilute acid {Ifjicl.).

120. Anisic Aldehyde;
Faramethoxybenzoic Aldehyde.

CHO

OCH3

Natural Sources.

Russian oil of aniseed (from Pim-
pinella anismn) contains a small quantity
of this aldehyde (Bouchardat and Tardy,
Bull. Soc. [3] 15, 612). French oil of
bitter fennel contains anisic aldehyde
(Tardy, Rid. [3] 17, 580). In Chinese
star-anise oil (itjid. [3] 27, 990). The
existence of the aldehyde in these oils
may be due to the oxidation of ane-
thole.

Synthetical Processes.

[A.] Yrovc^p-hydroxyhenzaldehyde [119]
by methylation with potassium hydr-
oxide and methyl iodide [13] in methyl

alcoholic solution (Tiemann and Herz-
feld, Ber. 10, 6-^).

[B.] From phenol [6O] through ani-
sole by methylation (Cahours, Ann. 78,
236 ; Vincent, Bull. Soc. [2] 40, 106 ;
Kolbe, Joum. pr. Ch. [2] 27, 425;
Auer, Ber. 17, 672 ; Kralft and Roos,
Germ. Pat. 76574 of 1893; Ber. 17,
Ref. 955 ; Ullmann and Wenner, Ber.
33, 2476). The latter combines with
hydrogen cyanide [172] in presence of
hydrogen chloride and aluminium chlor-
ide to form a compound which gives
anisic aldehyde on decomposition with
dilute acids (Gattermann, Ber. 31,

Or from anisole and carbon mon-
oxi le, the latter being converted into
carbonyl chloride, and then into chlor-
carbamide by the action of ammonium
chloride (Gattermann and Schmidt,
Ber. 20, 118; 858; Ann. 244, 30).
Chlorcarbamide and anisole combine in
the presence of aluminium chloride to
form anisamide (Gattermann, Ann. 244,
62), and this on reduction with sodium
amalgam in acid solution gives anisyl
alcohol (Hutchinson, Ber. 24, 175),
from which the aldehyde can be obtained
as under E. Or anisamide can be
hydrolysed to anisic acid and treated as
under P.

Or from anisole and ethyl alcohol [14]
through mercury fulminate (see under
benzoic aldehyde [114; A]). The latter
condenses with anisole in presence of
aluminium chloride and hydrate to form
0- and p-anisic aldehyde and oxime and
p-anisic nitrile (Scholl and Hilgers,
Ber. 36, 648).

Anisole also combines with ethyl-
oxalyl chloride = chlorethanalic ester
(from oxalic acid [Vol. II] and ethyl
alcohol [14] ; Henry, Ber. 4, 599 ;
Anschiitz, Ber. 19, 2159; Peiatoner
and Strazzeri, Gazz. 21, 301) in presence
of aluminium chloride to form anisole-
glyoxylic ester. The acid (p-methoxy-
phenylglyoxylic) obtained from the
latter by hydrolysis gives anisic alde-
hyde on heating per se, or (better) with
aniline (Bouveault, Bull. Soc. [3] 17,

943)-

[C] From anethole [68] by oxidation

(Cahours, Ann. Chim. [3] 14, 484 ; 23,

120 C-121.]

ANISIC ALDEHYDE

219

354 ; Rossel, Ann. 151, 25 ; Labbe,
Bull. Soc. [3] 21, 1076; Otto and
Verley, Germ. Pat. 97620 of 1895;
Ch. Centr. 1898, 2, 693), or by the
action of boron fluoride (Landolph, Ber.
12, 286).

[D.] From salicylic acid [Vol. II]
through anisole by distilling the methyl
ether with baryta (Cahours, Ann. 48,
6^), and then as above under B.

[E.] From p-hydroxyhenzyl alcohol
[56] through p-methoxybenzyl = anisyl
alconol by methylation (Biedermann,
Ber. 19, 2376) and the aldehyde by
oxidation (Cannizzaro and Bertagnini,
Ann. 98, 189).

[F.] Anisic acid [Vol. II] gives the
aldehyde on distilling the calcium salt
with calcium formate [Vol. II] (Piria,
Ann. 100, 105).

[G.] From benzene [6 ; I, &c.] through
nitrobenzene and aniline. The latter,
on conversion into a diazonium salt and
treatment with methyl alcohol, gives
anisole (Beeson, Am. Ch. Journ. 16,
234 ; Cameron, Ibid. 20, 250 : see also
Hantzsch and Spear, Ber. 33, 2538 ;
Hantzsch and Jochem, Ber. 34, 3337).
Subsequent steps as above under B.

Or benzenesulphonic acid gives ani-
sole directly on distilling its sodium
salt with sodium methylate (Moureu,
Bull. Soc. [3] 19, 403).

121. Vanillin; Methylproto-

catechuic Aldehyde ;

3-Methoxy-4-hydroxybenzoic

Aldehyde.

CHO

OCH3
HO

Natural Sources.

In pods of the vanilla bean, from
Vanilla planifolia and its varieties, V.
sativa, V. sylvedris, and V. pompona, all
from Mexico. In V. guyanensis from
Guiana and Surinam ; in V. palmarum
from Bahia; in V. aromatica from
Brazil and Peru ; in V. planifolia var.

from Reunion, and in Y. ensifolia from
New Granada. The isolation of vanillin
from the pods of V. aromatica is due to
Gobley (Jahresber. 1858, 534 : see also
Stokkebye, Ibid. 1864, 612).

Vanillin occurs in Siam benzoin
(Jannasch and Rump, Ber. 11, 1635;
Liidy, Arch. Pharm. 231, 461), in assa-
foetida (Schmidt, Arch. Pharm. [3] 24,
534; Tschirch and Polacek, Ibid. 235,
126), in small quantities in certain beet
sugars (Weger, Ding. poly. Journ. 237,
146; Scheibler,Ber. 13, 335; v.Lippmann,
Ibid. 662}, in asparagus (v. Lippmann,
Ber. 18, 3335), in the seeds of Lupitius
albics (Campani and Grimaldi, Gazz. 17,
545), in flowers of the orchid, Nigritella
snaveolens (v. Lippmann, Ber. 27, 3409),
and in resins from pine and larch (Max
Bamberger and Landsiedl, Monats. 18,
481 ; 502). Vanillin is possibly present
in yellow acaroid or Botany Bay resin
from XanthorrJioca hastilis (Tschirch and
Hildebrand, Arch. Pharm. 234; Ch.
Centr. 1897, 1, 422).

Vanillin occurs in cinnamein from
Peru balsam, San Salvador (Thoms,
Ber. deutsch. pharm. Gesell. 8, 264;
Ch. Centr. 1898, 2, 1030; Tschirch
and Knitl, Arch. Phaim. 237, 271 ; Ch.
Centr. 1899, 2, 315), and in opoponax
from Opoponax c/iironium (Tschirch and
Knitl, loc. cit. 256; Ch. Centr. 1899,

Vanillin has been found in oriental
storax from Liquidambar orientalis and
American storax from L. styraciflua
(Tschirch and Van Itallie, Arch. Pharm.
239,506; 532).

A vanillin glucoside occurs in the
husk of oats (Rawton, Com p. Rend.
125,797). According to Singer (Monats.
3, 409), vanillin is widely distributed
in traces in all woody portions of plants
(see also Czapek, Zeit. physiol. Ch. 27,
148). Vanillin occurs in cork (Kiigler,
Journ. Pharm. [5] 10, 123 ; Brautigam,
Ch. Centr. 1898, 2, 858; 889; Thoms,
Ibid. 1102), and in the volatile oil of
Spiraea (Schneegans and Gerock, as
quoted by Gildemeister and Hoffmann,
p. 551). According to Brautigam, po-
tato peel contains a compound which
gives vanillin under the influence of
heat and atmospheric oxygen (Pharm.

220

AROMATIC ALDEHYDES AND KETONES

[121-C.

Zeit. 45, 164; Ch. Centr. 1900^ 1, 728).
Vanillin has been extracted in small
quantity from the new bark of the lime
tree, Tilia sp. ? (Brautigam, Arch.
Pharm. 238, SS6).

According to Busse (see Ch. Centr.
1900, 1, 557), vanillin is produced in
Vanilla species in the first place as a
glucoside. The same view is expressed
by Behrens (Ibid. 2, 769 : see also
Molisch, Ber, deutsch. bot. Gesell. 19,
350). Lecomte attributes the forma-
tion to the hydrolysis of coniferin and
oxidation of coniferyl alcohol by an
oxidase (Comp. Rend. 133, 745)'

Synthetical Processes.

[A.] From catechol [69] through
guaiacol by methylation with potassium
methyl sulphate (Gorup-Besanez, Ann.
147, 24S), and the action of chloroform
[1 ; D] and caustic alkali on guaiacol
(Reimer and Tiemann, Ber. 9, 424 j
Tiemann and Koppe, Ber. 14, 2023 ;
Traub, Germ. Pat. 80195 of 1894;
Ber. 28, Ref. 524; Soc. Chim. d.
Usines du Rhone, Eng. Pat. 21 106 of
1896; Journ. Soc. Ch. Ind. 16, 758).

Or guaiacol can be converted into its
carboxylic acid by heating its salts in
an atmosphere of carbon dioxide (F. v.
Heyden, Nachf. Germ. Pat. 5138 1 of
1889; Ber. 23, Ref. 418). Guaiacol-
earboxylic acid on heating with chloro-
form and alkali gives aldehydoguaiacol-
carboxylic acid, and the latter is de-
composed into vanillin on heating {Ibid.
Germ. Pat. 71162 of 1892; Ber. 26,
Ref. 995; Germ. Pat. 72600 of 1893;
Ber. 27, Ref. 218).

The aldehyde group can also be
introduced into guaiacol by means of
nitrobenzenesulphonic acid and formic
aldehyde [9l], and hydrolysis of the
product (Geigy & Co., Eng. Pat. 27236
of 1898; Journ. Soc. Ch. Ind. 19,
41). Or by the action of hydrogen
cyanide [172] and hydrogen chloride, in
presence or absence of aluminium
chloride, and hydrolysis of the product
(Bayer & Co., Germ. Pat. 106508 of
1898 and previous Patents; Ch. Centr.
1900,1,742).

Or aniline and formic aldehyde may

be condensed with guaiacol to form
hydroxymethoxybenzylaniline, which
can be oxidised to a benzylidene de-
rivative, and finally to vanillin (Meister,
Lucius, and Briining, Germ. Pat. 109498
of 1898 ; Ch. Centr. 1900, 2, 457 : see
also the Pats, of this Firm under p-
hydroxybenzaldehyde [119 ; E]).

Note :— Catechol can be converted into
protocatechuic aldehyde by chloroform and
alkali (Tiemann and Eeimer, Ber. 9, 1269 ; T.
and Koppe, Ber. 14, 2015), or by the action of
formic aldehyde and aromatic hydroxylamine
sulpho-acids, &c., as in the process applied to
guaiacol above (Geigy & Co., loc. cit. and
Germ. Pat. 105798 of 1898 ; Ch. Centr. 1900, 1,
523). From protocatechuic aldehyde as below
under E.

[B.j From phenol [6O] through o-
nitrophenol and its methyl ether (o-
nitroanisole), o-anisidine, and guaiacol
(for references see under catechol [69 ;
a]), and then as above.

Or from anisidine through its com-
pound with alloxan [Vol. II], which is
decomposed on heating with sulphuric
acid with the formation of p-amino-
m-methoxybenzoic aldehyde (Pellizari,
Gazz. 17, 412; Bohringer & Sohne,
Germ. Pat. 108026 of 1898 ; Ch. Centr.
1900, 1, 1115). The latter can be con-
verted into vanillin as below under C.

Or phenol on bromination at 150-
1 80" gives o-bromphenol (see under
catechol [69; A]). The latter can be
converted into 3-brom-4-hydroxybenzoic
aldehyde (Geigy & Co., Germ. Pat.
105798 of i89'8; Ch. Centr. 1900, 1,
523), and this yields protocatechuic
aldehyde on heating with caustic soda-
lye to 150-200° (Baum, Germ. Pat.
82078 of 1894; Ber. 28, Ref. 803).
From the aldehyde as below under E.

Note : — o-Bromphenol is obtained also from
o-nitrophenol through o-aminophenol by the
diazo-method (Meldola and F. H. Streatfeild,
Trans. Ch. Soc. 73, 685).

[C] From benzoic aldehyde [114]
through the m-nitro-aldehyde by nitra-
tion (Widmann, Ber. 13, 678; Fried-
liinder and Henriques, Ber. 14, 2802 ;
Ehrlich, Ber. 15, 2010; Camps, Arch.
Pharm. 240,T),the m-amino-aldehyde by
reduction, and the m-hydroxy -aldehyde
[118] by the diazo-method (Meister,
Lucius, and Briining, Germ. Pat. 18016

121 C-I]

VANILLIN

221

of 1 88 1 ; Ber. 15, 1098; Tiemann and
Ludwi^j Ibid. 2044). The hydroxy-
aldehyde by methylation gives the
methoxy- aldehyde, and this, on heating
with acetic anhydride and sodium ace-
tate, yields m-methoxycinnamic acid.
The latter (methyl ester) on nitration
gives m-methoxy-p-nitrocinnamic ester,
and this, on hydrolysis and oxidation
with potassium permanganate, yields
m-methoxy-p-nitrobenzoic aldehyde. The
latter, on reduction and application of the
diazo-method, gives vanillin (M. L. & B.
loc. cii. ; Ulrich, Ber. 18,2571; Germ.
Pat. 32914 of 1884 ; Ber. 18, Ref. 68a).
[D.] From p-hydroxyhenzoic aldehyde
[119] through the m-nitro-aldehyde by
nitration (Mazzara, Jahresber. 1877,
61 7 ; Paal, Ber. 28, 241 3), the m-amino-
aldehyde by reduction, and replacement
of the amino- by the methoxy-group by
the diazo-method followed by methyla-
tion (Bergmann, Am. Pat. 571917 of
1896; Ber. 29, Ref. 1192). Or p-hy-
droxybenzoic aldehyde on bromination
gives the 3-bromo-derivative (Paal, Ber.
28, 2409). From the latter through
protocatechuic aldehyde (Baum: see
above under B), and then as below
under E.

Note : — m-ITydroxybensoic aldehyde [118] on
bromination gives 4-brom-3-hydroxybenzoic
aldehyde, and this also yields protocatechuic
aldehyde on heating with soda-lye (Baum,
loc. ciL).

[E.] Piperonal [122] on heating with
dilute hydrochloric acid at 200°, or on
boiling the dichloro-derivative with
water, gives protocatechuic aldehyde
(Fittig and Remsen, Ann. 159, 148 ;
168, 97 : see also Wegscheider, Monats.
14, 382). The disodium salt of the
aldehyde, or the sodium salt of the
monoacetyl derivative, on methylation
by methyl chloride or by methyl alkali
sulphate, yields vanillin or its acetyl-
derivative; the latter can be hydrolysed
(Bertram, Germ. Pat. 63007 of 1890;
Ber. 25, Ref. 823 : the yield is better
with dimethyl sulphate and alkali,
Sommer, Germ. Pat. 1 22851 of 1900;
Ch. Centr, 1901, 2, 517).

Or the potassium salt of the alde-
hyde on treatment with chloroformic-
methyl ester gives two carboxylic esters

of protocatechuic aldehyde, of which the
p-modification yields vanillin on heating
with dimethyl sulphate in alcoholic
alkaline solution and subsequent acidifi-
cation (Soc. .Chim. d. Usines du Rhone,
Germ. Pat. 93187 of 1896; Ch. Centr,
1897, 2, 1016 j Eng. Pat. 16239 of
1896; Journ. Soc. Ch. Ind. 16, 633).

Notes: — The chloroformic ester (= methyl-
chlorocarbonate) is obtained by the action of
phosgene on methyl alcohol (Dumas, Ann. 10,
277 ; Ann. Chim. 58, 52 ; Meyer and Wurster,
Ber. 6, 965 ; Klepl, Journ. pr. Ch. [2] 26, 447 ;
Hentschel, Ber. 18, 1177).

Processes depending on the combination of
protocatechuic aldehyde with benzene- or
toluenesulphonic acid, methylation of the ester,
and subsequent decomposition into vanillin
will be found in the following Germ. Pats, of
the Ch. Fab. vorm. E.Schering : — 80498 of 1893 ;
Ber. 28, Ref. 581 ; 82747 of '894 '> Ber. 28, Ref.
878. The aldehyde may also be converted first
into a benzyl ether, and the latter methylated
and then decomposed by heating with acid
{Ibid. 82816 of 1893 ; Ber. 28, Ref. 878).

[P.] From m-cresol [62], which gives
on nitration a mixture of 6-nitro- and
4-nitro-m-cresol (Stiidel, Ann. 217,
51; 259, 208; Ber. 22, 215; Reissert
and Scherk, Ber. 31, 393). The methyl
ether of the latter condenses with oxalic
ester in the presence of sodium ethylate
or methylate, with the formation of the
nitromethoxyphenylpyroracemic acid
(see under p-hydroxybenzoic aldehyde
[119; E, p. 218]; Reissert, Ber. 31,
397). The latter can be converted into
vanillin by replacement of the nitro-
group by hydroxyl, and the pyroracemic
acid residue by the aldehyde-group,
CHO (Reissert, Germ. Pat. 94630 of
1897; Ch. Centr. 1898, 1, 296).

[G.] From vanillic acid [Vol. II] by
distilling the calcium salt with calcium
formate (Tiemann, Ber. 8, 1124), or by
heating with chloroform [l ; D] and caus-
tic alkali in aqueous solution (Tiemann
and Mendelsohn, Ber. 9, 1280).

[H.] Ferula/ic acid [Vol. II] gives
vanillin on oxidation (Ulrich, Germ.
Pat. 32914 of 1884; Ber. 18, Ref. 682).

[I.] From veratric acid [Vol. II]
through veratrole (see under catechol
[69 ; F]). The latter combines with
ethyloxalyl chloride or amyloxalyl
chloride in presence of aluminium chlor-
ide to form veratroylglyoxylic esters
(Bouveault : see under anisic aldehyde

222

AROMATIC ALDEHYDES AND KETONES [121 1-122 A.

[120 ; B])^ which hydrolyse to vera-
troylcaibonic acid. The latter^ on heat-
ing- with aqueous potash at 160-170°,
gives, among the products of its de-
methylation, vanilloylearbonic acid, and
this yields vanillin as below under K.

[J.] Isoeugenol [79] gives vanillin on
oxidation by ozone or on electrolysis of
a solution of one of its salts (E. v.
Heyden, Nachf. Germ. Pat. 92007 of
1895; Ch. Centr. 1897, 2, 454; Otto
and Verley, Germ. Pat. 97620 of 1895 ;
Ch. Centr. 1898, 2, 693; Verley, Am.
Pats. SS^^9?, and 563039 of 1896).
Also by oxidation with metallic per-
oxides in alkaline solution (Haarmann
and Reimer, Germ. Pat, 93938 of 1896;
Ch. Centr. 1897, 2, 1166). Isoeugenol
gives vanillin by ' contact ' oxidation
on passing the vapour mixed with air
over heated platinum (Trillat, Comp.
Rend. 133, 822).

y Isoeugenylsulphuric acid (potassium
salt) on oxidation with ozone gives po-
tassium vanillyl sulphate, and this yields
vanillin on decomposition by dilute
acids (Verley, Bull. Soc. [3] 25, 48).
Or isoeugenol can be benzylated by
means of benzyl chloride (see under
benzyl alcohol [54 ; A]), and the
benzyl ether oxidised to the methyl
benzyl ether of protocatechuic aldehyde,
which splits off benzyl and gives
vanillin on heating with hydrochloric
acid (Bohringer & Sohne, Germ. Pat.
65937 of 1891 ; Ber. 26, Ref. 211).

Or isoeugenyl acetate, on oxidation
with potassium permanganate, gives
vanilloylearbonic = p-hydroxy-m-meth-
oxybenzoylcarbonic acid, and this yields
vanillin on heating above its melting
point (Tiemann, Ber. 24, 2878), on
heating with aniline and decomposing
the anilide by heating with dilute sul-
phuric acid (Gassmann, Comp. Rend.
124, 38), or by heating with dimethyl-
aniline (I3ouveault, Bull. Soc. [3] 19, 76).

Note : — For production of vanillin by the
oxidation of isoeugenyl acetate or benzoate see
also Haarmann and Reimer, Germ. Pat. 57568
of 1890 ; Ber. 25, Ref. 93 \ also Germ. Pat.
63027 of 1891 ; Ber, 25, Ref. 824.

Isoeugenol can be combined with
phenylhalogenacetic acids or their

amides, nitriles, or ethers, or with co-
halogen-toluic acids so as to form the
corresponding isoeugenol-ether acids.
These are oxidised by acid and a di-
chromate with the formation of the cor-
responding vanillin-ether acids, and the
latter give vanillin (and the ether-acid)
on decomposition by mineral acid
(Majert, Germ. Pat. 82924 of 1894;
Ber. 28, Ref. 878).

[K.] From toluene [54] through m-
chlor-p-nitrotoluene, the corresponding
chlornitrobenzyl chloride or bromide, and
the corresponding aldehyde by oxidation
with lead or copper nitrate. The chlor-
nitrobenzoic aldehyde on heating with
sodium methoxide exchanges chlorine
for the methoxy-group, and the p-nitro-
m-methoxybenzoic aldehyde can be con-
verted into vanillin as above under C
(Landsberg, Germ. Pat. 37075 of 1886 ;
Ber. 19, Ref. 861).

Or from toluene through ortho- or
paratoluidine, m-(3)-nitro-p-toluidine,
and m-nitrotoluene (Beilstein and Kuhl-
berg, Ann. 158, 346). The latter gives
m-nitrobenzoie aldehyde by electrolytic
oxidation (Pierron, Bull. Soc. [3] 25,
852). Subsequent steps as above
under C.

122. Fiperonal ; Frotocatecliuic

Aldehyde Methylene Ether ;

Heliotropin.

CHO

Natural Soueces.

Said to occur in oil of Spir^p.a (Schnee-
gans and Gerock, as quoted by Gilde-
meister and Hoffmann, p. 551). Ac-
companies vanillin from certain species
of Vanilla (Busse, Ch. Centr. 1900, 1,

Synthetical Processes.

[A.] From catechol [69] through
protocatechuic aldehyde by the action of

122 A-124 A.]

PIPERONAL

223

chloroform [l ; D] in presence of aqueous
caustic soda (Tiemann and Reimerj Ber.
Q, 1 369 ; Tiemann and Koppe^ Ber. 14,
2015). The aldehyde gives piperonal
on treatment with meth/jleue iodide (see
under ethyl alcohol [14 ; I ; M]) and
potassium hydroxide in methyl alcohol
(Wegscheider, Monats. 14, 388).

[B.] Piperic acid [Vol. II] gives
piperonal on oxidation with potassium
permanganate in neutral or alkaline
solution (Fittig and Mielck, Ann. 152,
•^^ ; Doebner, Ber. 23, 2375).

123. Ciunamic Aldehyde ;
Phenepropenylal ; /3-Pheiiylacrolein.

CH : CH . CHO

Natural Sources.

In oil of cinnamon from Cinnamomiim
zejjlanicum, Ceylon (Dumas and Peligot,
Ann. Chim. 57, 305 ; Ann. 14, 50), and
in oil of cassia from C. cassia {Ibid. ;
Ann. 12, 24; 13, 76; 14, 50). The oil
is obtained from the bark, waste twigs,
and root of C. zeylanicum. Oil of
cinnamon leaf contains eugenol and
but little cinnamie aldehyde (Weber,
Arch. Pharm. 230, 728).

Oil of cassia (Chinese) is prepared
from leaves, flower and leaf stalks, buds
and twigs of C. cassia, the oils from
these parts of the shrub all containing
the aldehyde as well as the oil from the
bark (Schimmel's Ber. Oct. 1892).

Occurs also in oil of Cinnamomum
loureirii from Japan (Shimoyama;
Gildemeister and Hoffmann, p. 509),
and in rassamala resin from the Javan
AUingia exce/sa (Tschirch and Van
Itallie, Arch. Pharm. 239, 541).

Cinnamie aldehyde is said to be
among the products of the pancreatic
fermentation of fibrin (Ossikowszky,
Ber. 13, 326).

Synthetical Processes.

[A.] From he7izoic aldehyde [ll4] and
acetic aldehyde [92] by saturating a
mixture of the two aldehydes with hy-
drogen chloride, and then heating
(Chiozza, Ann. 97, 350). Or by allow-
ing the mixed aldehydes to remain in
contact with dilute caustic soda solution
(Peine, Ber. 17, 2117). The condensa-
tion of the aldehydes is best effected
by alcoholic sodium hydroxide at — 10°
(Bohringer & Sohne, Eng. Pat. 10003
of 1896 ; Journ. Soc. Ch. Ind. 16,

463)-

[B.] From cinnamie acid [Vol. II]
by distilling the calcium salt with cal-
cium, formate [Vol. II] (Piria, Ann. 100,
105)-

124. Orthocoumaric Aldehyde

Methyl Ether; Orthomethoxy-

ciunamic Aldehyde.

CH : CH . CHO

OCH,

Natural Source.

In oil of cassia, from Cinnamomum
cassia (Bertram and Kursten, Journ.
pr. Ch. [2] 51, 316).

Synthetical Process.

[A.] From salicylic [117] and acetic
aldehydes [92] and methyl alcohol [l3].
Salicylic aldehyde is converted into its
methyl ether by methylating the sodium
salt with methyl iodide (Perkin, Trans.
Ch. Soc. 55, ^^o ; Voswinckel, Ber. 15,
2024). o-Methoxy benzoic aldehyde and
acetic aldehyde condense when allowed
to stand in contact with dilute caustic
soda solution to form o-coumaric alde-
hyde methyl ether (Bertram and Kiir-
sten, Journ. pr. Ch. [2] 51, 316).

224

AROMATIC ALDEHYDES AND KETONES [125-126 A.

125. Asaryl Aldehyde ;

2:4: 5-Triiuethozybenzoic Aldehyde ;

2:4: S-Fhenetriolmethylal

Trimethyl Ether.

CHO

O.CH,

CHo.O

O.CH3

Natural Source.

The complex^ if not the free aldehyde,
occurs with asarone [89] in oil of Acorus
calamus (Thorns and Beckstroem, Ber.
34, 1021; 35, 3188).

Synthetical Processes.

[A.] From asarone [89] by oxidation
with chromic acid or potassium per-
manganate and sulphuric acid (Butleroff
and Rizza, Journ. Russ. Soc. 19, 3).

[B.] From hydroxy qinnol [85], methyl
alcohol [13], and hydrogen cyanide [172].
The trimethyl ether of hydroxyquinol
is treated in benzene solution with hy-
drogen cyanide and hydrogen chloride
in the presence of dry aluminium
chloride, and the product decomposed
by cold water (Gattermann and Eggers,
Ber. 32, 289).

126. Furfaral; Furfurol;

Fyromucic Aldehyde ;
Fnrancarboxylic Aldehyde.

HC-

HC

-CH

C.CHO

Natural Sources.

Furfural has been found in oil of
cloves (SehimmeFs Ber. Oct. 1896 ;
Ch. Centr. 1896, 2, 977 ; E. Erdmann,
Journ. pr. Ch. [2] 56, 154; SchimmeFs
Ber. April, 1897 ; Gerber, Mon. Sci.
[4] 11, 880), in the distillation water
from oil of caraway and oil of ambrette
seeds from Hibiscus abelmoschus (Schim-
mePs Ber. Oct. 1899 ; Ch. Centr. 1899,

2, 880). Also in the distillation water
from vetiver oil from Andropogon muri-
eatiis, E. and W. Indies, Brazil, &c.
{Ibid. April, 1900; Ch. Centr. 1900,

1, 907), and from oil of bay [Ibid. April,
J90I).

Ceylon oil of cinnamon contains fur-
fural (SchimmeFs Ber. April, 1902 ;
Walbaum and Hiithig, Journ. pr. Ch.
[2] 66, 47)-

The aldehyde is contained also in
petit-grain oil from Paraguay (Schim-
meFs Ber. Oct. 1902 ; Ch. Centr. 1902,

2, J 208), in the cohobation water of
savin oil from Jiiniperus sabina, and in
the distillation water of W. Indian
sandal-wood oil {Ibid. April, 1903 ; Ch.
Centr. 1903, 1, 1086).

Furfural has been found in brandy,
in certain fusel oils, in malt wort, and
beer (Morin, Comp. Rend. 105, 10 19 ;
Udranszky, Zeit. physiol. Ch. 13, 248 ;
Forster, 13er. 15, 230 ; 322 ; Brand,
Journ. Fed. Inst. 4, 562 ; Windisch,
Ibid. 561 ; Heim, Ibid. ^6 2,)'

According to Van Laer the furfural
found in the secondary products of
alcoholic fermentation is not of bio-
chemical origin, but due to subsequent
decomposition of furfural-yielding com-
pounds (Journ. Fed, Inst. 4, 2). This
may be true also of the furfural found
in the above plant oils.

Synthetical Processes.

[A.] From dextrose [l54] by heating
with dilute acids (Berthelot and Andre,
Comp. Rend. 123, 567). It has long
been known that sugars and other
carbohydrates yield furfural on dry
distillation or on heating with dilute
acids (Dobereiner, Ann. 3, 141 ; Volckel,
Ann. 85, 6^; Forster, Ber. 15, 230;
322 ; Stenhouse, Phil. Mag. [3] 18,
122; 37, 226; Fownes, Phil. Trans.
1 845, 253 ', Cahours, Ann. Chim. [3]
24, 277 ; Emmet, Am. Journ. Sci. 32,
140 ; Gudkoff, Zeit. [s] e^ 3^2;
Guyard, Bull. Soc. [2] 41, 289 ; SchifP,
Ber. 20, 540; Ann. 239, 382; Stone
and Tollens, Ann. 249, 237).

[B.] Mannose [156] gives furfural on
heating with water at 140° (Fischer
and Hirschberger, Ber. 22, 369).

126 C-K.]

FURFURAL

225

[C] From formic aldehyde [9l]
through a-acrose and a-acrosone (see
under mannitol [51; A]). The latter
gives furfural on heating with acids or
per se (Loew, Ber. 20, 141; 3039;
Fischer and Tafel, Ber. 22, 99).

[D.] From glycerol [48] through
a-acrose (see under mannitol [51 ; B]),
and then as above.

[E.] Tartaric acid [Vol. II] on oxida-
tion with hydrogen peroxide in presence
of ferrous salts gives dihydroxymaleic
acid, the aqueous solution of which
decomposes on heating with the forma-
tion of glycollic aldehyde. The latter
on heating at 100° in a vacuum poly-
merises to a 'sugar/ which yields fur-
fural on heating with water at 140°
(Fenton, Trans. Ch. Soc. 65, 899; 67,
48; 774 J 69,546; 71,375).

Note: — The 'sugar' is a mixture of a- and
i3-acrose (Jackson, Trans. Ch. Soc. 77, 129).
The polymerisation of glycollic aldehyde takes
place in presence of dilute caustic soda at 0°
{lUd.).

[P.] From acetal [93] through brom-
acetal (Pinner, Ber. 5, 149; Fischer
and Landsteiner, Ber. 26, 2551), brom-
acetaldehyde by distilling bromaeetal
with dry oxalic acid (F. and L. loc. cit),
glycollic aldehyde by the action of
barium hydroxide solution {Ibid. 2552),
and then as above under E.

Or brom- or chloracetal on heating
with alcoholic potash gives the acetal
of glycollic aldehyde (Pinner, loc. cit.
1 50 ; Marckwald and Ellinger, Ber.
25, 2984), from which the aldehyde
can be obtained by heating with very
dilute hydrochloric acid (M. & E. loc.
cit.).

[G.] From ethyl alcohol [14] through
ethylene, ethylene iodide, and 3-iodo-
ethyl ether by heating the latter with
water (Baumstark, Ber. 7, 1172). The
iodo-ether, by the action of sodium
ethylate, gives vinyl ethyl ether (Henry,
Bull. Soc. [2] 44, 458), which combines
with bromme to form i : 2-dibromethyl
ether (Wislicenus, Ann. 192, iii), from
which bromaeetal is obtained by the
action of sodium ethylate (Ibid. 112).
Subsequent steps as above under P
and E.

Or from ethyl alcohol through chlor-

acetal by the action of chlorine (Lieben,
Ann. 104, 114), glycollic aldehyde
acetal, and the aldehyde, &c., as above
under P.

Or from ethyl alcohol through ethyl
ether, i : 2-dichlorethyl ether by chlorina-
tion (Malaguti, Ann. 32, 15), chloracetal
by the action of sodium ethylate or
alcohol on the dichlorether (Lieben,
Ann. 146, 193 ; Paterno and Mazzara,
Ber. 6, 1 202; Natterer, Monats. 3, 444),
and then as above.

Note : — Generators of ethylene thus become
generators of furfural through glycollic alde-
hyde and the ' sugar ' obtainable from it.

[H.] From choline [Vol. II] through
ethylene glycol [45] (see under isopropyl
alcohol [I6 ; NN]), and then as below
under K and above under G.

[I.] Glycuronic acid [Vol. II] gives
furfural on distillation with acids
(Mann, Inaug. Diss. Gottingen, 1894;
TJdianszky, Zeit. physiol. Ch. 12, 389 ;
Giinther and Tollens, Ber. 23, 1751 ;
De Chalmot, Inaug. Diss. Gottingen,
1891).

[J.] d-Arabinose [153] gives furfural
on distillation with dilute sulphuric acid
(Wohl, Ber. 26, 735).

[K.] From ethylene glycol [45], the
glycol ethyl ether by the interaction
of ethyl iodide and sodium glycol
(Wurtz, Ann. Ch. [3] 55, 429), 2-iodo-
ethyl ether by the action of phosphonis
triiodide on the glycol ether (Demole,
Ber. 9, 746), and then vinyl ethyl ether,
I : 2-dibromethyl ether, and bromaeetal,
&c., as above.

Or ethylene glycol gives glycollic
aldehyde directly by oxidation with
hydrogen peroxide and ferrous sulphate
(Fenton and Jackson, Trans. Ch. Soc.
75, 2).

Note :— The alcohol, C4H3O . CHj . OH, corre-
sponding to the aldehyde, has been found in
the oil (steam distilled) from roasted coffee
berries (E. Erdmann, Eer. 35, 1846). It is not
strictly a biochemical product. The alcohol
can be obtained from furfural by the action of
alcoholic or aqueous potasli (Ulrich, Jahresber.
1860, 269 ; Schiff, Ann. 239, 374 ; Wissell and
Tollens, Ann. 272, 293 ; E. Erdmann, Ber. 35,
^855), or by reduction with sodium amalgam
(Beilstein and Schmelz, Ann. Suppl. 3, 275;
Baeyer, Ber. 10, 357).

226

AROMATIC ALDEHYDES AND KETONES [127-128 A.

127. Carvone.

CH^CHs)^
CH

H,C

CH,

HC C:0

CH,

Natueal Sources.

d-Carvone occurs in oil of caraway
from Carum canii (Volckel, Ann. 35,
308 ; 85, 246 ; Wallach, Ann. 277,
107), and in oil of dill irom. Peucedanum
graveolena (Gladstone, Journ. Ch. Soe.
25, I ; Beyer, Arch. Pharm. 221,
283).

1-Carvone occurs in oil of spearmint
from Mentha aquatica, var. crispa (Ger-
many), and from M. viridis, N. America
(Gladstone, loc. cit. ; Fliickiger, Ber. 9,
473 ; Beyer, loc. cit. ; Kremers and
Schreiner, Pharm. Rev. 14, 244 ; Wal-
lach, Ann. 305, 223 ; in Russian oil,
see SchimmeFs Ber. April, 1898; Ch.
Centr. 1898, 1, 991), and in oil of
kuromoji from the Japanese Lifidera
sericea (Kwasnik, Ber. 24, 81 ; Arch.
Pharm. 230, 265).

Synthetical Processes.

[A.] From dipentene (limonene) [9]
by combination with nitrosyl chloride
and decomposition with alcoholic potash,
whereby the oxime of carvone is pro-
duced (Goldschmidt and Ziirrer, Ber.
18, 1732; Wallach, Ann. 245, 268).
The same nitrosochloride is obtained
by mixing d- and 1-limonene nitroso-
chlorides (Wallach, Ann. 252, 124;
270, 175).

Or limonene tetrabromide (Wallach,
Ann. 227, 280), on heating with methyl
alcoholic sodium methoxide, gives brom-
carveol methyl ether {Ibid. Ann. 281,
129), and this, by the further action of
sodium ethoxide in absolute alcohol,
yields carveol methyl ether {Ibid. 132).
The latter on oxidation with chromic
acid in acetic acid solution gives i-
carvone.

[B.] Terpineol [39] gives a nitroso-
chloride (Wallach, Ann. 277, I2i),
which on heating with sodium ethoxide
gives ^ oxybishydrocarvoxime ^ = HO .
CioH5:N.OH. The latter yields i-
carvone on heating with dilute sulphuric
acid {Ibid. Ber. 28, 1773 ^ Wallach and
Arny, Ann. 291, 342).

128. Fnlegone.

CH,

H,C

H,C

CH

\

CHj

C:0

c/

C(CH3),

Natural Sources.

In oil of European pennyroyal from
Mentha pulegimn (Beckmann and Ploiss-
ner, Ann. 262, 1 ; Bull. Soc. [3] 25,
no; Tetry, Ibid. 27, 186), and of N.
American wild mint from Mentha cana-
densis (Gage, Pharm. Rev. 16, 412).

Has been found also in oil of Ameri-
can pennyroyal from Hedeoma pule-
gioides (Habhegger, Am. Journ. Pharm.
65, 417), in oil from the mountain
mint, Pycnanthemum lanceolaticm =
Thymus virginicus (Alden, Pharm. Rev.
16, 414), in the oil of Bystropogon
origanifolium fromTeneriffe (SchimmeFs
Ber. Oct. 1902; Ch. Centr. 1902, 2,
1208), and in oil of sweet marjoram
from Origanum major ana (Genvresse
and Chablay, Pharm. Centr. 43,
419; Pharm. Journ. 69, '>,'>i^', Journ.
Soc. Ch. Ind. 21, 1347).

The natural product is d-pulegone.

Synthetical Processes.

[A.] Citronellal [105] on heating
with acetic anhydride gives isopnlegol
[42], and this on oxidation with chromic
acid in acetic acid yields isopulegone.
The latter is transformed into pulegone
by contact with barium hydroxide solu-
tion at ordinary temperatures (Tiemann
and Schmidt, Ber. 29, 903 ; 30, 29 ;

128 A-129 D.]

PULEGONE

227

Tiemann, Ber. 32, 825 ; Harries and
Roeder, Ibid. ^'^Sl)-

Note : — Isopulegol is formed (with mentho-
glycol) by agitating citronellal with 5 per cent,
sulphuric acid (Barbier and Leser, Comp.
Rend. 124, 1308).

[B.] From isopulegol [42] as above.

129. Meuthone;
Methylisopropyl-ketohexametliyleue.

CH3
CH

H,C CH2

H.,C C:0

CHCCHs)^

Natural Soueces.

With menthol [4l] in oil of pepper-
mint from Mentha piperita and vars.
(Moriya, Trans. Ch. Soc. 39, 82;
Andres and Andrejeff, Journ. Russ.
Soc. 23, 26; Ber. 25, 617; Wallach,
Ber. 28, 1955; Power and Kleber,
Arch. Pharm. 232, 639 ; Charabot,
Bull. Soc. [3] 19, 117 : see also
SchimmeFs Ber. April, 1895: for
ocemTcnce in essence of Mentha pule-
giimi see Tetry, Bull. Soc. [3] 27, 186;
in Italian oil of peppermint, SchimmeFs
Ber. Oct. 1902).

In Bourbon geranium oil (Flatau and
Labbe, Bull. Soc. [3] 19, 788). In oil
of Eucalyptus hfsmastoma (SchimmeFs
Ber. April, 1888), and in the oil of
Bystropogon origauifolius, Teneriffe
{I/Ad. Oct. 1902; Ch. Centr. 1902, 2,
1208). Possibly occurs in oil from
' bucco-leaves •* from S. African species
of Barosma (Gildemeister and Hoff-
mann, p. 599 ; also Kondakoff and
Bachtschieff, Journ. pr. Ch. [2] 63, 49 :
see also under dipentene [9, p. 37]).

The natural product is 1-menthone.
According to Charabot (Ann. Chim.
[7] 21, 207 ; 279), menthone is probably
formed in plants from the oxidation of
citronellol.

Synthetical Processes.

[A.] From menthol [41] by oxidation
with sulphuric acid and potassium di-
chromate (Moriya, loc. cit. 77 ; Atkin-
son and Yoshida, Trans. Ch. Soc. 41,
49; Beckmann, Ann. 250, 325; 289,
362).

1-Menthone, on treatment with strong
acids or alkalis at ordinary tempera-
tures, or by keeping per se, is trans-
formed into d-menthone (Beckmann,
Ann. 250, 334).

[B.] Citronellol [38] is said to give
menthone among the products of its
oxidation ( Barbier and Bouveault, Comp.
Rend. 122,673; ^^T, 795).

Note : — The citronellol referred to is the
* rhodinol ' of Barbier and Bouveault. Ac-
cording to Bouveault rhodinal is transformed
into menthone by the same process as that by
which citronellal is transformed into pulegone
(see above). Tiemann and Schmidt on the
other hand consider rhodinol and citronellol to
be the same compound and the corresponding
aldehydes to be also identical (Tiemann and
Schmidt, Ber. 29, 925 ; Harries and Roeder,
Ber. 32, 355 : compare Bouveault, Bull. Soc.
[3] 23, 458 ; 463).

[C] From metacresol [62] through
m-(y)-cresotic acid (m-nomosalicylic
= m-hydroxy-p-toluic acid) by the
action of sodium and carbon dioxide
(Engelhardt and Latschinoff, Zeit. [2]
5, 623 ; Biedermann and Pike, Ber. 6,
324). Dibrom-m-cresotic acid, on heat-
ing with sodium in amyl alcohol and
oxidation of the product with alkaline
permanganate, gives /3-methylpimelic
acid (Einhorn and Ehret, Ann. 295,
173). The diethyl ester of the latter
condenses under the influence of sodium
with the formation of methyl-/3-keto-
hexamethylenecarboxylic ester, and this
on treatment with sodium and isopropyl
iodide [16] gives the isopropyl methyl
derivative. The latter on heating with
strong alcoholic potash yields a ketone,
which is probably methylisopropylketo-
hexamethylene = i-menthone (Einhorn
and Klages, Ber. 34, 3793)-

[D.] Thymol [67] on distillation with
phosphorus pentasulphide gives thio-
thymol (Fittica, Ber. 6, 938 ; Ann.
172, 325), and this on oxidation with
nitric acid yields 3-sulpho-p-toluic acid
(Ilj'uh Ann. 172, 329). The latter on

Q2

228

AROMATIC ALDEHYDES AND KETONES [129 D-130 E.

fusion with potash gives m-(y)-cresotic
acid (Weber, Ber. 25, 1743). Subse-
quent steps as above under C.

"Note:— Toluene [54] gives 3-sulpho-p-toluic
acid through p-nitrotoluene, p-toluidine, p-
toluidinesulphonic acid, cyanotoluenesulphonic
acid by the diazo-method, the siilphonamide
and sulphaminotoluic acid, which on heating
gives the imide (methylsaccharin). The latter
on evaporating with hydrochoric acid yields
the ammonium salt of 3-sulpho-p-toluic acid
(Bad. An. Sod. Fab. Germ. Pat. 48583 of 1889 ;
Bei-. 22, Ref. 719 ; Weber, Ibid. 25, 1741).

Or p-toluidine can be acetylated, nitrated,
and the o-nitro-p-toluidine converted into the
nitrile by the diazo-method. The nitrile on
reduction gives 3-amino-p-cyanotoluene, and
this by hydrolysis 3-amino-p-toluic = homo-
anthranilic acid (Niementowski, Journ. pr.
€h. [2] 40, 6; 15 ; Glock, Ber. 21, 2662).

Or the nitrocyano-derivative can be hydro-
lysed to 3-nitro-p-toluic acid and then reduced
to 3-amino-p-toluic acid (Niementowski and
Rozanski, Ber. 21, 1997 ; Noyes, Am. Ch.
Journ. 10, 479). The latter gives m-(7>cresotic
acid by the diazo-method (N. and R. loc. cit.
1998 : see also under m-cresol [62, pp. 128,
1 29] for further details).

[E.] From pulegone [128] and iso-
propyl alcohol [16]. Pulegone on boil-
ing with formic acid gives methylcyclo-
hexanone = 3-keto-i-methjlhexahydro-
benzene (see under phenol [60; S]),
and this on treatment with sodium and
ethyl acetate gives acetylmethylcyclo-
hexanone (Leser, Bull. Soc. [3] 23,
370). The potassium derivative of the
latter condenses with isopropyl iodide
to form acetylmenthone, and this yields
menthone on hydrolysis with methyl
alcoholic potassium hydroxide {IL'uL
Comp. Kend. 134, 1115).

130. Orthohydroxyacetophenone ;

Ortho-Acetylphenol ;

2-Etlianoylphenol.

CO . CH3
OH

Natueal Source.

In the volatile oil from the wood and
bark of Chione glabra, W. Indies (Dun-
stan and Henry, Trans. Ch. Soc. 76,
66). The methyl ether probably occurs
also in the oil (HAcl. 71).

Synthetical Piiocesses.

[A.] From cinnamic acid [Vol. II]
through the o-nitro-acid (see under
quinol [71; E] and salicylic aldehyde
[117; E]),thedibromide by bromination,
o-nitrophenylpropiolic acid by the action
of alkali, and o-nitrophenylacetylene by
heating the latter acid with water
(Baeyer, Ber. 13, 2259). o-Amino-
phenylacetylene obtained by reduction
of the nitro-compound (Baeyer and
Landsberg, Ber. 15, 60; Baeyer and
Bloem, Ber. 17, 964) gives o-amino-
acetophenone on treatment with sul-
phuric acid and water (Baeyer and
Bloem, loc, cit. ; Kippenberg, Ber. 30,
II 30), from which o-hydroxyacetophe-
none can be obtained by the diazo-
method (Friedlander and Neudorfer,
Ber. 30, 1080; Dunstan and Henry,
loc. cit. 71).

Or o-nitrophenylpropiolic acid can be
reduced to the amino-acid (Baeyer and
Bloem, Ber. 15, 2147 ; Richter, l/jxl.
16, 679), and this on heating with water
gives o-aminoacetophenone (B. and B.
loc. cit. 2153).

Or from cinnamic acid through
phenylpropiolic acid, phenylacetylene,
and acetophenone (see under benzoic
aldehyde [114; E]), and then through
the o-nitro- and o-amino-ketone (see
under salicylic aldehyde [117 ; D]), and
o-hydroxyacetophenone as above.

[B.] From benzoic and acetic acids

[Vol. II] through acetophenone [114;

A and G-1, and then as under salicylic

aldehyde [117 ; D] and A above.

Or from benzoic acid and zinc methi/l

[13] through acetophenone [114; C],

and then as above.

Or from benzoic acid and acetoacetic

ester [Vol. II] through o-nitro- and o-

aminoacetophenone [ll7; P and D],

and then as above under A.

[C] From salicylic acid [Vol. II]

and acetic ester through 2-methoxyben-

zoylacetic ester, &c., as under salicylic

aldehyde [117 ; G].

[D.] From couniMrin [Vol. II] through

o-coumarilic acid as under salicylic

aldehyde [117; H].

[E.] From orthocoumaric acid [Vol. II]

through dibrom-melilotic acid and o-

130 E 131 C] ORTHOHYDROXYACETOPHENONE

229

coumarilic acid as under salicylic alde-
hyde [117; I].

[P.] From styrene [7] through phenyl-
acetylene and acetophenone (see under
benzoic aldehyde [114; B]), and then
o-nitroacetophenone, &c.^ as under A
above.

[G.] From cymene [6] through cumic
aldehyde [116] and acid, isopropylben-
zene, acetophenone [ll4 ; K], and then
as above under A.

[H.] Benzene [6 ; I, &c.] becomes a
generator of acetophenone, and there-
fore of the o-hydroxy-ketone, through
ethylbenzene and normal or isopropyl-
benzencj or by interaction with acetyl
chloride in presence of aluminium
chloride [114; A]. Also through acet-
anilide and o-aminoacetophenone (see
under salicylic aldehyde [117; J]).

131. Ficeol; Parahydroxyaceto-
pheuone ; Fara-Acetylphenol.

CO . CH,

OH

Natural Source.

Occurs in the form of a glucoside,
pieein, in the needles of Pinus picea
(Tanret, Comp. Rend. 119, 8o ; Bull.
Soc. [3] 11, 944). The hydrolysis of
picem is capable of being effected by
certain enzymes.

Synthetical Peocesses.

[A.] From phenol [60], methyl alcohol
[13], and acetic acid [Vol. II]. Phenol
is converted into anisole (see under
anisic aldehyde [120 ; B]), and the
latter into p-acetyl anisole by adding
acetyl chloride to the solution of anisole
in carbon disulphide in presence of
aluminium chloride (Gattermann, Ehr-
hardt, and Maisch, Ber. 23, 120a;
Holleman, Rec. Tr. Ch. 10, 2^5). p-
Acetylanisole is demethylated by the
action of hydrogen bromide, giving p-

hydroxyacetophenone (Charon and Za-
manos, Comp. Rend. 133, 742).

Note : — Phenol and acetyl chloride condenbe
also in carbon disulphide solution under the
influence of dry ferric chloi-ide with the forma-
tion of p-hydroxyacetophenone (Nencki and
Stoeber, Ber. 30, 1769 : see also Michael and
Palmer, Am. Ch. Journ. 7, 277).

[B.] Aneihole [68] on oxidation with
iodine and mercuric oxide gives p-
methoxyhydratropie aldehyde (Bou-
gault, Comp. Rend. 130, 1766; 131,
44; Bull. Soc. [3] 25, 446; Ann.
Chim. [7] 25, 514), and this, on oxida-
tion with alkaline silver oxide, yields the
corresponding acid {Ibid. Comp. Rend.
130, 1767; 131, 44). The latter, on
further oxidation by chromic acid mix-
ture, gives p-methoxyacetophenone(/(5?V/.
Comp. Rend. 132, 782), which can be
demethylated as under A.

Note: — The following synthetical products
are generators of p-methoxyacetophenone via
p-methoxyhydratropic acid : —

Toluene through benzyl chloride and cyanide,
from which, by the action of methyl iodide and
sodium hydroxide, tlie nitrile of hydratropic
acid is obtained (Meyer, Ann. 250, 123 ;
Oliveri, Gazz. 18, 574). The acid obtained by
hydrolysis gives, on nitration, a mixture of
o- and p-nitrohydratropic acid and the latter, by
reduction, p-aminohydratropic acid (Trinius,
Ann. 227, 262 ; 267), By the diazo-method
the amino-acid yields p- hydroxy hydralropic
acid {Ibid.- 268), and this, by methylation, the
corresponding p-methoxy-derivative (Bougault,
Comp. Rend. 131, 270),

Acetophenone and hydrogen cyanide yield a cyan-
hydrin which, on heating with strong hydriodic
acid and red phosphorus, gives hydratropic
acid (Janssen, Ann. 250, 136). Subsequent
steps as above.

The esters ol plienylacetic and oxalic acids con-
dense under the influence of sodium ethoxide
to form the diethyl ester of phenyloxalacetic
acid (Wislicenus, Ber. 27, 1092), and this on
distillation in vacuo gives phenylmalonic ester
{Ihid. 1093). The latter, with methyl iodide
and sodium ethoxide, yields phenylmethyl-
malonic diethyl ester (Wislicenus and Gold-
stein, Ber. 28, 815), the acid of which gives
hydratropic acid on fusion {Ibid. 816).

[C] Anisic aldehyde [120] on heating
with acetic anhydride and sodium
acetate gives p-methoxycinnamic acid
(Perkin, Jahresber. 1877, 792 ; Journ.
Ch. Soc. 31, 408), which combines with
bromine to form p-methoxydibrom-
dihydrocinnamic acid = the methyl ether
of i^ : i^-dibrom-p-hydrocoumaric acid
(Eigel, Ber. 20, 2536). The ethyl

230

AKOMATIC ALDEHYDES AND KETONES [131 C-132 B.

ester of the latter acid by the action of
alcoholic potash gives p-methoxyphenyl-
propiolic acid (Reychler, Bull. Soc. [3]
17^ 512); and this on heating with
water to 130° yields p-methoxyaceto-
phenone {Ihid. 514), which can be
demethylated as above.

[D.] Ajjigenhi [140] gives p-hydroxy-
acetophenone among the products of
decomposition by heating with caustic
alkali (Vongerichten, Ann. 318, 131 ;
A. G-. Perkin, Trans. Ch. Soc. 71, 810).

[E.] From cinnamio acid [Vol. II]
through the p-nitro-acid by nitration
(see under p-hydroxybenzoic aldehyde
[119; B]). The nitro-acid (ester) on
bromination gives p-nitrophenyldibrom-
propionic acid (ester), and this by the
action of alcoholic potash yields p-nitro-
phenylpropiolic acid (Miiller, Ann. 212,
138; Drewsen,7^/r/. 154; W. H. Perkin,
junr., and Bellenot, Tmns. Ch. Soc. 49,
441). The latter on heating with dilute
sulphuric acid gives p-nitroacetophenone
(Drewsen, loc. cit. 160 ; Engler and
Zielke, Ber. 22, 303), which reduces to
p-aminoacetophenone (Drewsen, loc. cit.
162). The latter yields p -hydroxy aceto-
phenone by the diazo-method (KHngel,
Ber. 18, 2691).

[P.] From benzene [6; I, &c.] and
acetic acid [Vol. II] through aniline,
which, on heating with acetic anhydride
and zinc chloride, gives p-aminoaceto-
phenone (Klingel, Ber. 18, 3688 ; Rous-
set. Bull. Soc. [3] 11, 320 : see also
Kohler, Germ. Pat. 56971 of 1889;
Ber. 24, Ref. 685). From the latter
as above under E.

From benzene or toluene through p-
nitrobenzoic aldehyde (see under p-hydr-
oxybenzoic aldehyde [119; E]). The
latter by interaction with walonic acid
[Vol. li] in presence of aniline or alco-
holic ammonia gives p-nitrocinnamic
acid (Knoevenagel, Baebenroth, and
Wollweber, Ber. 31, 261 2). Subsequent
steps through p-nitrophenylpropiolic
acid, &c., as above under E.

Note -.—Shjrene [7] and all other generators
of p-nitrobenzoic aldehyde referred to under
p-hydroxybenzoic aldehyde [119 ; C, &c.] thus
become generators of p-hydroxyacetophenone.

Also from benzene through aniline,
p-nitraniline, p-nitrobenzonitrile and

acid, and p-nitrobenzoyl chloride. The
latter with sodio-acetoacetic ester [Vol.
II] gives p-nitrobenzoylacetoacetic
ester, and this, on boiling with dilute
sulphuric acid, yields p-nitroacetophe-
none (Gevekoht, Ann. 221, 335). From
the latter as above under E.

p-Nitrotoluene can also be oxidised
to p-nitro-benzoic acid (Glenard and
Boudault, Ann. 48, 344 ; Beilstein and
Wilbrand, Ann. 126, 255; 128, 257;
G. Fischer, Ann. 127, 137; 130, 128;
Beilstein and Geitner, Ann. 139, 335 ;
Korner, Zeit. [2] 5, ^^fi', Rosenstiehl,
Ibid. 701). From the latter p-nitro-
benzoyl chloride can be obtained by the
usual method (Gevekoht, loc. cit.).

132. Eetocoumaran ; Conniarauoue.

/CO, ,, ,C(OH)

)CH.

Natural Source.

CH

The compound itself has not been
found among natural products, but the
complex appears to be present in genis-
tein, a colouring-matter obtained from
dyer's broom. Genista tinclona (A. G.
Perkin and Newbury, Trans. Ch. Soc.
75, 837).

Synthetical Processes.

[A.] From o-hydroxyacetophenone\\ZQ>\
by acetylation, bromination, and the
action of boiling water in presence of
chalk on the acetyl-o-hydroxy-w-aceto-
phenone bromide (Friedlander and
Neudorf er ; see under salicylic aldehyde
[117; D]).

[B.] From salicylic aldehyde [117]
and acetic acid [Vol. III. Chloracetic
acid acts on sodium salicylic aldehyde
with the formation of o-aldehydophen-
oxyacetic acid, CHO . CgH^ . OCHg .
COOH (Rossing, Ber. 17, 2990). The
latter, on oxidation with potassium per-
manganate, gives salicyloxyacetic acid,
COOH . CgH^ . OCH2 . COOH {Ibid.

132 B-134 A.]

KETOCOUMARAN

231

2995), the dialkyl ester of which, on
treatment with sodium in benzene solu-
tion, yields ketocoumarancarboxylic
ester. On treating the ester with alkali
ketocoumaran is formed (Friedlander,
Ber. 32, 1868).

[C] From phenol [eo] and acetic acid
[Vol. II] through phenoxyacetic acid
by the interaction of chloracetic acid
(or ester) and sodium phenoxide (Heintz,
Jahresber. 1859, 361 ; Hantzsch, Ber.
19, 1 296 j Giacosa, Journ. pr. Ch. [2]
19, 396 ; Fritzsche, Ibid. 20, 269).
Phenoxyacetic acid, on heating with
dehydrating agents, gives ketocoumaran
(Stoermer, Ber. 30, 1712; Stoermer
and Bartsch, Ber. 33, 3175).

Schmid, Journ. pr. Ch. [2] 25, 82;
Michael, Am. Ch. Journ. 5, 434).
^-Methylumbelliferone gives resaceto-
phenone on fusion with potash (v. Pech-
mann and Duisberg, loc. cit. 2123).

Or resorcinol and sodio-acetoacetic
ester condense in alcoholic solution to
give a carboxylic acid which yields /3-
methylumbelliferone on heating (Mi-
chael, Journ. pr. Ch. [2] 35, 454 ; 37,
470 ; V. Pechmann, Ann. 261, 169).

Resorcinol and citric acid [Vol. II]
also give /3-methylumbelliferone on
heating with sulphuric acid (Witten-
berg, Journ. pr. Ch. [2] 24, 125; v.
Pechmann, Ber. 17, 931).

133. Faeonol ; Resacetophenoue

Methyl Ether ; 2-Hydroxy-4-Meth-

ozyacetophenone ; Ethaiioyl-2 : 4-

Fhenediol 4-Methyl Ether.

CO.

CH3

OH

CO.

CH

:0

0.CH3 0.CH3

N.

ITURAL Sou

RCE.

In the root bark of Ffeonia moutan from
Japan and China (Martin and Yagi,
Arch. Pharm. 213, ^'^^ \ Nagai, Ber.
24, 2847).

Synthetical Processes.

[A.] Besorcinol [70] and acetic acid
[Vol. II] when heated with zinc
chloride, or resorcinol alone, when heated
with the latter, gives resacetophenone =
ethanoyl-2 : 4-phenediol (Nencki and
Sieber, Journ. pr. Ch. [2] 23, 147).
The latter is methylated by methyl
iodide [13] and potassium hydroxide in
methyl alcoholic solution (Tahara, Ber.
24, 2460).

Or from resorcinol and acetoacetic ester
[Vol. II] through ^-methylumbelli-
ferone by treating a mixture in the
cold with sulphuric acid, or by heating
with zinc chloride (v. Pechmann and
Duisberg, Ber. 16, 21 19; Ann. 261, 169;

134. Hydrocotoi'n ; 2:4: 6-Trihy-
droxybenzophenone Dimethyl Ether ;
Benzocotoin ; Benzoylphloroglucinol

Dimethyl Ether ; 2 : 4-Methozy-6-
Hydrozybenzophenoue.

CO.CeHo
HO^ \OCH,

OCH,

Natural Source.

In coto bark from Bolivia (Jobst
and Hesse, 199, 57). The botanical
origin is unknown, but the tree is
probably Lauraceous or Monimiaceous.

Synthetical Process.

[A.] From phloroglucinol [86], hen-
zoic acid [Vol. II] through benzoyl
chloride, and methyl alcohol [13]. The
dimethyl ether of phloroglucmol is pre-
pared by passing hydrogen chloride
through a methyl alcoholic solution of
phloroglucinol (Will, Ber. 21, 603). The
dimethyl ether is benzoylated by ben-
zoyl chloride in presence of alkali, and
the benzoyl-dimethyl ether heated with
benzoyl chloride in benzene solution in
presence of zinc chloride. The benzoyl-
hydrocotoin thus formed gives hydro-
cotoi'n on hydrolysis (Pollak, Monats.
18, 736).

232

AROMATIC ALDEHYDES AND KETONES [135-136 D.

135. Methylhydrocotoin ;

2:4: 6-Trimethoxybenzopheuoiie ;

Benzoylphloroglucinol Trimethyl

Ether.

CO.CsH,
OCH,

CH,

OCH3

Natural Souece.

Occurs in paracoto bark (see above
under hydrocotoin) (Jobst and Hesse,
Ann. 199, 5^; Ciamician and Silber,
Ber. 26, 799).

Synthetical Process.

[A.] From hydrocotoin [l34] and
methyl alcohol [13] by further methyla-
tion with methyl iodide and potassium
hydroxide in methyl alcohol (Ciamician
and Silber, Ber. 24, 300; 25, 11 20).

Or directly from phloroglucinol [86]
through the trimethyl ether (Will, Ber.
21, 603), and the action of benzoyl
chloride on the latter in benzene solu-
tion in presence of zinc chloride (Ciami-
cian and Silber, Ber. 27, 1497)-

136. Etixantlioiie.

HO

CO

OH

Natural Source.

The complex exists in euxanthic acid,
the glycuronic congugate acid of eux-
anthone which occurs in * purree' or
Indian Yellow,, prepared from the urine
of cows fed upon mango leaves. Eux-
anthone is sometimes found in the free
state in the colouring-matter, resulting
from the decomposition (? bacterial) of
euxanthic acid.

Note : — For the constitution of euxanthic acid
see Graebe, Ber. 33, 3360 ; Graebe, Aders, and
Heyer, Ann. 318, 345.

Synthetical Processes.

[A.] From resorclnol [70] and quinol
[7l]. Resorcinol is converted into /3-
resorcylic acid by heating with aqueous
ammonium carbonate or acid potassium
carbonate (Brunner and Senhofer, Ber.
13, 2356 ; Bistrzycki and Kostanecki,
Ber. 18, 1985). Quinol is converted
into its carboxylic acid, gentisie = 2:5-
phenediolcarboxylic = a : 5-dihydroxy-
benzoic = 5-hydroxysalicylic acid, by a
similar process (Senhofer and Sarlaz,
Monats. 2, 448). Gentisie and ^-re-
sorcylic acids or resorcinol when heated
together with acetic anhydride give
euxanthone (Graebe, Ber. 22, 1405 ;
Kostanecki and Nessler, Ber. 24, 3983).

[B.] From resorcinol [70] and salicy-
lic acid [Vol. II]. The latter can be
converted into gentisie acid by the
following processes : —

By iodising with iodine in presence
of alkali, or by the action of iodine on
silver salicylate 5-iodosalicylic acid is
formed (Lautemann, Ann. 120, 302;
Demole, Ber. 7, 1437 ; Birnbaum and
Beinherz, Ber. 15, 458). Or 5-brom-
salicylic acid is obtained by the brom-
ination of the acid (Henry, Ber. 2, 275 ;
Hiibner and Heinzerling, Zeit. [2] 7,
709; Hand, Ann. 234, 133), The5-iodo-
or bromo-acid gives gentisie acid on
fusion with alkali (Lautemann, loc. cit.
311; Liechti, Ann. Suppl. 7, 144;
Demole, loc. cit. 1438 ; Goldberg, Journ.
pr. Ch. [2] 19, 371 ; Miller, Ann. 220,
124; Rakowski and Leppert, Ber. 8,

789). . . . .,^

Or salicylic acid on nitration yields
5-nitro-, and the latter on reduction 5-
aminosalicylic acid (see under quinol
[71; C]). The amino-acid gives gen-
tisie acid by the diazo-method (Gold-
berg, loc. cit.).

[C] From resorcinol [70] and phenol
[6O]. The latter on nitration gives
(with 0-) p-nitrophenol, and this on
heating with carbon tetrachloride [l ; L]
and alcoholic potash yields5-nitrosalicy-
lic acid (Hasse, Ber. 10, 2188), which
can be transformed into gentisie acid as
above under B.

[D.] From resorcinol [70] and benzoic
acid [Vol. II]. The latter can be con-

136 D-138 A.]

EUXANTHONE

233

verted into 5-aminosalicylic acid (see
under quinol [71; D]), which gives
gentisic acid as above under B.

Benzoic acid can also be converted
into gentisic acid through o-nitro- and
anthranilic acid, o-uraminobenzoic acid,
dinitrouraminobenzoic acid, 5-nitro-
2-aminobenzoic acid, 5-nitro- and 5-
aminosalicylic acid, and then as above
under B. Or through 3-brombenzoie
acid, the3-brom-6-nitro- and correspond-
ing amino-acid, 5-bromsalicylic acid,
and then as above under B [71; D].

[E.] From resorcinol [70] and an-
thranilic { = i-aminohe^izoic) acid [Vol.
II]. The latter can be converted into
gentisic acid as above under D.

[F.] From resorcinol [70] and gentisin
[137]. The latter gives gentisic acid
on fusion with potash [71 ; L].

[G.] From resorcinol, [70], furftiral
[126], and acetone [1O6]. The two
latter can be made to furnish p-nitro-
phenol (as under resorcinol [70; H]),
from which gentisic acid can be ob-
tained as above under C.

[H.] From quinol [7l] and umhelli-
ferone [Vol. II], the latter yielding j8-
resorcjlic acid on fusion with potash
(see under resorcinol [70 ; E]).

Notes :— ^-Resorcylic acid can bo obtained
also from toluetxe directly [70 ; B]. Euxanthic
acid has been synthesised by the action of
acetbromglycuronic acid on the sodium deriva-
tive of euxanthone (Neuberg and Niemann,
Centr. med. Wiss. 40, 529; Ch. Centr. 1902,
2, 844). For constitution of euxanthone see
Kostanecki, Ber. 27, 1989.

137. Gentisin;

Methylgentisein ; Gentianin ;

1 : 7-Hydroxy-3-Methoxyxanthone.

HO

CO

HO

OCH3

Natural Source.

In the root of Gentiana lutea from
Switzerland and the Tyrol (Tromms-
dorff, Ann. 21, 134; Leconte, Ann. 25,
202 ; Baumert, Ann. 62, 106 ; A. G.
Perkin, Trans. Ch. Soc. 73, 672).

Synthetical Processes.

[A.] From quinol [7l] through gen-
tisic acid (see under euxanthone [136 ;
a]), phloroghicinol [86], and methyl
alcohol (methyl iodide) [13]. Phloro-
glucinol and gentisic acid, when heated
with acetic anhydride, give gentisei'n,
and this yields gentisin on methyla-
tion (Kostanecki and Tambor, Monats.
15, 4).

The quinol may be replaced by the
other generators of gentisic acid referred
to under exanthone [136 ; B ; C ; D ;
E ; F; G], viz. salicylic acid [Vol. II],
phenol [6O], benzoic or anthranilic acid

[Voh II], furfural [126], and acetone
106].

138. Chrysin;
1 : 3-Dihydroxyflavone.

HO

C.C.H,

CH

\/\co/

HO

Natural Source.

In the buds of various species of
poplar, such as Populus nigra, P. bal-
samifera, P. pyramid alis, &c. (Piccard,
Ber. 6, 884; 7, 888; 10, 176).

Synthetical Processes.

[A.] Yxovs\.phloroglucinol [86], bejizoic
and acetic acids [Vol. II], methyl [13],
and ethyl alcohol [14]. Phloroglucinol
is converted into its trimethyl ether
(see under methylhydrocotom [l35 ;
A]), and the latter condensed with
acetyl chloride (by means of aluminium
chloride) so as to giwQ phloroaceto-
phenone trimethyl ether (Friedlander
and Schnell, Ber. 30, 2152). The
latter condenses with ethyl benzoate
in presence of sodium ethoxide with the
formation of 2 : 4 : 6-trimethoxybenzoyl-
acetophenone, (01136)3 . C6H2 • CO .
CH2 . CO . CgHg. The latter on heating
with strong aqueous hydriodie acid gives
chrysin (Emilewicz, Kostanecki, and
Tambor, Ber. 32, 2448).

234

AROMATIC ALDEHYDES AND KETONES [139-141 A.

139. Tectochrysin ;
l-Hydroxy-3-Methoxyflavone.

CH,0

C . C5H3

ll
CH

\/\co/

HO

Natural Source.

In poplar buds with chrysin (Piccard,
Ber. 6, 890).

Synthetical Process.

^ [A.] From chri/sin [l38] by methyla-
tion with methyl iodide and potassium
hydroxide (Piccard, Ber. 10, 176;
Emilewicz and Kostanecki, Ber. 32,
3449).

140. Apigeniu ;
1:3: 4^-Trihydroxyflavone.

HOi

CH

>0H

HO CO

Natural Source.

Occurs as glucoside (apiin) in stem,
leaves, and seeds of parsley, Apium
petroselinum (Braconnot, Ann. 48, 349 ;
Planta and Wallace, Ann. 74, 262 ;
Lindenborn, Ber. 9, 1123; Vongerich-
ten, i^/f?. 1 1 24 ; 33, 2334 ; 2904; Ann.
318, 121 : see also under phloroglucinol
[86]).

A methyl ether of apigenin (acacetin)
is present in the leaves of Robinia pseud-
acacia (A. G. Perkin, Trans. Ch. Soc.
77, 430)-

Synthetical Processes.

[A.] From anisic acid [Vol. II],
pJiloroglucinol [86], acetic acid [Vol. Ill,
and methyl and et/iyl alcohols [13 ; 14]
as accessories. Anisic ethyl ester is
condensed with phloracetophenonetri-
methyl ether (see under chrysin [138;

A]) by heating with sodium in xylene
solution. The product = 2:4:6 :4^-
tetramethoxybenzoylacetophenone, on
heating with strong hydriodic acid,
gives apigenin (Czajkowski, Kostanecki,
and Tambor, Ber. 33, 1988).

141. Luteolin;
1:3:3^: 4^-Tetraliydroxyflavoue.

HO

OH

C— <

II
CH

)0H

HO

Natural Sources.

In weld from Reseda luteola (Chev-
reul, Jouin. Chim. Med. 6, 157 ; Berz.
Jahresber. 11, 280 ; Moldenhauer, Ann.
100, i8oj Schiitzenberger and Paraf,
Bull. Soc. [i] 1861, 18; Journ. pr. Ch.
[i] 83, 368 ; Ann. Suppl. 1, 256 ;
Jahresber. 1861, 707 ; Rochleder and
Breuer, Zeit. [2] 2, 602 ; Hlasiwetz
and Pfaundler, Journ. pr. Ch. [1] 94,
94 ; A. G. Perkin, Trans. Ch. Soc. 69,
206 j 799 ; A. G. P. and Horsfall,
Ibid,. 77, 1314).

Luteolin occurs in the colouring-
matter from the flowers of dyer's
broom. Genista tinctoria (A. G. P. and
Newbury, Proc. Ch. Soc. 15, 179).

A glucoside contained in parsley with
apiin is a derivative of luteolin methyl
ether (Vongerichten, Ber. 33, 2334;
2904).

Scoparin from broom, Spartitim sco-
parium, may be a glucoside of methyl-
luteolin (A. G. Perkin, Proc. Ch. Soc.
16, 45 ; Trans. 77, 423): .

Digitoflavone from Digitalis leaves is
identical with luteolin (Kiliani and
Mayer, Ber. 34, 3577).

Synthetical Process.

[A.] YxciVix phloroglucinol [86], acetic
and veratric acids [Vol. II], methyl and
ethyl alcohols [13; 14]. Phloraceto-
phenonetrimethyl ether (see under
chrysin [l38 ; A]) and ethyl veratrate

141 A-143 B.]

LUTEOLIN

235

are condensed by treatment with sodium
so as to form 2:4:6:3^: 4^-penta-
methoxybenzoylacetophenone. The

latter gives luteolin on heating with
strong- aqueous hydriodic acid (Kosta-
necki^ Rozycki, and Tambor, Ber. 33,
3415 ; Diller and Kostanecki, Ber. 34,
1449)-

142. Quinone ; Faradiozybeuzene.
O 0-

Natural Soueces.

Quinone appears to be among the
products of the fermentation of grass,
and is probably the result of oxidation
by Bacteria (Emmerling, Ber. 30,
1870).

Quinone is formed in albumin (pep-
tone) cultures by Strejjtothrix chromo-
gena, Gasperini (Beyerinck, Centr.
Bakter. II, 6, i ; Ch. Centr. 1900, 1,
429 : see also Furuta, Ch. Centr. 1902,

The skin secretion of the Millipede,
Tulns /ff^r^tf^r/-?, possibly contains quinone
(Behal and Phisalix, Comp. Bend. 131,

1004).

Synthetical Processes.

[A.] From quinol [7l] by oxidation
(Wohler, Ann. 51, 152 ; Nietzki, Ber.
19, 1468; Clark, Am. Ch. Journ. 14,

555).

[B.] From phenol [6O] by oxidation
of the p-sulphonic acid (Schrader, Ber.
8, 760) ; or through p-nitro- and p-
aminophenol, and oxidation of the latter
(Schmitt and. Siepermann, Journ. pr.
Ch. [2] 19,317).

[C] From /M^/wm/ [126] duxxdi acetone
[IO6] thi'ough pyromucic and muco-
bromic acids, nitromalonic aldehyde,
and p-nitrophenol (see unde'r phloro-
glucinol [86 ; l] and resorcinol [70 ;
H]).

[D.] ^vomtjerizene [6; I, &c.] by the
oxidation of many derivatives with
open p-position or with easily removed
substituents in this position : —

From aniline (Hofmann, Jahresber.
1863, 415; Nietzki, Ber. 10, 1934;
2005; 11, 1004; 19, 1467; Ann. 215,
12,5; Seyda, Ber. 16, 687; Schniter,
Ber. 20, 3283) by sodium dichromate
and sulphuric acid or other oxidising
agents. Also by the oxidation of
sulphanilic = aniline-p-sulphonic acid
(Meyer and Ador, Ann. 15 9, 7 ; Schrader,
JBer. 8, 760).

Or from benzene (or aniline) through
p-phenylenediamine and oxidation of
the latter (Hofmann, lac. cit. 422).
Or directly from benzene by combina-
tion with chromium oxychloride and
decomposition of the product with
water (Etard, Ann. Chim. [5] 22,

The oxidation of aniline by chromic
acid mixture is facilitated by electro-
lytic action (Darmstadter, Germ. Pat.
109012 of 1897; Ch. Centr. T900, 2,
151 : for electrolytic oxidation in sul-
phuric acid of benzene to quinone see
Kempf, Germ. Pat. 11 7251 of 1899;
Ch. Centr. 1901, 1, 348).

143. Thymoquiuoue.

:0

CH3

0—

0:

.CH.

CH3

— 0
CH,

.CH.(

3H3

Natural Source.

Occurs in wild bergamot oil from
Monardafistulosa (Brandel and Kremers,
Pharm. lie v. 19, 200; 244).

Synthetical Processes.

[A.] From thymol [67] by oxidation
(see under thymoquinol dimethyl ether
[83; A]).

[B.] From carvacrol [66] by oxida-
tion (83; B).

236

AROMATIC ALDEHYDES AND KETONES [144-C.

144. Metahydroxyanthraqninone ;
2-Hydroxyanthraquiuone.

CO.

CO

OH

Natural Source.

In Chay root {Oldenlandia umbellala)
from N. Burma, Ceylon, Madras
Presidency, Malabar and Coromandel
coasts (A. Gr. Perkin and Hummel,
Trans. Ch. Soc. 63, 1177).

Synthetical Processes.

[A.] From phenol [6O] and phthalic
anhydride (see under benzyl alcohol
[54; B,]). A mixture of these gives
(with I -hydroxy-) 2-hydroxyanthra-
quinone on heating with strong sul-
phuric acid (Caro and Baeyer, Ber. 7,
969).

[B.] From benzoic acid [Vol. II]
through m-nitro-, m-amino-, and m-hy-
droxy benzoic acid(see under phenol [60 ;
E]). The latter, when heated with
benzoic acid and strong sulphuric acid
at 200°, gives m-hydroxyanthraquinone
(Liebermann and Kostanecki, Ann. 240,
263).

[C] Anthracene and anthraquinone can
be synthesised by various processes : —

Syntheses of Anthracene,.

From toluene through benzyl chloride
(see under benzyl alcohol [54 ; A]).
The latter gives anthracene on heating
with water at 180° (Limpricht, Ann.
139, 308 ; Zincke, Ber. 7, 278), or by
the action of aluminium chloride (W.
H. Perkin, junr., and Hodgkinson, Trans.
Ch. Soc. 37, 726; Schramm, Ber. 26,
1706).

Or benzyl chloride and ethyl alcohol
give benzyl ethyl ether (Cannizzaro,
Jahresber. 1856, 581), which on heating
with phosphorus pentoxide gives (with
ethylene) anthracene (Henzold, Journ.
pr. Ch. [2] 27, 518).

Benzyl trichloracetate (from benzyl

chloi'ide and trichloracetic acid) interacts
with benzene^ in presence of aluminium
chloride, to form a compound which
gives anthracene on distillation (Delacre,
Bull. Soc. [3] 13, 302).

Dihydroanthracene (furnishing an-
thracene by oxidation) is probably
among the products of the oxidation of
toluene by manganese dioxide and sul-
phuric acid (Weiler, Ber. 33, 464).

Or from toluene through the o-bromo-
derivative and o-brombenzyl bromide
(Jackson, Ber. 9, 932), and the action of
sodium on the latter in ethereal solution
(Jackson and White, Am. Ch. Journ. 2,
391; Ber. 12, 1965).

From benzene and acetylene dibromide
(or tetrabromide) by treating a mixture
with aluminium chloride or bromide
(Anschiitz, Ann. 235, 156; 165; An-
schiitz and Eltzbacher, Ber. 16, 623).

Or from benzene and methylene chloride
[55; E, p. 117] by the action of
aluminium chloride (Friedel, Crafts, and
Vincent, Ann. Chim. [6] 11, 264; Bull.
Soc. [2] 40, 97 ; 41, 325). Hexa- and
pentachlorethane and perchlorethylene,
triehlorethane, and dichlorethyl ether all
give anthracene when condensed with
benzene by means of aluminium chloride
(Mouneyrat, Bull. Soc. [3] 19, 554;
557 ; Gardeur, Bull. Acad. Boy. Belg.
[3] 34, 920).

Naphthalene [12] can be converted
into o-toluic acid (benzyl alcohol [54;
B,]), and this, when heated in brom-
ine vapour at 140°, gives phthalide,

CO
CgH^^pxT )>0. The latter, on distillation

with lime, yields anthracene (Krczmar,
Monats. 19, 456).

Note : — Toluenethusalso becomes a generator
of anthracene through o-toluic acid (see under
m-cresol [62 ; A]).

Phenol [60] and benzyl chloride (or
benzyl alcohol [54]) condense to form
p-benzylphenol under the influence of
zinc chloride or other condensing agents
(Paternb, Gazz. 2, 2; 3, I2i; Paterno
and Fileti, Ibid. 5, 382 ; Liebmann,
Ber. 14, 1844; W. H. Perkin, junr.,
and Hodgkinson, Trans. Ch. Soc. 37,
723). p-Benzylphenol gives anthracene
among other products on distillation

144 C]

METAHYDROXYANTHRAQUINONE

237

with phosphorus pentoxide (Paternb and
Fileti, loc. cit. 3, 252).

p-Benzylphenol can also be obtained
from phenol and benzoic aldehyde [114].
The latter on treatment with potassium
cyanide forms benzoin (Liebig- and
Wohler, Ann. 3, 276 ; Zinin, Ann. 34,
186 ; Zincke, Ann. 198, 151). A mix-
ture of benzoin and phenol g-ives p-
desylphenol on treatment with strong-
sulphuric acid (Japp and Wadsworth,
Trans, Ch. Soc. 57, 965), and this on
fusion with potash yields p-benzylphenol
{Ibid. 972).

Or benzoic acid [Vol. II] and toluene,
when heated to 200° with phosphorus
pentoxide, give phenyl-o-toluyl ketone
(Kollarits and Merz, Ber. 6, 538 : the
p-modification is simultaneously formed).
The latter yields anthracene on heating*
with zinc dust (Behr and Van Dorp,
Ber. 7, 17).

Note : — Phenyl-o-toluyl ketone is among the
products of the oxidation of toluene by man-
ganese dioxide and sulpliuric acid (Weiler,
Ber. 33, 464).

Anthracene is formed by passing the
vapours of many synthetical hydro-
carbons through red-hot tubes : — Thus,
from ethylene and benzene, benzene and
styrene, o-benzyltoluene, &c. (Berthelot,
Bull. Soc. [2] 7, 223; 8, 231 ; 9, 295 ;
Ann. 142, 254 ; Van Dorp, Ann. 169,
216 : for pyrogenic syntheses of anthra-
cene from benzene and ethylene, from
toluene vapour, and from ethylbenzene,
see Ferko, Ber. 20, 660).

Anthracene is among the hydro-
carbons formed by passing through a
hot tube ethylene (Norton and Noyes,
Am. Ch. Journ. 8. 362), ethylene and di-
phenyl (Barbier, Comp. Rend. 79, 121),
heptane and octane at 900° (Worstall
and Burwell, Am. Ch. Journ. 19, 815).

Anthracene is among the products
formed by the action of dry aluminium
chloride on acetylene (Baud, Comp.
Rend. 130, 13T9), and by the action at
600-800° of certain metallic carbides,
e. g. barium, on the corresponding hy-
droxides (Bradley and Jacobs, Germ.
Pat. 125936 of 1898 \ Ch. Centr. 1902,

Styrene on combination with bromine

gives i^ : i^-dibromethylbenzene (Blyth
and Hofmann, Ann. 53, 306 ; Glaser,
Ann. 154, 154; Zincke, Ann. 216, 288).
The same dibromethylbenzene can be
obtained by the bromination of ethyl-
benzene (Radziszewski, Ber. 6, 493 ;
Friedel and Balsohn, Bull, Soc. [2] 35,
^^). 1^ : I ^-Dibromethylbenzene gives
anthracene by the action of aluminium
chloride on its benzene solution
(Schramm, Beilstein^s ' Handbuch,^ 3rd
ed. II, 257).

Syntheses of Anthraquinone.

From phthalic anhydride (see under
benzyl alcohol [54; R]) and benzene,
a mixture (solution) of these giving,
when treated with aluminium chloride,
o-benzoylbenzoic acid (Friedel and
Crafts, Ann. Chim. [6] 14, 446 ; Comp.
Rend. 86, 1368). The latter, on heat-
ing per se or with phosphorus pentoxide
or strong sulphuric acid, yields anthra-
quinone (Ullmann, Ann. 291, 24 ; Behr
and Van Dorp, Ber. 7, 578; Liebermann,
Ibid. 805 ; W. H. Perkin, junr.. Trans.
Ch. Soc. 59, 1012).

Note :— o-Benzoylbenzoic acid is among the
products of oxidation of toluene by potassium
permanganate (Weiler, Ber. 33, 465).

Calcium phthalate gives anthraquin-
one on dry distillation (Panaotovits, Ber.
17, 313). Or phthalic acid can be eon-
verted into phthaloyl chloride (Miiller,
Jahresber. 1863, 393). The latter yields
anthraquinone when heated with zinc
dust and benzene at 320°, or when
treated with aluminium chloride in
benzene solution (Piccard, Ber. 7, 1785 ;
Friedel and Crafts, Ann. Chim. [6]
1, 523 ; Bull. Soc. [2] 29, 49).

Anthraquinone is among the products
of the distillation of calcium benzoate
[Vol. II], and is formed in small
quantity by distilling benzoic acid with
phosphorus pentoxide (Kekule and
Franchimont, Ber. 5, 908).

Phenyl-o-toluyl ketone (see above)
gives anthraquinone on heating with lead
oxide, or on oxidation with manganese
dioxide and sulphuric acid (Behr and
Van Dorp, Ber, 6, 754; 7, 16) ; also by
chlorination at 110°, and decomposition

238

AROMATIC ALDEHYDES AND KETONES [l44 c-145 B.

of the product with water (Thorner and
Zineke, Ber. 10, 1479).

Anthracene is converted into anthra-
quinone by oxidation (Laurent, Berz.
Jahresber. 16, $66; Ann. Chim. [2]
60, 220; 72, 415; Ann. 34, 2«7 ;
Anderson, Journ. Ch. Soc. 15, 44 ; Ann.
122, 301 ; Graebe and Liebermann,
Ann. Suppl. 7, 285 ; Kopp, Jahresber.
1878, 1 1 88; Darmstadter, Germ. Pat.
1090 1 2 of 1897; Ch. Centr. 1900, 2,

150-

Anthracene and anthraquinone give
m-hydroxyanthraquinone as follows : —
Anthracene by the action of bromine
gives dibromanthracene bromide (An-
derson, loc. cif.; Graebe and Liebermann,
loc. cit. 275), and this on heating at
300° yields tribromanthracene. The
latter on oxidation (with chromic acid in
acetic acid) gives 2-bromanthraquinone
(G. and L. loc. cit. 290), and this yields
3-hydroxyanthraquinone on fusion with
potash {Ibid. Ann. 160, 141 ; Suppl. 7,
290 ; 212, 25).

Anthraquinone on sulphonation gives
(with disulpho-acid) 2-sulpho-acid {Ibid.
Ann. 160, 131)) and this yields the 2-
hydroxyquinone by potash fusion {Ibid.
141 ; Simon, Ber. 14, 464 ; Lieber-
mann, Ann. 212, 25 : see also A. G.
and W. H. Perkin, junr., Trans. Ch. Soc.
47, 680). Or the solution of the sulphonic
acid (salt) may be heated with lime and
water under pressure at 160° (Meister,
Lucius, and Briining, Germ. Pat. 106505
of 1898; Ch. Centr. 1900, 1, 741).

Or the 2-sulphonic acid heated with
excess of aqueous ammonia at 1 90° gives
2-aminoanthraquinone (Perger, Ber. 12,
1567 : see also Bourcart,/(5'?V/. 1418), and
this yields the 2-hydroxyquinone by the
diazo-method (Perger, loc. cit. 1569).

By the action of nitric acid on di-
bromanthracene (Clans and Hertel, Ber.
14, 978), or on anthraquinone (Bottger
and Petersen, Ann. 166, 147), the a-
nitro-quinone is formed, and this on
reduction with potassium sulphydrate
gives the a-amino-quinone {Ibid. 149 :
see also Claus and Hertel, loc. cit. 979).
The latter yields the m-hydroxyquinone
by the diazo-method (B. and P. loc. cit.

151)-

[D.] From alizarin [l45] by treat-
ment with alkaline stannite (Lieber-
mann and Fischer, Ber. 8, 975). Or
through a-alizarinamide by heating
alizarin with aqueous ammonia at 200°
(Liebermann, Ann. 183, 207), and
elimination of the NHg-group by the
diazo-method {Ibid. 208).

145. Alizarin ;
1 : 2-Dihydroxyanthraquiuoue.

CO

CO

HO

OH

Natural Sources.

Occurs as the glucoside ruberythric
acid (CggH^gOi^) in madder from the
root of Ihibia tinctoria (Robiquet and
Colin, Ann. Chim. [2] 34, 225 ; Runge,
Journ. pr. Ch. 5, 362 ; Schunek, Ann.
66, 174; 201; 81, 336; 87, 344;
Phil. Mag. [4] 5, 410; 495; 12, 200;
270; Journ. pr. Ch. 59, 465; Debus,
Ann. 66, 351 ; Wolff and Strecker,
Ann. 75, 1 ; Rochleder, Ber. 3, 295 ;
Ann. 80, 321; 82, 205; Wartha, Ber.
3, 545 ;. 673 > Willigk, Ann. 82, 339 ;
Rosenstiehl, Ann. Chim. [5] 18, 235 ;
Comp. Rend. 88, 1194; Wurtz, Comp.
Rend. 96, 465 ; Liebermann, Ber. 20,
2241 ; Bergami, Ibid. 2247).

Alizarin occurs also in Chay root
from Oldenlandia timbellata (see under
m-hydroxyanthraquinone [144] ; A. G.
Perkin and Hummel, Trans. Ch. Soc.
63, 1167}.

Synthetical Processes.

[A.] From catechol [69] and pldlialic
anhydride (see under benzyl alcohol
[54 ; B,]), a mixture of these com-
pounds giving alizai'in when heated
with strong sulphuric acid (Baeyer and
Caro, Ber. 7, 972).

[B.] Anthracene [144; C] is chlori-
nated or brominated, and the product
oxidised to dichlor- or dibromanthra-

145 B-146 B.]

ALIZARIN

239

quinone. The halo-quinone gives
alizarin on fusion with alkali (Graebe
and Liebermann, Ann. Suppl. 1, 300 ;
Ber. 3, 359 ; Bull. See. [2] 11, 516),

Or anthr a quinone is sulphonated, and
the monosulphonic acid (see under m-
hydroxyanthraquinone [144 ; C]) fused
with alkali and potassium chlorate
(G. and L. loc. cit. ; Perkin, Journ. Ch.
Soc. 23, 133 ; Ber. 9, 281). The latter
is the technical process.

a-Nitroanthraquinone, a-dinitro-, and
diaminoanthraquinone give alizarin on
fusion with alkali (Bottger and Peter-
sen, Ber. 4, 227 ; Ann. 160, 145; 166,
147 ; Meister, Lucius, and Briining,
Jahresber. 1873, Ii22; Glaus, Ber. 15,

Or anthraquinonesulphonic acid gives
on nitration a mixture of two nitro-
sulphonic acids (Glaus, loc. cit.) ; the
a-acid yields alizarin on fusion with
alkali. Or the nitrosulphonic acid can
be reduced to the corresponding amino-
acid (Claus, loc. cit. 15 19)^ and this
converted into i -hydroxyanthraquinone-
2-sulphonic acid by the diazo-method
(Lifschiitz, Ber. 17, 900). The latter
gives alizarin on alkaline fusion {Ibid.
901).

[C] m-Hyclroxymithraquinone [l44]
(and the isomeric i-hydroxyquinone
simultaneously formed from phenol and
phthalic anhydride) gives alizarin on
alkaline fusion.

[D.] Gallic acid [Vol. II] on heating
with strong sulphuric acid gives rufi-
gallic acid =1:2:3:5:6: 7-hexahydr-
oxyanthraquinone (Robiquet, Ann. 19,
204; Wagner, Ch. Centr. 1861, 47;
Lowe, Journ. pr. Gh. 107, 296 ; Jaffe,
Ber. 3,694; Klobukowski and Noelting,
Ber. 8, 819; 9, 1256; 10, 88oj Wid-
mann, Ber. 9, 856). The latter yields
alizarin on reduction with sodium amal-
gam (Widmann, loc. cit. ; Bull. Soc.
[2] 24, 359).

[E.] From vanillin [l2l] and benzene
[6 ; I, &c.] through the following pro-
cesses : — Acetvanillin (Tiemann and
Nagai, Ber. 11, 647 ; Pschorr and
Sumuleanu, Ber. 32, 3405) on nitra-
tion and hydrolysis of the product gives
o-nitrovanillin, and this on methylation
yields the methyl ether. The latter on

oxidation by alkaline permanganate
gives o-nitroveratric acid, the nitro-acid
o-aminoveratric acid by reduction, and
hemipic acid (through the -nitrile) by
the diazo-method, followed by hydro-
lysis of the nitrile (Pschorr and Sumu-
leanu, loc. cit. 3411). Hemipic acid in
benzene solution under the influence of
aluminium chloride gives hydroxy-
methoxybenzoylbenzoic acid, and this,
by the action of strong sulphuric acid,
yields alizarin methyl ether, which gives
alizarin by demethylation on heating
with strong hydriodic acid at 127°
(Lagodzinski, Ber. 28, 1427).

[F.] From hystazarin [l47] by heat-
ing with strong sulphuric acid to 200-
205° (Liebermann and Hohenemser,
Ber. 35, 1778).

146. Furpurozantliin ;

Xanthopurpurin ;

1 : S-Dihydrozyanthraqmnone.

CO

CO

HO

OH

Natural Source.

Occurs with alizarin and purpurin
in madder root (Schiitzenberger and
Schiffert, Bull. Soc. [2] 4, 12). The
carboxylic acid also is present in madder
(Schunck and Romer, Ber. 10, 172).

Synthetical Processes.

[A.] From benzoic acid [Vol. II]
through the 3 : 5-disulphonic acid (Barth
and Senhofer, Ann. 159, 217), the 3 : 5-
dihydroxy-acid {Ibid. 222), and the
action of strong sulphuric acid on
a mixture of the latter with benzoic
acid at 105-110° (Noah, Ber. 19, '^^'^^'i;
Ann. 241, 266 : anthrachrysone =
1:3:5: 7-tetrahydroxyanthraquinone
is simultaneously formed in this pro-
cess).

[B.] From j)?(rpurin [l49] by reduc-
tion with phosphorus iodide and water.

240

AROMATIC ALDEHYDES AND KETONES [l46 B-149.

stannous chloride, sodium stannite, or
phosphorus and water (Schiitzenberger
and Schiffert, Bull. Soc. [2] 4, 12;
Eosenstiehl, Ann. Chim. [,5], 18, 224;
Corap. Rend. 79, 764; Liebermann
and Fischer, Ann. 183, 213).

Or purpurin on heating with aqueous
ammonia gives an amide (Stenhouse,
Ann. 130, 337 ; Liebermann, Ann.
183, 212), which yields purpuroxanthin
by the diazo-method (Liebermann, loc.
cit. 213).

147. Hystazariu ;
2 : S-Dihydroxyanthraquiuone.

148. Anthragallol ;
1:2: S-Trihydroxyaiithraqtiiiione.

CO

CO'

OH
OH

Natural Source.

The methyl ether occurs in Chay root
from Olclenlandia umhellata (see under
m-hydroxyanthraquinone [l44] ; A. G.
Perkin and Hummel, Trans. Ch. Soc.
67, 822).

Synthetical Processes.

[A.] Catechol [69] and phthalie an-
hydride [54; B,] give (with alizarin)
hystazarin when heated at 140-150"
with strong sulphuric acid (Liebermann,
Ber. 21, 2501 ; Seholler, Ihid. 2503).

Or veratrole (see under methyl-
eugenol [81 ; A]) on condensation with
phthalie anhydride by means of alu-
minium chloride gives 3 : 4-dimethoxy-
benzoylbenzoic acid, which, on heat-
ing with strong sulphuric acid, yields
hystazarin dimethyl ether, and finally,
by demethylation, free hystazarin (La-
godzinski and Loretan, Ber. 28, 118;
Liebermann and Hohenemser, Ber. 35,
1778).

Note : — The monomethyl ether has not been
synthesised.

CO

CO'

HO

OH

OH

Natural Source.

The three isomeric dimethyl ethers
occur in Chay root (A. G. Perkin and
Hummel, Trans. Ch. Soc. 63, 1168;
67, 819).

Synthetical Processes.

[A.] Y r ova. pi/ r Of/ alio I [84] 2ja.A ■phthalie
anhydride [54 ; R] by heating a mixture
of the two compounds with strong sul-
phuric acid (Seuberlich, Ber. 10, 39).

[B.] From benzoic and gallic acids
[Vol. II] by heating a mixture with
strong sulphuric acid {Ibid.).

[C] From alizarin [145] through
P-nitro- and /3-aminoalizarin (Schunck
and Romer, Ber. 12, 584 ; 588 : see also
Rosenstiehl, Bull. Soc, [2] 26, 63;
Brunner and Chuard, Ber. 18, 445).
Bromanthragallol from /3-aminoalizarin
gives a sulphonic acid on heating with
sulphurous acid, and this yields anthra-
gallol on heating with sulphuric acid
(Bayer & Co., Germ. Pat. 125575;
Journ. Ch. Soc. 82, Abst. I, 383).

Note : — The dimethyl ethers have not been
synthesised.

149. Purpurin;
1:2; 4-Triliydrozyauthraquinoue.

CO

HO

OH

HO

Natural Source.

Occurs with alizarin, purpuroxanthin,
&c., in madder root, probably as an
unstable glucoside (Colin and Robiquet,
Ann. Chim. [2] 48, 69; 51, no;

149-150 A.]

PURPURIN

241

Gaulthier de Claubry and Persoz, Ann.
Chim. [a] 48, 69; 51, no; Runge,
Ibid. 63, 282; Schiel, Ann, 60, 74;
Debus, Ann. 66, 351 ; 86, 117 ; Wolff
and Strecker, Ann. 75, i ; Rochleder,
Ann. 80, 321 ; 82, 205 ; Stenhouse,
Proc. Roy. Soc. 12, 6'^^; 13, 145;
Kopp, Jahresber. 1861, 938 ; Schiitzen-
berger. Bull. Soc. [2] 4, 12; Jahresber.
1864, 542; Auerbach, Ber. 4, 979;
Schiinck and Romer, Ber. 10, 551)'

The carboxylic acid also occurs in
madder (Schiitzenberger and Schiffert,
Bull. Soc. [2] 4, 13; Rosenstiehl, Comp.
Rend. 84, 561 ; Liebermann, Ber. 10,
1618).

Synthetical Processes.

[A.] From phenol [6O] and phthalic
anhydride [54; rJ. The phenol is
converted into p-chlorphenol (see under
resorcinol [70; C]), and this, when
heated witn phthalic anhydride and
strong sulphuric acid, gives (with
I : 4-dihydroxyanthraquinone) a small
quantity o£ purpurin (Liebermann and
Giesel, Ber. 10, 608). The i : 4-di-
hydroxy-quinone (quinizarin) yields
purpurin on oxidation with sulphuric
acid and manganese dioxide (Baeyer
and Caro, Ber. 8, 152).

[B.] From quinol [7l] and phthalic
anhydride through quinizarin by heat-
ing a mixture of these two compounds
with strong sulphuric acid (Grimm,
Ber. 6, 506; Liebermann, Ann. 212, 11),
and then as above under A.

[C] From alizarin [145] by oxida-
tion with manganese dioxide and sul-
phuric acid (De Lalande, Comp. Rend.
79, 669 ; Ber. 7, 1545 ; Jahresber.
1874, 486). Or by heating with strong
sulphuric acid to 225° (Liebermann and
Hohenemser, Ber. 35, 1781).

Or alizarin on nitration of the di-
acetate gives a-nitro- = 4-nitroalizarin
(Perkin, Ber. 8, 780 ; Journ. Ch. Soc
1876, 2, 578 ; Jahresber. 1877, 587
Schunck and Romer, Ber. 12, 587
Brasch, Ber. 24, 161 2), and this on

reduction with sodium amalgam or
ammonium sulphide yields a-amino-
alizarin (Perkin, loc. cit. ; Brasch, loc.
cit.). The latter gives purpurin by the
diazo-method (Brasch, loc. cit. 1614 :
see also Meister, Lucius, and Briining,
Germ. Pat. 97688 of 1897; Ch. Centr.
1898, 2, 696).

[D.] From purpuroxanthin [146] by
fusion with caustic potash (Noah, Ber.

19. 333)'

[E.] Anthraquinone [l44; C] gives
purpurin by brominating to a-dibrom-
and finally to tribromanthraquinone
(Graebe and Liebermann, Ann. Suppl.
7, 289; Diehl, Ber. 11, 181). The
latter yields purpurin on fusion with
potash at 200° (Diehl, loc. cit. 184).

150. Methylpurpuroxantliiu ;

1 : 3-Dihydroxy-6-MetIiylauthra-

qniuone.

CO HO

CH

CO

)H

Natural Source.

In the colouring-matter ' mang-
koudu ' from the root bark of Morinda
umlellata from Java and the Malay
Peninsula, and from E., S., and S. W.
India (A. G. Perkin and Hummel,
Trans. Ch. Soc. 65, 863).

Synthetical Process.

[A.] From benzoic acid [Vol. II]
through 3 : 5-dihydroxybenzoic acid (see
under purpuroxanthin [l46 ; A]) and
toluetie [54; A, &c.] through p-toluic
acid (see under o-cresol [61 ; A]).
A mixture of the two acids gives
methylpurpuroxanthin on heating with
strong sulphuric acid (Marchlewski,
Trans. Ch. Soc. 63, 1142).

242

CARBOHYDRATES AND GLUCOSIDES [151-152 A.

CARBOHYDRATES AND GLUCOSIDES.

151. Dihydroxyacetone ;
Fropauediolone.

HO.CH2.CO.CH2.OH

Natueal Sources.

A product of fermentation of glycerol
by the sorbose bacterium (Bertrand,
Comp. Rend. 126, 843 ; 984 ; Bull.
Soc. [3] 19, 502 ; Bertrand and Sazerac,
Comp. Rend. 132, 1504). According
to Emmerling (Ber. 32, 541) the sor-
bose bacterium is Bacterium xyllnum of
A. J. Brown (Trans. Ch. Soc. 49, 432).
Other micro-organisms are capable of
acting upon glycerol in a similar way
(Bertrand, Comp. Rend. 133, 887).

Glucose appears to give dihydroxy-
acetone among the products of its f er-
mentationby^aci//w« roseus yme(Bordas,
Joulin, and Raczkowski, Comp. Rend.
126, 1050), and the same Bacillus pro-
duces the dihydroxyketonef rom glycerol
{[bid. 1443).

Synthetical Peocesses.

[A.] ¥rom formic aldeliyde [9l] and
methyl alcohol [13] through nitroiso-
butylglycerol and dihydroxyacetone-
oxime (see under glycerol [48 ; L]).

[B.] From citric acid [Vol. II] through
acetonedicarboxylic acid and diamino-
acetone [48; M].

[C] From hippuric acid [Vol. II]
through diaminoacetone [48 ; N].

[D.] Glycerol [48] gives ' glycerose '
on oxidation with nitric acid or by
electrolysis (Van Deen, Jahresber. 1863,
501 ; Stone, Am. Ch. Journ. 15, 6^6 ;
Fischer and Tafel, Ber. 20, 1088), by
oxidation with platinum black (Gri-
maux, Comp. Rend. 104, 1276; Bull.
Soc. [2] 45, 481 ; 49, 251 ; Emmer-
ling, Ber. 32, 542), with sodium hypo-
bromite or bromine and lead glycerate
(Fischer and Tafel, loc. cit. 3384 ;
21, 2634; 22, 106), or with hydrogen
peroxide in presence of ferrous sulphate

(Fenton and Jackson, Trans, Ch. Soc.
75, 5). Glycerol gives glycerose on
oxidation by quinone in the presence of
light (Ciamician and Silber, Ber. 34,

1532)-

Glycerose is a mixture of dihydroxy-
acetone with glyceric aldehyde, the
former predominating (Fischer and
Tafel, Ber. 20, 3384; see also Piloty,
Ber. 30, 3162; Wohl and Neuberg, Ber.
33, 3099).

152. d-Erythrulose ;
Butanetriolone.

HO

I
HO.H2C.C.CO.CH2

I
H

OH

Natural Source.

A product of fermentation of ery-
thritol by the sorbose bacterium (Ber-
trand, Comp. Rend. 126, 762 ; 130,
1330; 1472; Bull. Soc. [3] 19, 347;
23, 681).

Synthetical Processes.

[A.] From erythritol [50] by oxida-
tion with nitric acid (Fischer and Tafel,
Ber. 20, 1088), with platinum black
(Grimaux, Comp. Rend. 104, 1276;
Bull. Soc. [2] 45, 481; 49, 251), or
with hydrogen peroxide and ferrous
sulphate (Fenton and Jackson, Trans.
Ch. Soc. 75, 7; Neuberg, Ber. 35,
2627).

Note : — The synthetical product is i-erythru-
lose. Tlie ketose character of the synthetical
sugar, and therefore its identity with the bio-
chemical sugar, has only been proved (apart
from optical properties) in the case of the pro-
duct obtained by the last method, viz. hydrogen
peroxide and ferrous sulphate (Neuberg, loc. cit.).
Other synthetical tetroses (probably aldoses)
have been obtained, but not from biochemical
sources. In order to complete the history of
these compounds the synthetical processes are
given below.

152 B-153 B.]

d-ERYTHRULOSE

243

OUier Syntheses of Tetroses.

[B.] From tartaric acid [Vol. II]
through g-lycolHc aldehyde (see under
furfural [126 ; E]). The latter in eon-
tact with dilute alkali at o° undergoes
aldol condensation with the formation
of erythrose (Fischer and Landsteiner,
Ber. 25, 2^^^ ; Jackson, Trans. Ch.
Soc. 11, 131 : see also Fischer, Ber. 27,
3200 ; Neuberg, Ber. 35, 2630).

Note : — The generators of glycollic aldehyde
referred to under furfural [126 ; F ; G, &c.]
thus become generators of erythrose. These
are : — acetal [93] ; ethyl alcohol [14] ; ethylene.

[C] From d-gluconic acid [Vol. II]
through d-arahinose [l53] by oxidising
the calcium salt with bromine in presence
of lead carbonate or with hydrogen
peroxide and ferric acetate (see under
153 ; B). d-Arabinose on further
oxidation with bromine and water gives
d-arabonic acid, and this on oxidation
as above yields d-erythrose (Ruff, Ber.
32, 3672). The erythrose has the
constitution : —

CHO-

HO HO

-C

C CHa . OH

I I

H H

[D.] Dextrose [154] gives an oxime
which on treatment with acetic anhy-
dride yields the nitrile of pentacetyl-
gluconic acid (see under 153; A).
The nitrile gives d-arabinose on hydro-
lysis with acids {Ibid.). Subsequent
steps as above under C.

[E.] From (jlycerol [48] through
acrolein [lOl], which, on treatment with
hydrogen chloride in alcoholic solution,
gives the diethylacetal of /3-chlorpro-
pionic aldehyde (Alsberg, Jahresber.
1864, 495 ; Wohl, Ber. 31, 1797). The
latter yields acrolein- acetal on treat-
ment with potassium hydroxide {lljid.
1798), and the acetal, on heating with
dilute sulphuric acid, gives (racemic)
glyceric aldehyde (Ibid. 2394), of which
the oxime on heating with aqueous
caustic alkali yields glycollic aldehyde
(Wohl and Neuberg, Ber. 33, 3106).
Subsequent steps as above under B.

Note : — A conversion of 1-arabinose into
a tetrose is possible through the following

steps : — 1-arabinoseoxime ; tetra-acetylarabonic
nitrile ; tetrose (Wohl, Ber. 26, 743).

1-Arabinose has been converted through 1-ara-
bonic acid into 1-erythrose by oxidising the
calcium arabonate vv^ith hydrogen peroxide in
presence of a ferrous salt. An isomeric tetrose
(1-threose) is obtained by similar processes from
1-xyIose through 1-xylonic acid (Ruff, Ber. 34,
1362). The 1-arabinose and 1-xylose employed
in these processes ai-e not synthetical products.

153. d-Arabinose; Fentanetetrolal.

H HO HO

CHO C C C-

HO H H

-CHo.OH

Natural Source.

A pentose has been found in the
urine in a case of morphinism (Sal-
kowski and Jastrowitz, Centr. med.
Wiss. 1892, Nos. 19 and 32) which,
according to Neuberg (Ber. 33, 2243),
is racemic arabinose, and may therefore
be considered to contain the d-arabinose
complex. (For behaviour of the stereo-
isomeric arabinoses in the animal body
see Neuberg and Wohlgemuth, Ber.
34, 1745.) This urine pentose is
synthesised in the organism (Neuberg,
Ber. 35, 1472 : for the separation
of d-arabinose from the racemic com-
pound by 1-menthylphenylhydrazine see
Neuberg, Ber. 36, 1192).

Synthetical Processes.

[A.] From dextrose [154], the oxime
of which on treatment with sodium
acetate and acetic anhydride gives the
cyanacetate = pentacetylgluconitrile.
The latter on hydrolysis yields d-ara-
binose. Or the nitrile, on treatment
with ammoniacal silver oxide solution,
gives the pentose in combination with
acetamide (Wohl, Ber. 26, 730 : see
also Neuberg and Wohlgemuth, Zeit.
physiol. Ch. 35, 31).

[B,] From d-gluconic acid [Vol. II] by
oxidation with bromine in presence of
lead carbonate, or with hydrogen per-
oxide in presence of basic ferric acetate
(Ruff, Ber. 31, 1573 ^ 32, ^^'>,', 33,
1799; 35, 2360, note).

R 2

244

CARBOHYDRATES AND GLUCOSIDES

[154.

154. Dextrose; d-Glncose;

Grape Sugar ; Starch Sugar ;

Eexanepeutolal.

HO

I
CHO C-

H HO HO

I I I

-c — c — c-

I I I I

H HO H H

-CH, . OH

Natueal Sources.

Widely distributed throug-hout the
vegetable kingdom, being found in the
sap of plants and in most fruits and
flowers. It is generally accompanied
by Isevulose and sometimes by certain
Cj2-sugars_, especially saccharose.

Honey contains from 33 to 42 per
cent, of dextrose (Dubrunfaut and Sou-
beiran, Jahresber. 1849, 464; Roeders,
Ibid. 1863,574; Brown/Analyst/1878,
2^J : see also Konig and Karsch, Zeit.
anal. Ch. 34, i ; Beckmann, Idid. 35,
263 ; V. Raumer, I/Ad. 41, 333).

Manna, an exudation from the manna
ash (Ornus europaa and 0. rotundifolid),
contains from 2-3 per cent, of dextrose
(Tanret, Bull. Soc. [3] 27, 947).

A honey-like exudation from 'Enoyiy-
mus japonica, produced by insect punc-
tures, contains dextrose (Maquenne,
Bull. Soc. [3] 21, 1082).

The sugar from mahwa-flowers from
Bassia latifolia consists of ' invert sugar'
(v. Lippmann, Ber. 35, 1448).

Crocin and picrocrocin from the saf-
fron plant, Crocus sativa, contain the
dextrose complex (Kastner, Ch. Centr.
1902, 2, 383).

The natural products known as gluco-
sides, which are found in such large
numbers of plants, are esters, in which
generally some sugar, and most fre-
quently glucose, plays the part of
a polyhydric alcohol (see Beilstein's
' Handbuch,' III, e^6s, and ' Die Glyko-
side'' by Van Rijn, Berlin, 1900).

Saccharose (cane-sugar) is resolved
by the majority of yeasts into dextrose
and Isevulose. Moulds such as Asper-
gillus niger and Penicillium glaucum
exert the same action (Gayon, Comp.
Rend. 86, 52 ; Duclaux, ' Chimie bio-
logique,' 1883; Fernbach, These, 1890 :
for two last see J. R. Green's 'Fer-
mentation,' p. 115)-

Penicillium duclauxi as well as P.
glaucum can invert cane-sugar (Bour-
quelot ; J. R. Green, loc. cit.). Monilia
Candida can also hydrolyse saccharose
(Fischer and Lindner, Ber. 28, 3037).
Mucor racemosus is said to be capable
of inverting saccharose (Fitz, Ber. 17,
1196 ; Brefeld, Landw. Jahrb. 5, 308,
as quoted by Fitz). Saccharose is not
hydrolysed by SaccJiaromi/ces apiculatus
(Fischer and Lindner, loc. cit. 3039).

Monilia javanica, one of the fungi
present in the ferment ' raggi ' used
for preparing arrack in Java (see under
ethyl alcohol [14]), can invert saccharose
(Went and Prinsen Geerligs, Bot. Zeit.
1895, p. 143). The ferment ' koji ' used
in Japan for preparing 'sake' is also
capable of inverting saccharose (Kellner,
Mori, and Nagaoka, Zeit. physiol. Ch.
14, 297 ; Kozai, Centr. Bakter. II, 6,

385).

The enzymes of various yeasts, &c.,
which are capable or incapable of
hydrolysing polysaccharides have been
investigated by Kalanthar (Zeit. physiol.
Ch. 26, 88).

Certain bacteria {Clostridium, Clado-
thi'ix, and Sarcina) are capable of invert-
ing saccharose (Laxa, Centr. Bakter. II,
6, 286; Ch. Centr. 1900, 1, 1298).
This sugar is inverted in bouillon by
Bacillus megatherium, B. jiuorescens
liquefaciens, and Proteus vulgaris (Fermi
and Montesano, Centr. Bakter. II, 1,
482; 542; Ch. Centr. 1895, 2, 712).
The sugar Bacteria of Marshall Ward
and J. R. Green can invert saccharose
(Proc. Roy. Soc. 65, 79). So also can
the gum-producing Bacillus levani'
formans (Greig- Smith and Steel, Journ.
Soc. Ch. Ind. 21, 1381) and the sugar-
gelatinising Clostridium gelatinosum
(Laxa, Zeit. Zuekerind. 26, 122 ; Journ.
Fed. Inst. 8, 639). Streptococcus Jiornen-
sis probably inverts saccharose (Boek-
hout, Centr. Bakter. II, 6, 161).

Maltose is fermentable only by those
yeasts which contain the enzyme malt-
ase {Sacch. cerevisia and octosporus), and
not l3y those containing invertin (Sacck.
marxianus). It is thus probable that
the hydrolysis of maltose to dextrose
precedes fermentation (Fischer, Ber. 28,
1433 : see also Maquenne's work for

154.]

DEXTROSE

243

general summary ; ' Las Sucres/ Paris,
1900, p. 646). Sacch. apiculatus does
not directly ferment maltose (Amthor,
Zeit. physiol. Ch. 12, 558). The 'koji '
ferment (see above) produces dextrose
from maltose (Kozai, Centr. Bakter. II,

Lactose or milk-sugar is hydrolysed
into dextrose and galactose (Bouchardat,
Ann. Chim. [4] 27, 68 ; Kent and
Tollens, Ann. 227, 33 1). The lactic
bacteria can effect this hydrolysis (Von
Freudenreich, Centr. Bakter. II, 6,

Frohberg yeast is capable of hydro-
lysing the biose trehalose (Fischer, Ber.
28, 1433 ; Kalanthar, Zeit. physiol.
Ch. 26, 88). Trehalose is slowly fer-
mented by certain yeasts, such as Saatz
(surface and sedimentary), Frohberg
(surface), Logos, Sacch. eliij^soidens and
paslorianus, and by Monilia Candida with
the formation of dextrose ; other species
{Sacch. apiculahis and pombe) are with-
out action (Bau, Ch. Centr. 1899, 2,

130)-

Certain mould-fungi such as Asper-

ffillus niger, PeniciUinm gUmcim, and

Voharia speciosa contain an enzyme, by

virtue of which they hydrolyse trehalose

with the formation of dextrose (Bourque-

lot, Comp. Rend, lie, 836 ; Bull. Soc.

Mycol. 9, 189). Bacilhs jiuorescens

liquefaciens slowly hydrolyses trehalose

(Emmerling and Reiser, Ber. 35, 703).

Strophanthin from the seeds of Stro-
jJianthus kombe yields on hydrolysis
(with strophantidin) a carbohydrate,
' strophantobiose methyl ether,' which
on further hydrolysis gives mannose,
rhamnose, and dextrose (Feist, Ber. 33,
3095).

Raffinose (melitriose) is hydrolysed
by Aspergillus viger with the formation
of melibiose and finally dextrose and
galactose (Gillot, Bull. Acad. Roy.
Belg. 1899, 311; Ch. Centr. 1899, 2,
139).

Melibiose is not affected by surface
yeast, but is resolved into dextrose and
d-galactose, and finally fermented by
sedimentary yeast (Bau, Woeh, Brau.
16, 397 ; Fischer and Lindner, Ber. 28,
3035). The resolution of raffinose by
feeble ferments was observed by Ber-

thelot (Comp. Rend. 109, 548), and
the product identified as melibiose by
Scheibler and Mittelmeier (Ber. 22,
3118).

Gentianose (?a triose), contained in
gentian root, is hydrolysed by dilute
sulphuric acid or the enzyme of Asper-
gillus uiger into dextrose (3 mols.) and
Isevulose (i mol.). The gentiobiose
obtained (with Isevulose) by partial
hydrolysis gives dextrose (3 mols.) on
complete hydrolysis (Bourquelot and
Herissey, Comp. Rend. 132, 571 ; 135,

399)-

Melezitose, a triose found in the
mannas from Pinus larix, &c., is re-
solved by hydrolysing agents (dilute
acids or the enzyme of Aspergillus niger)
into dextrose and the biose turanose,
the latter giving dextrose as a final
product of hydrolysis {Ibid. Journ.
Pharm. [6] 4, 385 ; Alekhine, Ann.
Chim. [6] 18, 533).

Starch is saccharified with the pro-
duction of dextrin, maltose, and dextrose
by the mould- fungi used in making the
Javanese ' raggi ' (see under ethyl alco-
hol [14] for full references). The
species chiefly concerned are Chlamydo-
mucor oryzcp. and llhizopus oryzce. The
ferment (' koji ') used in the above pro-
cess can produce dextrose from raffinose
(Kozai, Zeit. Bakter. II, 6, 385). The
mould-fungi concerned in the produc-
tion of the Japanese ' sake ' can also
saccharify starch (see under ethyl alco-
hol [14] for references).

The ferments concerned in the pro-
duction of the Japanese 'awamori'
comprise, among others, the starch-
saccharifying Aspergillus luchuensis of
Inui (Journ. Imp. Coll. Sci. Tokio,
1 90 1, 15; Journ. Fed. Inst. 8, Abst.

529)-

The mould-fungus Mucor erectus can
resolve starch into dextrose among other
carbohydrates (see under ethyl alcohol
[14]). Mucor {Amylomyces) rouxii of
Calmette, which is contained in Chinese
yeast, is capable of hydrolysing starch
(see under ethyl alcohol [14] for refer-
ences : for industrial formation of
dextrose by Mucor or Aspergillus see
Calmette's Fr. Pat., Journ. Fed. Inst.
7; 393). Mucor (3- and y-AmylomyccSy

246

CARBOHYDRATES AND GLUCOSIDES

[154-E.

found on Japanese and Tonquin rice
respectively, are starch saccharifying*
moulds (Sitnikoff and Rommal, Journ.
Fed. Inst. 7, 112). Chinese yeast from
Cambodia contains Mzicor camhodia,
which also can saccharify starch
(Chrzascz, Zeit. Bakter. II, 7, 326).

A Monilia {? M. sitopH^a, Saccardo)
found on earth-nuts in Java can
saccharify starch (Went, Centr. Bakter.
II, 7, 544; 591 ; also Journ. Ch. Soc.
80, II, Abst. 412).

Bacillus anthracis can produce sugar
(? dextrose) from starch (Maumus,
Comp. Rend. Soc. Biol. 1893, io7)-
Starch is slowly hydrolysed by Bacillus
jiuorescens Uqiiefacieyis (Emmerling and
Reiser, Ber. 35, 702). Dextrose is
among the products of hydrolysis of
starch by Bacillus suaveolens (Sclavo
and Gosio, Bied. Centr. 20, 419 ; Journ.
Ch. Soc. 60, Abst. 1284).

Dextrose is present as a normal con-
stituent of the blood of man and
animals, and of the lymph, chyle, and
urine (Miura, Zeit. Biol. 32, 279 ;
Seegen, Ber. 21, Ref. 849 ; Abeles,
Ibid. 850 ; Pickardt, Zeit. physiol. Ch.
17, 217 ; Bence Jones, Journ. Ch. Soc.
14, 22 ; Baisch, Zeit. physiol. Ch. 19,
338 ; 20, 249 ; Quinquaud, Comp.
Rend. Soc. Biol. 41, 285 : for occur-
rence in normal blood of hen see Saito
and Katsuyama, Zeit. physiol. Ch. 32,
231). It has been found also in the
aqueous humour of the eye (Pautz,
Zeit. Biol, 31, 212), in aqueous extract
of liver (Seegen and Kratschmer,
Pfliiger's Arch. 22, 206; 24, 52), in
muscle (Panormoff, Zeit. physiol. Ch.
17, S9^)> ^^d i^ the cerebrospinal
fluid (Nawratzki, Du Bois-Reymond's
Arch. 1897, p. 136; Ch. Centr. 1897,

The source of dextrose in the animal
body is probably glycogen, the latter
giving dextrose on hydrolysis (Berthe-
lot and De Luca, Comp. Rend. 49,
213 ; Ann. Chim. [3] 58, 448 ; Kiilz
and Vogel, Zeit. Biol. 23, 100 ; 108).

Sugar is present in considerable
quantity in the blood and urine in
cases of diabetes. The sugar is ordinary
dextrose (Thenard, 1806; Chevreul,
Ann. Chim. [i] 95, 319 ; Bouchardat,

Comp. Rend. 6, '^'^'j ; Peligot, Ibid. 7,
106; Ann. Chim. [2] 67, 113; Le
Goff, Comp. Rend. 127, 817; Patein
and Dufau, Ibid. 128, ^JS)-

Dextrose occurs in the urine in cases
of diaceturia (Kobert, Ch. Centr. 1900,
2, 920), and is formed by muscular
fibre and in the liver after death
(Cadeac and Maignon, Comp. Rend.
134, 1443).

Synthetical Processes.

[A.] From formic aldehyde [91] or
glycerol [48] through a-acrose, a-acrosa-
zone, a-acrosone, i-fructose, i-mannitol,
i-mannose, i-mannonic acid, and d-
mannonic acid (see under mannitol
[51; a]). The latter acid on heating
with quinoline at 140-150° is converted
(partially) into d-gluconic acid [Vol. II],
which can be separated from unaltered
mannonic acid by removing the latter
as brucine salt. d-Gluconic acid gives
dextrose = d-glucose on reduction with
sodium amalgam in acid solution
(Fischer, Ber. 23, 799; 2611).

[B.] From acetone [IO6] through
acrolein [lOl] and a-acrose (see under
mannitol [51; G]).

[C] From tartaric acid [Vol. II]
through glycollic aldehyde and a-acrose
[51; G].

Note : — Other generators of glycollic alde-
hyde, viz. acdal [93], eihxjl alcohol [14], and
choline ["Vol. II], are referred to under furfui-al
[126 ; F ; G ; H].

[D.] Sorbitol [52] gives dextrose on
oxidation with dilute potassium per-
manganate solution (Vincent and Dela-
chanal, Comp. Rend. 108, 354), with
bromine and water {llnd. Ill, 51 : see
also Fischer, Ber. 23, 3686), or with
hydrogen peroxide and ferrous sulphate
(Fenton, Trans. Ch. Soc. 75, 10).

[E.] Lceviilose [l55], under the in-
fluence of dilute caustic alkali, gives
(with mannose and ' glutose ') dextrose
(Lobry de Bruyn and Van Eckenstein,
Rec. Tr. Ch. 14, 156; 203; 16, 274;
282; Ber. 28, 3078). The salts of
weak organic acids at 100° and (to
a less extent) those of mineral acids
in aqueous solution are also capable
of transformino: Isevulose into dextrose

154 E-155.]

DEXTROSE

247

when the former is in excess [Ibid. 14,
162 ; 203 ; Prinsen Geerligs, Ch. Centr.
1898, 1, 712).

[P.] Mannose [l56l, under the in-
fluence of dilute alkali as above, gives
dextrose with Isevulose and other sugars
(Lobry de Bruyn and Van Eckenstein,
loc. cit. 14, 98; 156; 203; 16, 257;
274; Ber. 28,3078).

[G-.] (1- Gluconic acid [Vol. II] lactone
gives glucose on reduction with sodium
amalgam in acid solution (Fischer, Ber.
22, 2204 J 23, 804 : also A above).

155. Xsevulose; d-Frnctose;
Fruit Sugar ; Hexauepentolone.

H HO HO

I I I

HO . H,C . CO C C C-

I I I

HO H H

-CH,.OH

Natueal Sources.

Occurs throughout the vegetable
kingdom associated with dextrose. It
accompanies dextrose also in honey (see
under dextrose for references).

The sweet pods of the ^ mesquit tree,'
Prosopis dnlcis, from N. and S. America
contain over 5 per cent, of Isevulose, but
no dextrose (Steel, Rep. Aust. Assoc.
1 898, p. 946). Invert sugar is contained
in the mahwa-flowers from Bassia lafi-
folia (see under dextrose). Manna (see
under dextrose) contains 2'5-3-4 per
cent, of Isevulose, arising probably from
the hydrolysis of manneotetrose. (see
below: Tanret, Bull. Soc. [3] 27,

947)-

The yea&ts, moulds^ and Bacteria
capable of hydrolysing or ' inverting '
saccharose may be regarded as bio-
chemical producers of Isevulose from
the Cj2-sugar (see under dextrose).
Yeast allowed to infuse in chloroform
w^ater gives a 1-sugar, apparently Isevu-
lose (Salkowski, Zeit. physiol. Ch. 13,
506).

Saccharose is fermented by Lenconos-
toc mesetiteroides with the formation of
dextran and Isevulose (Van Tieghem,
Jahresber. d. Agrikulturch. 1879, 544).

Lsevulose is produced from mannitol

by Bacterium aceti and B. ocylinum
(A. J. Brown, Trans. Ch. Soc. 49, 182 ;
51, 638). B. aceti of Hansen resembles
B. aceti of Brown in its action on
mannitol (Seifert, Ch. Centr. 1897, 2,
871).

The sorbose bacterium { = B. xylinum,
according to Emmerling) produces Isevu-
lose from mannitol (Vincent and Dela-
chanal, Comp. Rend. 125, 716; Ber-
trand. Ibid. 126, 763). Mannitol is
not oxidised by Bacterium pafiteurianum ,
and is only converted slowly into Isevu-
lose by B. kiitzingianum (Seifert, Ch.
Centr. 1897, 2, 871 ; Bied. Centr. 27,
123; Joum. Ch. Soc. 74, II, 399;
Mayer, Journ. Fed. Inst. 4, 666).

Raffinose (melitriose) is hydrolysed
by high fermentation yeasts to meli-
biose and Isevulose, while low fermenta-
tion yeasts produce dextrose, Isevulose,
and d-galactose. The yeasts investi-
gated were Frohberg and Saatz, Sac-
charomyces cerevisia, S. ellijisoidens, S.
pastorianus, S. logos, S. marxianns, S.
anomalus, Schizosacch. pombe, and the
kefir ferment. S. apicidatus does not
resolve raffinose (Bau, Ch. Centr. 1898,
2, 682 ; Journ. Fed. Inst. 4, 644).

Raffinose is inverted and finally com-
pletely assimilated by Aspergillus niger
(Gillot, Bull. Acad. Roy. Belg. 1899,
p. 211). In a solution of raffinose in
presence of a mineral acid Benicillivm
glaucum also causes inversion {Ibid.
J9C0, p. 99).

Gentianose, from gentian root, gives
Isevulose on hydrolysis (see under dex-
trose for reference).

Inulin, a carbohydrate related to
starch and found in many plants as
a reserve material, is resolved by the
enzyme known as inulase into Isevulose.
(According to Tanret, Bull. Soc. [3] 9,
227, some dextrose is also formed by
ordinary hydrolysis.) Inulase is found
in Aspergillus niger (see J. R. Green's
' Fermentation,' Chap. VI ; also Bour-
quelot, Comp. Rend. 116, 1143), as well
as in association with inulin in various
tubers, bulbs, &c.

Lsevomannan, a complex polysac-
charide obtained from the ivory-nut
{PhyfelejiJias macrocarpa), gives Isevulose
and mannose on hydrolysis (Baker and

248

CARBOHYDRATES AND GLUCOSIDES

[155-156.

Pope, Proc. Ch. Soc. 16, 72 ; Trans. 77,
696).

Gratninin, a reserve carbohydrate
obtained from Arrhenatherum hulbosum,
appears to be a polysaccharide of laevu-
lose (Harlay, Comp. Rend. 132, I,

423)-

Manneotetrose iS^i^iJ^'^xi) a sugar
contained in 'manna,' is resolved by
Aspergillus^ by enzymes, and by hydro-
lysing- agents generally into Isevulose
and manninotriose, CjgHggOjg- The
latter contains the dextrose and galact-
ose complexes (Tanret, Comp. Rend.
134, 1586 ; Bull. Soc. [3] 27, 947).

A 1-sugar has been found in urine,
and this is probably Isevulose (Kiilz,
Zeit. Biol. 27, 228 ; Cotton, Bull. Soc.
[2] 33, 546). According to Bretet
(Cn. Centr. 1898, 1, 67), this sugar
occurs in diabetic urine. In certain
pathological cases Isevulose occurs in
the urine, serum, ascitic and pleural
fluids (Neuberg and Strauss, Zeit.
physiol. Ch. 36, 227).

Synthetical Processes.

[A.] Dextrose [l54] is converted into
the osazone by phenylhydrazine, the
osazone reduced by zinc dust and acetic
acid to isoglucosamine, and the latter
decomposed by nitrous acid. Or the
osazone is (more conveniently) heated
with fuming hydrochloric acid and con-
verted into the glucosone. The latter
gives Isevulose on reduction (see under
sorbitol [52 ; C] ; also Fischer and
colleagues, Ber. 19, 1920; 20, 2569;
21, 2631 ; 22, 94; 23, 370; 2I2i).

Dextrose gives Isevulose among other
sugars under the influence of caustic
alkaline solutions (Lobry de Bruyn and
Van Eckenstein ; see under dextrose
[154; E]).

Dextrose gives glucosone when oxi-
dised by hydrogen peroxide and ferrous
sulphate (Morrell and Crofts, Trans.
Ch. Soc. 75, 786; 81, 666), and this
can be reduced to Isevulose as above.

[B.] From (l-mannose [156] through
the osazone and osone, and then as
above (see under sorbitol [52 ; C]).

Lsevulose is foi-med with other sugars
by the action of alkali on mannose

(Lobry de Bruyn and Van Eckenstein,
Rec. Tr. Ch. 14, 98; 156; 203; 16,
257; 274; Ber. 28, 3078). _

[C] Mannitol [5l], on oxidation by
air in presence of platinum black, or by
potassium permanganate or nitric acid,
gives a mixture of mannose and Isevu-
lose (Gorup-Besanez, Ann. Chim. [3]
62, 489; Iwig and Hecht, Ber. 14,
1 760; Dafert, Ber. 17, 227 ; Ibid. Ref.
479; Fischer, Ber. 20, 831; Fischer
and Hirschberger, Ber. 21, 1805); also
by oxidation with nitroso-camphor
(Cazeneuve, Comp. Rend. 109, 185).

The oxidation of mannitol by bromine
water and sodium carbonate solution
also yields Isevulose (Fischer, Ber. 23,
3686).

156. d-Mannose ; Seminose;
Hexanepentolal.

H H HO HO

I I I I
CHO C C C C CH2 . OH

I I I I

HO HO H H

Natural Sources.

An anhydride of mannose occurs in
the leaves of AmorphophaUus Jconjac =
rivieri, and mannose itself has been
extracted from the stalk (Tsukamoto,
Bull. Imp. Coll. Agric. Tokio, 2, 406 ;
Journ. Ch. Soc. 72, Abst. 275 : see
also Tsuji, Ifjid. 70, 44 ; Kinoshita,
ILuL 60).

Mannose occurs in ordinary cane-
sugar molasses, but it appears to result
from the heating of the ' invert sugar '
with lime (Lobry de Bruyn, Rec. Tr.
Ch. 14, 125; 16, 257; 274).

The sugar contained in orange-peel is
possibly mannose (Flatau and Labbe,
Bull. Soc. [3] 19, 408).

The mannans or mannosides found
in many plants contain the mannose
complex. Among such sources are
salep mucilage from the tubercles of
the root of Orchis morio (Gans and
Tollens, Ber. 21, 2150 ; Ann. 249, 245 ;
Fischer and Hirschberger, Ber. 22,
369; Herissey, Comp. Rend. 134, 721),
and the reserve material contained in
many nuts, seeds, and berries, of which

156.]

d-MANNOSE

249

the following are given by Reiss (Ber.
22,612): — V3i\vi\di(ieiB{PIi7/telejohas macro-
carpa ; P/zcenix clactylifera ; Chamarops
humilis-=.Tr achy car pus exceUa; Lodoicea
seychellarmn ; Ela'isguineensis): Liliaeese
[Allium cepa ; Asparagus offi,c'malu) :
\x\(}ii2i.QQ^{Iris pseudacortis) : Loganiacese
[Slrychnos nux vomica) : Rubiacese [Coffea
arabica). (See also Sehulze and Steiger,
Ber. 20, 390; Zeit. physiol. Ch. 14, 227;
Scbulze, Ber. 22_, 1 192 ; 23, 2579 ; Zeit.
physiol. Ch. 16, 422.)

The nut of PhytelepJias macrocarpa,
used as 'vegetable ivory/ is a particularly
rich source of mannan (Reiss, loc. cit. ;
Fischer, Ber. 22, 1155; Fischer and
Hirschberger, Ibid. 3218). The com-
plex carbohydrate from this nut, which
gives mannose (and galactose) on hydro-
lysis, is a ' mannogalactan ' (Baker and
Pope, Proc. Ch. Soc. 16, 72; Trans.
77, 696).

The reserve carbohydrates of the
seeds of lucern {31edicago saliva) and of
Trigonella fcennm-grfecum are manno-
galactans (Bourquelot and Herissey,
Comp. Rend. 130, 731).

The carbohydrate of the albumins of
the St. Ignatius bean {Slrychnos ignalii)
and of S. nux vomica is a mixture of
mannan and galactan (Bourquelot and
Laurent, Ibid. J411; 131,276). The
reserve carbohydrate of the seeds of
Trifolium repens is a mannogalactan
(Herissey, /(^eV/. 130, 1719); also that
of the seeds of the American bean,
Gleditschia lriaca?ithos (Goret, Ibid. 131,
60).

The carbohydrate obtained by Wrob-
lewski (Ber. 31, 1134) from the ' in-
vertin ■" of yeast may be mannose (Sal-
kowski, Zeit. physiol. Ch. 31, 304).

The Japanese Alga, ' nori ' {Porphyra
laciniala), gives d-mannose (with i-
galactose) on hydrolysis (Oshima and
Tollens, Ber. 34, 1422).

A reserve carbohydrate found in the
bulb of Lilmm candidum and L. auralum,
and probably in L. bulbifernm, L. cro-
ceum, L. dauricum, L. lancifolium, L.
longijlorum, and L. marlagon, gives
mannose on hydrolysis (Parkin, Proc.
Cambridge Phil. Soc. 11, 139).

The seeds of Phcenix canariensis con-
tain mannans in sufficient quantity to

serve as a convenient source of mannose
on hydrolysis (Bourquelot and Herissey,
Comp. Rend. 133, 644).

Reserve carbohydrates contained in
the seeds of Ancubajaponica and Rusciis
aculealus are mannans (Champenois,
Comp. Rend. 133, 885; Dubat, Ibid.
942). The endosperm of the germi-
nating date contains a mannan (Griiss,
Ber. deutsch, bot. Gesell. 20, 36 ; Woch.
Brau. 19, 243; Ch. Centr. 1902, 1,
1227), Asparagus seeds contain a
mannan (Peters, Arch. Pharm. 240, 53) ;
so also do the seeds of (Enanthe phel-
landrium (Champenois, Journ. Pharm.
15, 228).

The reserve carbohydrates of the seeds
of the Palmaceous plants, Areca calechu,
Aslrocaryum vidgare, (Enocarpus bacaba,
Erythea eduUs, and Melroxylon sagu, con-
tain mannans (Lienard, Comp. Rend.
135, 593). The presence of mannan in
the seeds of Trachycarpus excelsa and
of Rohdea japonica, and in the wood of
Cryplomeria, has been shown by Kimoto
(Bull. Imp. Coll. Agric. Tokio, 5, 253 :
see also Reiss as quoted above).

Mannans have been found in coffee
berries and coco and palm nuts (Sehulze,
Ber. 23, 2582; 24, 2277, &c.); in
carob seeds from Ceralonia siliqna
(Effront, Comp. Rend. 125, 38; 116;
309 ; Van Eckenstein, Ibid. 719 j Bour-
quelot and Herissey, Ibid. 129, 228 ;
339; 391; 614); (probably) in gum
ammoniacum (Frischmuth, Ch. Centr.
1898, 1, 2)^), and in stalks of rye
(Ritthausen, Ibid.).

The carbohydrate ' strophanthobiose
methyl ether' resulting from the hy-
drolysis of strophanthin contains the
mannose complex (Feist, Ber. 33, 2095 :
see also under dextrose [l54]).

Mannose-yielding compounds are con-
tained in the seeds of Biospyros kaki and
in the root of Amorphophallus konjac =
rivieri (Loew and Ishii; Loew and
Tsuji, as quoted by Tollens, 'Kohlenhy-
drate,'' II, 229); in ergot of rye (Voswin-
kel, Ch. Centr. 1891, 2, 766); in various
woods (Weld, Lindsey, and Tollens, Ber.
23, 2990 ; Ann. 267, 341); in ligneous
tissue of gymnosperms (Bertrand, Bull.
Soc. [3] 7, 468; Comp. Rend. 114,
1492; 129, 1025); in cryptogams

250

CARBOHYDRATES AND GLUCOSIDES [156-158 A.

("Winterstein, Zeit. physiol. Ch. 21,
152) ; and in gum extracted from yeast
by lime or alkali (Hessenland, Zeit. d.
Ver. f. Riibenzuckerindustrie, 1892,
p. 67 1 ; Salkowski, Ber. 27, 497 ; Zeit.
physiol. Ch. 13, 506).

The woody tissue of cycads and coni-
fers and (to a small extent) that of
Ephedra distachya contains mannose-
yielding compounds (Bei-trand, Comp.
Rend. 129, 1025).

Note : — For general distribution of mannan
in the wood of the sugar maple and throughout
the vegetable kingdom see Storer in the Bulletin
of Bussey Institution, III, No. 2, 1902.

Synthetical Processes.

[A.] From formic aldehyde [9l]
through a-acrose, &c., as under manni-
tol [51; a]. d-Mannonic acid gives
d-mannose on reduction with sodium
amalgam in acid solution {loc. cit. ; also
Fischer, Ber. 22, 2204).

[B.] From glycerol [48] through a-
acrose, &c., as under mannitol [51 ; B].

[C] From manniiol [5l] with Isevu-
lose by oxidation (see under Isevulose
[155 ; C]). Also by oxidation with
hydrogen peroxide and ferrous sulphate
(Fenton and Jackson, Trans. Ch. Soc.
75, 8).

[D.] From tartaric acid [Vol. II]
through glycollic aldehyde and a-acrose
(see under mannitol [51; G]).

[E.] Dextrose [154] gives mannose
(with Isevulose, glutose, and (/)-fructose)
under the influence of alkali or lead
hydroxide (Lobry de Bruyn and Van
Eckenstein, Rec. Tr. Ch. 16, 257 ; 274).

[P.] LcPvvlose [155] gives mannose
with other sugars under the same con-
ditions as above [Ibid. 14., 156; 203;
16, 274; 282; Ber. 28, 3078).

157. Saliciu ; Saligenin Glucoside.
HO.CH,.CeH,.0(C,H,A)

Natural Sources.

In bark and leaves of Salix helix,
S. ' p7-acow,' S. jjentandra, and other
species. Occurs also in bark and leaves
of Popid/is tremula, F. tremuloides, &c.
(Tischhauser, Ann. 7, 280), and in

flower buds of Spircea ulmaria (Buchner,
Ann. 88, 0,2^).

Occurs also in castoreum (Wohler,
Ann. 67, 360).

Note :— For full references and list of species
see under saligenin [55].

Synthetical Process.

[A.] From salicylic aldehyde [ll7]
and dextrose [l54]. The latter is con-
verted into acetchlorglucose [CgH^OCl
[Q.^ip^^ (Colley, Comp. Rend. 70,
401 ; Ann. Chim. [4] 21, 363 : see
also Konigs, Ber. 21, 2207 ; Fischer
and E. F. Armstrong, Sitz. Pr. Akad.
1901, 13, 316; F. V. Arlt, Monats. 22,
144; Skraup and Kremann, Ibid.
375; F. and E. F. A., Ber. 34,
2885). Salicylic aldehyde and acet-
chlorglucose in presence of potassium
ethoxide give the glucoside helicin
(Michael, Am. Ch. Journ. 1, 309;
Comp. Rend. 89, 355; Ber. 12, 2260 ;
14, 21 00; 15, 1922 : see also Schiff, Ber.

14, 2559)- . . , ,.

Helicin on reduction with sodium

amalgam or zinc and sulphuric acid

gives salicin (Lisenko, Zeit. [i] 1864,

577 ; Michael, Am. Ch. Journ. 5, 172).

158. Fopulin ; Benzoylsaliciu.
(C,H,0,)CH,.CeH,.0(CeH,A)

Natural Sources.

In bark, leaves, and buds of Populns
trennda, P. 7iigra, P. pyramidalis, and
P. halsamifera (Braconnot, Ann. Chim.
[2] 44, 296 ; Berz. Jahresber. 11, 286
Biot and Pasteur, Comp. Rend. 34
606; Piria, Ann. Chim. [3] 34, 278
44, ofie-, Ann. 81, 245; 96. T^l^
Piccard, Ber. 6, 890 ; Hallwachs, Ann
101, 372; V. Lippmann, Ber. 12, 1648
Herberger, Arch. Pharm. 46, 104; 47,
250).

Synthetical Process.

[A.] From salicin [l57] and benzoic
acid [Vol. II] by heating the glucoside
with benzoic anhydride (Schiff, Ann.
164, 5).

159-160 G.]

METHYLARBUTIN

251

159. Methylarbntin ;
Glucoside of p-Methozypheuol.

Natural Sources.

Occurs with arbutin in the leaves of
the red bearberry, Arcfosiap^t/los uva-
vrsi, and in all the plants which contain
arbutin (Hlasiwetz and Habermann,

Ann. 177, 334; Sehiff, Ann. 206, 159 :
see also under quinol [71]).

Synthetical Process.

[A.] From quinol methyl ether [73]
and dextrose [154] by the interaction
of acetchlorglucose (see above under
salicin [157 ; A]) and potassium-quinol
methyl ether (Michael, Am. Ch. Journ.
5, 178; Ber. 14, 3097).

SULPHUR COMPOUNDS.

160. Carbon disulphide,

CS,

Natural Sources.

Schizophyllum lobatum , a, inngus found
in Java on fallen branches of Pedocarpus
and on dead bamboo, when cultivated
in sugar-peptone infusion gives carbon
disulphide or some compound from
which the CS2-complex is easily split
off (Went, Ber. deut. bot. Gesell. 1896,
p. 939; Ch. Centr. 1896, 2, 939).

Carbon disulphide occurs in mustard
oil, resulting possibly from the decom-
position of sinigrin or of the allyl iso-
thiocyanate (Gadamer, Arch. Pharm.
235, S3)-

Synthetical Processes.

[A.] By heating carbon in sulphur
vapour (Lampadius, 1796 ; Clement
and Desormes, Ann. Chim. 42, 121 ;
Vauquelin and Robiquet, Ibid. 61, 145;
Berthollet, Thenard, and Vauquelin,
Ibid. 72, 252 ; Berzelius and Marcet,
Schweigger's Journ. 9, 284; Gilbert's
Ann. 28, 427; 453; 48, 177; Ann.
Chim. 83, 252; Pogg. Ann. 6, 144;
Zeise, Schweigger's Journ. 26, i ; 41,
98; 170; 43, 160; Couerbe, Ann.
Chim. [2] 61, 225 ; Kolbe, Ann. 45,
S'^; 49, 143; Pelouze and Fremy,
' Traite d. Chim.' 4'«« ed. I, 923 ; Sidot,
Bull, Soc. [2] 13, 323; Comp. Rend.
69, 1303 ; Journ. Pharm. [4] 13, 239 :
for manufacture in the electric furnace

see Taylor, Trans. Amer. Electroch.
Soc. 1, 115; Journ. Soc. Ch. Ind. 21,
1236 ; also Eng. Pat. 16 SS^ of 1902).

[B.] From wethane [l] through car-
bon tetrachloride by extreme chlorina-
tion (Dumas, Ann. 33, 187). The latter
gives carbon disulphide on heating with
phosphorus pentasulphide at 200°
(Rathke, Ann. 152, 200).

[C] From ethyl alcohol [14] through
chloroform by distillation with bleaching
powder (see under methane [l ; D]).
By chlorination chloroform gives carbon
tetrachloride (Regnault, Ann, 33, 332 ;
Friedel and Silva, Bull. Soc, [2] 17, 537),
which can be treated as above under B,

[D.] From acetone [IO6] through
chloroform (Liebig, Ann. 1, 199), and
then as above.

[E.] From acetic aldehyde [92]
through chloral by chlorination (Pinner,
Ber. 4, 256 ; Wurtz and Vogt, Zeit.
[2] 7, 679). Chloral is decomposed by
alkali with the formation of chloroform
(Liebig, loc. cit.).

[P.] From acetic acid [Vol. II]
through the trichloro-acid by chlorina-
tion (Dumas, Ann. 32, loi ). Trichlorace-
tic acid gives chloroform on heating with
aqueous alkali [Ibid. 113; Ann. Chim.
[2] 56, T15).

[G,] From methyl alcohol [l3] through
methyl chloride (Dumas and Peligot,
Ann. 15, 17; Ann. Chim. 61, 193;
Groves, Journ. Ch. Soc. 27, 641). The
latter can be chlorinated to carbon
tetrachloride (Damoiseau, Comp. Rend.
92, 42), ard treated as under B.

252

SULPHUR COMPOUNDS

[160 H-iei c.

[H.] From tr'imeiliylamine [Vol. II]
through methyl chloride by heating
the hydrochloride to 326° (Vincent,
Journ. Pharm. [4] 30, 132; Jahresber.
1878, 1 135), and then as above under G.

[I.] 'Prom formic acid [Vol. II] and
methyl alcohol [13] through methyl
formate (Volhard, Ann. 176, 133).
The latter on extreme chlorination gives
perchlormethyl formate (Hentschel,
Journ. pr.Ch. [2] 36, lOO; 214; 305),
and this decomposes in contact with
aluminium chloride with the formation
of carbon tetrachloride {Ibid. 308).

[J.] Alli/l i^othiocyanate [I66] gives
carbon disulphide among the products
obtained by heating with water at 1 00-
105° (Gadamer, Arch. Pharm. 235, 53).

[K.] From gallic acid [Vol. II]
through trichlor-aa-glyceric acid by
the action of hydrochloric acid and
potassium chlorate (Schreder, Ann. 177,
282). The trichloro-acid gives chloro-
form by the action of alkali in the cold.

[L.] From salicylic acid [Vol. II]
through trichlor-aa-glyceric acid as
above.

[M.] From phenol [6O] through
trichlor-aa-glyceric acid as above.

[N.] Benzene [6; I, &c.] by the action
of potassium chlorate and sulphuric acid
gives trichlorphenomalic acid, CCI3 .
CO . CH : CH . CO,H (Carius, Ann.
142, 129 ; Kekule and Strecker, Ann.
223, 170; Anschiitz, Ann. 254, 152),
and this yields chloroform (with malei'c
acid) on heating with barium hydroxide
solution. Subsequent steps as under B.

161. Methyl Mercaptan ;
Methanethiol ; Methyl Sulphydrate.

CH3.SH

Natural Sources.

Among the products of anaerobic
putrefaction of albumin (Nencki and
Sieber, Monats. 10, 526). The Bacilli
known to produce this compound from
serum albumin are Bacillus magnns, B.
spivosus, B. liquefaciens, and the anthrax
Clostridinm.

Occurs among the products of putre-

faction of fish (Monier, Zeit. physiol.
Ch. 22, 514) and of elastin by anaerobic
micro-organisms (Zoja, Ibid. 23, 236).
Also among the products of in-
testinal decomposition of albumin (Ham-
marsten, ' Lehrbuch,'' 3rd ed. 277) and,
possibly, in urine after taking asparagus
{Ibid. 480; Nencki, Arch. exp. Path.

A bacterium found in the urine of
a patient suffering from pneumonia and
albuminaria caused production of methyl
mercaptan (Karplus, Virch. Arch. 131,
210 ; Journ. Ch. Soc. 64, II, '>,'>f^'

Bacillus esterijicans isolated from
putrefying litmus solution and Bac.
prcepollens from the intestinal contents
decompose peptone infusions with the
production of mercaptan (? methyl)
among other products (Maassen, Ch.
Centr. 1899, 2, 1058).

A mercaptan (? methyl) is among the
products of the anaerobic putrefaction
of milk by Bacillus putrijicus and by
the Bacilli of malignant oedema and
of symptomatic anthrax (Bienstock,
Ch. Centr. 1901, 1, 1209).

Synthetical Processes.

[A.] From methyl alcohol [l3]. Sodium
methyl sulphate is distilled with potas-
sium hydrosulphide (Gregory, Ann. 15,
239; Obermeyer, Ber.20, 2918; Klason,
Ibid. 3407).

[B.] From thiocyanic acid [174] and
methyl alcohol [13]. Potassium thio-
cyanate on distillation with calcium
methyl sulphate gives methyl thio-
cyanate (Cahours, Ann. Chim. [3] 18,
261 ; Ann. 61, 95). The latter on
beating to 180° yields (with the iso-
thiocyanate) methyl thiocyanurate (Hof-
mann, Ber. 13, 1349), and this on heat-
ing with ammonia gives (with mel-
amine) methyl mercaptan (Hofmann,
Ber. 18, 2758; Obermeyer, Ber. 20,
2919).

[C] Methyl sid^ihide [163] gives
methyl thiocyanate on heating with
cyanogen bromide (Cahours, Jahresber.
1875, 257). The latter is obtained by
the action of bromine on hydrogen
cyanide [172] or its salts (Serullas,
Berz. Jahresber. 8, 94; Ann. Chim.

161 C -164 A.]

METHYL MERCAPTAN

253

[2] 34, 100; 35,294; 315; Langlois,
Ann. Suppl. 1, 384; Ann. Chim. [3]
61, 482 ; Scholl, Beilstein's ' Hand-
bueh/ I, 1434).

[D.] From benzene [6; I, &c.] and
carbon disulpJiicle [I6O] through ani-
line and phenyl mustard oil by the
usual methods (Hofmann, Jahresber.
1858, 349; Ber. 2, 453; 15, 986;
Weith and Merz, Zeit. [3] 5, 589 ;
Rathke, Ber. 3, 861 ; Rudneff, Journ.
Russ. Soc. 10, 184; Werner, Trans.
Ch. Soc. 59, 400). The mustard oil is
reduced by aluminium amalgam to
diphenylthiourea and (through thio-
formaldehyde) methyl mercaptan (Gut-
bier, Ber. 34, 2033).

162. ITormal Bntyl Mercaptan ;
n-Butauethiol.

CH3.CH,.CH2.CH2.SH

Natural Source.

Occurs in the secretion of the Philip-
pine badger. My dans »xarc/^(?2(Beckmann,
Pharm. Centr. 1896 [n. f.], 17, SSl)-

Note : — The secretion contains also n-butyl
sulphide, probably a product of oxidation of
the mercaptan {Jbid. 558).

SYNTHETICAL PROCESS.

[A.] From n-lutyl alcohol [l7] and
potassium hydrosulphide as above under
methyl mercaptan [I6I; A](Saytzeff and
Grabowsky, Ann. 171, 251, • 175, 348).
Or by the interaction of the n-butyl
haloid and potassium hydrosulphide, or
by distillation of the alcohol with phos-
phorus pentasulphide (general method ;
see Kekule, Ann. 90, 311).

163. KEethyl Sulphide.

(CH3),S

Natural Source.

In American oil of peppermint
(SchimmeFs Ber. Oct. 1896; Kleber,
Pharm. Rev. 14, 269 ; Gerber, Mon.
Sci. [4] 11, 880).

Synthetical Processes.

[A.] Yvommethane [l] through methyl
chloride by chlorination (Berthelot, Ann.
Chim. [3] 52, 97), and interaction of
the latter with potassium sulphide (Re-
gnault, Ann. Chim. [2] 71, 391 ; Ann.
34, 26).

[B,] Yvom methyl alcohol llB] through
methyl chloride (Dumas and Peligot,
Ann. Chim. 61, 193 ; Groves, Journ.
Ch. Soc. 27, 641), and then as above.
Or by heating sodium methyl sulphate
with potassium sulphide (Klason, Ber.
20, 3407).

[C] From trimethylamine [Vol. II]
through methyl chloride by heating
the hydrochloride of the base to 326°
(Vincent, Journ. Pharm. [4] 30, 132 ;
jahresber. 1878, 1135).

164. Ethyl Sulphide.

(^'2^5)28

Natural Source.

Occurs in urine of dogs (Abel, Zeit.
physiol. Ch. 20, l^"^.

Synthetical Process.

[A.] From ethyl alcohol [l4] through
ethyl chloride or ethyl potassium sul-
phate, and the interaction of these with
potassium sulphide (Regnault, Ann.
Chim. [2] 71, 387 ; Loir, Comp. Rend.
26, 195; Riche, Ann. Chim. [3] 43,
297 : see also Dobereiner, Ann. 4, 172,
and Finckh^ Ber. 27, 1239).

Notes : — Vinyl sulphide, (CHj : CH)aS, the chief
constituent oftheoilof^ Ilium ursinum (Semmler,
Ann. 241, 92), does not appear to have been
synthesised, but could no doubt be prepared
from vinyl bromide and potassium sulphide by
the general method.

Allyl sulphide, {GK^ : CK , 0IL,\8, which is
generally stated to be a constituent of oil of
garlic, &c, (Wertheim, Ann. 51, 289 ; 65, 297 ;
Pless, Ann. 58, 36), according to Semmler
(Arch. Pharm. 230, 434) does not exist in
this oil, and is therefore most probably absent
from the other plant oils in which it is supposed
to have been found.

254

SULPHUR COMPOUNDS

[165-D.

165. Secondary Butyl Isothiocyanate
or Thiocarbimide ;
Oil of Spoonwort.

CH3.CH2.CH(CH3).NCS

Natural Source.

In oil of spoonwort or scurvy-grass,
Cochlearia officinalis (Hofmann, Ber. 2,
1 o3 j 1, 508 ; Gadamer, Arch. Pharm.
237, 92). According to Gadamar {loc.
cit.) it probably exists as glucoside in
the plant.

Synthetical Processes.

[A.] From n-butyl alcohol [17] and
carbon clisuljjhide [I6O]. The alcohol
is converted into n-butylene through
n-butyl iodide (Linnemann, Ann. 161,
196) and the action of alcoholic potash
on the latter (Lieben and Rossi, Ann.
158, 164 ; Saytzeff, Journ. pr. Ch. [2]
3, 88 ; Grabowsky and Saytzeff, Ann.
179, 330). n-Butylene combines with
hydrogen iodide to form 2-iodobutane
= secondary butyl iodide (Wurtz, Ann.
152, 23 ; Saytzeff, Ber. 3, 870). The
latter, by the action of ammonia, gives
the amine = 2-aminobutane (Hofmann,
Ber. 7, 513), and this on combination
with carbon disulphide in alcoholic or
ethereal solution, precipitation of the
product [di-(sec. )-butyldithiocarbamate]
with mercuric chloride, and decomposi-
tion of the mercury compound by boiling
with water yields the isothiocyanate
(Hofmann, Ber. 7, 512).

[B.] hobuty I alcohol [18] by the action
of hot zinc chloride gives a mixture of
two butylenes, of which one is pseudo-
butylene = symmetrical dimethylethyl-
ene (Nevole, Bull. Soc. [2] 24, 122 ; Le
Bel and Greene, Am. Ch. Journ. 2, 23 ;
Bull. Soc. [2] 29, 306 ; Faworsky and
Desbout, Journ. pr. Ch. [2] 42, 152 ;
J. Wislicenus and Schmidt, Ann. 313,
aio : see also Nef, Ann. 318, 38).
The latter combines with hydrogen
iodide to form secondary butyl iodide,
which can be converted into the amine
and treated with carbon disulphide [I60],
&c., as above under A.

Isobutyl alcohol also gives pseudo-

butylene' (with isobutylene) by the
action of sulphuric acid (Konowaloff,
Bull. Soc. [2] 34, '3^'>,'>, ; Puchot, Ann.
Chim. [5] 28, 508), or by pyrogenic
contact decomposition by plumbago
crucible material (Ipatieff, Ber. 35,
1061).

Isobutyl chloride gives all three
butylenes on pyrogenic decomposition
by passing over heated lime (Nef, Ann.
318, 22).

Note : — For conversion of psoudobutylene
into methylethyl ketone see under methylacetyl
carbinol [44 ; D]. The ketone is convertible
into secondary butyl alcohol and amine as
below under K.

[C] From methyl alcohol [13], glycerol
[48], and carbon disulphide [I60].
Methyl alcohol is converted into methyl
iodide, and glycerol into allyl iodide
(see under isobutyl alcohol [18; D]).
A mixture of the two iodides on
treatment with sodium gives (by iso-
meric transformation?) pseudobutylene
(Wurtz, Bull. Soc. [2] 8, 365 ; Ann.
144, l-^,^; Grosheintz, Bull. Soc. [2]
29, 201), which can be converted into
2-iodobutane, &e., as above.

[D.] From acetic aldehyde [92] and
carbon disulphide [I6O]. Aldehyde is
convertible by the action of sulphuretted
hydrogen into a solid trithioaldehyde,
CgHjySg (Weidenbusch, Ann. 66, 158 ;
Pinner, Ber. 4, 358 -, Klinger, Ber. 9,
1893; 11, 1024; Bbttinger, Ber. 11,
3205 ; Friedel and Crafts, Ann. 124,
114; Baumann and Fromm, Ber. 22,
3602; 24, 1464; Fromm, Ber. 32,
3650), and' this gives pseudobutylene
on heating with copper (Eltekoff, Ber.
10, 1904).

Or from aldehyde, ethyl alcohol [14],
and carbon disulphide. Zinc ethyl and
aldehyde combine to form a compound,
which is decomposed by water with the
formation of 3-butanol (Wagner, Ann.
181, 361). Subsequent steps as below
under G.

Or aldehyde combines with hydrogen
chloride to form ethylidene oxychloride
= I : i^-dichlorether (Lieben, Comp.
Rend. 46, 662 ; Ann. 106, o^-ifi ; Kessel,
Ann. 175,44; Geuther, Ann. 218, 16),
which by the action of zinc ethyl gives
secondary butyl ether. The latter on

165 D-M.] SECONDARY BUTYL ISOTHIOCYANATE

255

heating witli hydriodic acid at 130°
yields a-iodobutane (Kessel, loc. ciL).

[E.] From angelic or tiglic acid
[Vol. II] and carbon disulpliicle [I6O]
through brom-methylethylacetie acid =
3-brombutane-3-carboxylic acid by com-
bination of either of the isomeric acids
with hydrogen bromide (Pagenstecher,
Ann. 195, 109)' Pseudobutylene is
among the products of decomposition
of the bromo-acid by alkali (Ibid. 113).

Or the acids can be combined with
hydrogen iodide (Schmidt, Ann. 208,
254 ; J. Wislicenus, Talbot, and Henze,
Ann. 313, 207) ; the products give the
stereo-isomeric pseudobutylenes on treat-
ment with alkali (W. T. and H. loc. cit. :
see also Ch. Centr. 1897, 2, 261).

[F.] From et/iyl alcohol [14] and
carbon disulphide [I6O]. The alcohol
is converted into ether, and the latter
into I : 2-dichlorether (Malaguti, Ann.
32, 15; Ann. Chim. [2] 70, 338; [3]
16, 5 j 19; Lieben, Ann. Ill, 121 ;
123, 130; 133, 287; 141, 236; 146,
180; 150, 87). By the interaction of
dichlorether and zinc ethyl ethylchlor-
ether = 2-ethyl-i-chlorbutyl ether is
obtained, and this on heating with
hydriodic acid at 140° gives 2-iodo-
butane (Lieben, Ann. 150, 96). Subse-
quent steps as above under A.

Or from ethyl alcohol through ethylene
glycol [45]. The latter can be con-
verted into the iodhydrin = iodethyl
alcohol (Simpson, Proc. Roy. Soc. 10,
119; Butleroff and Ossokin, Ann. 144,
42 ; 145, 257), which by the action of
zinc ethyl gives 2-butanol (B. and O.
Ann. 145, 263). Subsequent steps as
below under G.

Note : — Generators of ethylene thus become,
with carbon disulphide, generators of secondary
butyl isothiocyanate.

[G.] From methyl and ethyl alcohols
[13 ; 14], formic acid [Vol. II], and
carbon disulphide [16 O]. A mixture of
methyl and ethyl iodides with formic
ethyl ester is treated with zinc, and
the product decomposed by water so as
to give 2-butanol = secondary butyl
alcohol (Saytzeff, Ann. 175, 374). The
alcohol can be converted into the corre-
sponding iodide (= 2-iodobutane) by the

usual methods, and the latter into the
amine and isothiocyanate as before.

[H.] From erythritol [50] and carbon
disulphide [I6O]. Erythritol on heat-
ing with hydriodic acid gives 2-iodo-
butane (De Luynes, Bull. Soc. [2] 2, 3 ;
Ann. 125, 252). Subsequent steps as
above under A.

[I.] Thiocyanic acid [l74] can be
converted into secondary butyl thio-
cyanate by interaction of the potassium
salt and secondary bxityl iodide (see
above under G). The alkyl thiocyanate
is probably convertible into the isothio-
cyanate by the action of heat (general
method : see Hofmann, Ber. 13, 13.50).

[J.] Isovaleric acid [Vol. II] gives
a small quantity of pseudobutylene
among the products of the dry distilla-
tion of the calcium salt (Dilthey, Ber.

34, 21 19). Subsequent steps as above
under B, &c.

[K.] From acetoacetic acid {ester)
[Vol. II] and methyl alcohol [l3]
through methylethyl ketone (see under
methylacetyl carbinol [44 ; Bj). The
ketone gives secondary butyl alcohol
on reduction (Norris and Green, Am.
Ch. Journ. 26, 293 : for electrolytic
reduction see Elbs and Brand, Zeit.
Elektroch. 8, 783). The alcohol with
carbon disulphide gives the mustard oil
as above under G.

Note : — The generators of methylethyl ke-
tone referred to under methylacetyl carbinol
[44, p. 95] thus become, with carbon disulphide,
generators of secondary butyl mustard oil : —
acetic and propionic acids ; acetic and butyric acids ;
sine methyl and propionyl chloride ; sine ethyl and
acetyl chloride ; ethyl iodide and acetic anhydride, &c.

[L.] From isoamyl alcohol [22] and
carbon disulphide [I6O]. The alcohol
gives pseudobutylene among the pro-
ducts of pyrogenic contact decomposi-
tion by passing the vapour through
a hot iron tube (Wurtz, Ann. 104, 249 ;
Butleroff, Ann. 145, 277 ; Ipatieff, Ber.

35, 1053). From pseudobutylene as
above under B.

[M.] From n-propyl alcohol [l5]
through n-hexane (see under n-hexyl
alcohol [23 ; A]) and carbon disulphide.
Hexane gives, among other products,
n- and pseudobutylenes when mixed
with air and passed over heated platinum
(v. Stepski, Monats. 23, 773).

156

SULPHUR COMPOUNDS

[165 N-ieV A.

[N.] From mannitol [5l] throug-h
hexane (see under n-hexyl alcoliol [23 ;
B]) and carbon dmdpldde, and then as
above.

Note : — All generators of n-hexane referred
to under n-hexyl alcohol [23] thus become,
with carbon disulphide, generators of this mus-
tard oil. n-Hexyl alcohol itself is a generator
of hexane through n-hexyl iodide and reduction
of the latter.

166. Allyl Isothiocyauate or
Thiocarbimide ; Mustard Oil.

CH^iCH.CH^.NCS

Natural Sources.

Occurs as glueoside, potassium myro-
nate or sinigrin, in black mustard from
the seeds of Sinapis nigra and S. juncea.
(For references see Gildemeister and
Hoffmann^s ' Die aetherischen Oele/
p. 533 ; Gadamer, Arch. Pharm. 235^
44 j Ber. 30, 2322.)

A glucoside (probably sinigrin) is
contained in horse-radish root, Cochlearia
armoracia (Hubatka, Ann. 47, 153;
Sani, SchimmeFs Ber. April 1 894 ;
Gadamer, Arch. Pharm. 235, 577).

The root of garlic-mustard {Sisym-
hrium aUiaria) gives an oil on distilla-
tion which apparently contains allyl
mustard oil (Wertheim, Ann. 52, 52 ;
Pless, Ann. 58, 38).

The plant and seeds of penny-cress,
Thlaspi arvense, give an oil which, ac-
cording to Pless [loc. cit. 36), contains
allyl mustard oil. The recent work of
Semmler (Arch. Pharm. 230, 434)
throws doubt on the existence of allyl
mustard oil in these two last plants.
According to Bitthausen (Journ. pr.
Ch. [2] 24, 273) sinigrin (potassium
myronate) occurs in the seeds of turnip,
Brassica rapa.

According to Bokorny (Ch. Zeit. 24,
771; 817; 832) Iberis amara, I. mn-
bellata, and /. sempervirens, scurvy-
grass [Cochlearia officinalis), winter cab-
bage [Brasnca oleracea\ and radish [Ra-
phanus sativus), contam some glucoside
which yields mustard oil (? allyl) under
the influence of myrosin. (For occur-
rence of mustard oil in seeds of Cruci-

ferse see also Jorgensen, Ch. Centr.
1898,2,927; 1899,2, 781).

Note : — Many mustard oils which were at
one time thought to contain allyl have by
later investigation been proved to be isothio-
cyanates of other radicles.

Synthetical Process.

[A.] From glycerol [48] through
allyl iodide (see under iso butyl alcohol
[I8 ; D]) and thiocyanic acid [174], by
the distillation of potassium or silver
thiocyanate with allyl iodide (Zinin,
Ann. 95, 128 ; Berthelot and De Luca,
Ann. Chim. [3] 44, 495 ; Comp. Bend.
41, 21). The normal ester produced
at first is transformed into the mustard
oil by the action of the heat (Oeser,
Ann. 134, 7 ; Billeter, Ber. 8, 464 ;
Gerlich, Ann. 178, 89).

Note : — Sinigrin when hydrolysed at 0° by
myrosin (the mustard seed enzyme) gives, with
allyl mustard oil, a trace of allyl thiocyanate
(E. Schmidt, Ber. 10, 187). The latter can be
synthesised from ammonium thiocyanate and
allyl bromide in alcoholic solution at 0° (Ger-
lich, loc. cit. 85), or from allyl iodide and potas-
sium hydrosulphide through allyl mercaptan,
the lead compound of the latter giving allyl
thiocyanate on treatment with cyanogen chlor-
ide in ethereal solution (Billeter, loc. cit).

167. Crotonyl Isothiocyanate

or Thiocarbimide;

Crotonyl Mustard Oil.

C4H, . NCS =
CH2 : CH . CH2 . CH,. N : C : S (?)

Natural Sources.

This mustard oil is apparently con-
tained in the oil-cake from rape seed
(Jorgensen, Ch. Centr. 1899, 2, 781 ;
Landw. Versuchs-Sta. 52, 269, &c.);
also in the seeds of Brassica glauca, B.
dichotoma, &c. {Ibid. Ch. Centr. 1898, 2,
928), and B. najms (SjoUema, Bee. Tr.
Ch. 20, 237).

Synthetical Processes.

[A.] From isohdyl alcohol [I8]
through isobutylene bromide (see under
isobutyl alcohol [18; A] and tertiary
butyl alcohol [19; B]), and carbon

167 A-169 A.] CROTONYL ISOTHIOCYANATE

257

(Usvlphide [160]. On heating- the isobu-
tylene bromide with alcoholic ammonia
at 1 00°, a product containing a croton-
ylamine is formed (Hofmann^ Ber.
7, 515; 12j 992). The latter is heated
with carbon disulphide in alcoholic
solution^ and the product (the crotonyl-
amine salt of crotonyldithioearbamic
acid) treated with an aqueous solution
of mercuric chloride^ silver nitrate^ or
ferric chloride, and then boiled {Ibid.
Ber. 7, 516; 8, io8j Ann. Chim.
Physiol. [7] 17, 263 : see also for
l^eneral method Rudneff, Ber. 12, 1023;
Hecht, Ber. 23, 282 ; Ponzio, Gazz.

26, 323)-

[B.] From crotonic aldehyde [102]
through crotonyl alcohol by reduction
(Lieben and Zeisel, Monats, 1, 825 ;
Charon, Ann. Chim. [7] 17, 223 ; Comp.
Rend. 128, 737). The alcohol com-
bines with hydrogen bromide to form
a-brom-/3-butylene = crotonyl bromide,
and this by interaction with potassium
or ammonmm tJiiocyanate [l74] gives
crotonyl isothiocyanate {Ibid.).

Note : — The generators of isobutylene re-
ferred to under isobutyl alcohol [18 ; B ; C, &c.]
thus become, with carbon disulphide, generators
of ci'otonyl mustard oil. These are isovaleric
acid [Vol. II] ; glycerol and acetone [48 ; 106] ;
acetic acid and acetone ; amyl alcohol of fusel oil
[22]. Tertiai-y butyl alcohol [19] is also a generator
of isobutylene (see under isobutyl alcohol
[18 ; A]).

The identity of the synthetical mustard oil
with the natural product requires confirmation.
According to SjoUema (loc. cit.) the crotonyl
mustard oil from Brassica napus is not identical
with either Hofmann's or Charon's compounds.

168. Angelyl Isothiocyanate

or Thiocarbimide ;

Angelyl Mustard Oil.

C5H9

NCS

Natural Source.

Said to have been obtained from rape
seed oil-cake (Jorgensen as above under
167).

Synthetical Processes.

[A.] From amyl alcohol of fusel oil
[22] through ^isoamylene^ (see under

acetone [IO6 ; E]) and carbon disul-
phide [I60]. The amylene is converted
into angelylamine by heating the brom-
ide with alcoholic ammonia, and the
amine into the mustard oil by the
general method as described above
under 167 ; A (Hofmann, Ber. 8, 106 ;
12, 991).

Note : — The identity of the natural with the
synthetical product has not been established.

169. Benzyl Isothiocyanate

or Thiocarbimide;

Benzyl Mustard Oil.

CgHg . CH2 . NCS

Natural Sources.

Occurs in the ethereal oil of the
Capuchin cress, Tropceolum majuSy and
of the garden cress, Lepidnim sativum ;
also as the glucoside, glucotropaeolin,
in seeds of the same plants (Gadamer,
Arch. Pharm. 237, 11 1; 507; Ber.
32, 2335 ; Beyerinck, Centr, Bakter.
II, 6, 72).

Synthetical Processes.

[A.] From benzoic acid [Vol. II] and
carbon disulphide [I6O]. Ammonium
benzoate is converted into benzonitrile
(Fehling, Ann. 49, 91 ; Laurent and
Gerhardt, Jahresber. 1849, 327 ; Wohler,
Ann. 192, 362 ; Anschiitz and Schultz,
Ann. 196, 48 ; Buckton and Hofmann,
Ann. 100, 155 ; Gerhardt, ' Traite, &c.,'
IV, 762; Henke, Ann. 106,276; Henry,
Ber. 2, 307 : see also under benzoic
aldehyde [ll4; C]), and the latter
reduced to benzylamine (Mendius, Ann.
121, 144; S pica, Gazz. 10, 515; Bam-
berger and Lodter, Ber. 20, 1709).
Or benzonitrile and ethyl alcohol [14]
and hydrogen chloride condense to the
hydrochloride of benzimidoethyl ether
(Pinner, Ber. 16, 353 : general synthe-
sis), and this by interaction with ammo-
nia gives an amidine which, on reduction
by sodium amalgam in acid solution,
yields benzylamine (Henle, Ber. 35,

3044).

Benzylamine and carbon disulphide

258

SULPHUR COMPOUNDS

[169 A-D.

give the mustard oil by the general
method (Hofmann, Ber. 1, lioi).

Benzamide,f rom ammonium benzoate
or from benzoyl chloride and ammonia,
gives benzylamine among the products
of its electrolytic reduction in sulphuric
acid (Baillie and Tafel, Ber. 32, 71).

Ethyl benzoate yields benzonitrile by
interaction with sodamide (Titherley,
Trans. Ch. Soc. 81, 1527).

Benzoic acid also gives benzonitrile
through benzoyl chloride, and the inter-
action of the latter with benzamide
(Sokolofe, Gerhardt's 'Traite, &c.,' I,
^S^), or with potassium tliiocyanate [l74]
or cyanate (Limpricht, Ann. 99, 1 17;
Schiff, Ann. 101, 93). Also by the
interaction of cyanogen bromide and
potassium benzoate (Cahours, Ann. 108,
319; Ann. Chim. [3] 52, 200), of ben-
zoic acid and potassium thiocyanate
(Letts, Ber. 5, 673) or lead thiocyanate
(Kriiss, Ber. 17, 1767).

Also from benzoic and acetic acids
via acetophenone and mandelic acid (see
under benzoic aldehyde [ll4 ; G]), and
then through phenylbrom- and phenyl-
amino-acetic acid and benzylamine, &c.,
as below under B.

Benzoyl chloride and metJiylamine [Vol .
II] give methylbenzamide (Van Hom-
burgh, Rec. Tr. Ch. 4, 388), which, by
the action of phosphorus pentachloride,
yields an imidochloride (v. Pechmann,
Ber. 28, 2367). Benzenylmethylimido-
chloride on heating decomposes into
methyl chloride and benzonitrile {Ibid.
33, 611). The latter can be reduced to
benzylamine as above.

[B.] From benzoic aldehyde [114] and
carbon disuljjhide [160]. Benzaldoxime
by the action of acetic anhydride gives
benzonitrile (Lach, Ber. 17, 1571). Also
by the action of monopersulphuric acid
(Carols reagent: Bamberger andScheutz,
Ber. 34, 2023). Subsequent steps as
above.

Or benzaldoxime gives benzylamine
directly on reduction with sodium
amalgam and acetic acid (Goldschmidt,
Ber. 19, 3232).

Or the oxime (' syn- ' or ' anti- ') by the
action of chlorine in chloroform solution
gives benzhydroximic chloride (Werner
and Buss, Ber. 27, 2197), which, by

interaction with hydroxylamine, yields
benzenyloxyamidoxime, CgHj . C(:N .
OH) . NH . OH, and this gives benzo-
nitrile when treated with acetic anhy-
dride (Ley, Ber. 31, 2127).

Or benzaldehyde cyanhydrin (from
the aldehyde and hydrogen cyanide [l72])
with alcoholic ammonia gives the nitrite
of phenylaminoacetic acid, from which
the acid can be obtained by hydrolysis
(Tiemann, Ber. 13, 383). The acid
yields benzylamine on dry distillation
(Tiemann and Friedlander, Ber. 14,
1969). Or the cyanhydrin hydrolyses
to mandelic acid (Winckler, Ann. 18,
310; Miiller, Ber. 4, 980; Wallach,
Ann. 193, 38), and this combines with
hydrogen bromide to form phenylbrom-
acetic acid (Glaser and Radziszewski,
Zeit. [2] 4, 142). The latter gives
phenylaminoacetic acid on heating with
aqueous ammonia (Stockenius, Ber. 11,
2002).

Benzoic aldehyde with aqueous ammo-
nia yields ' hydrobenzamide ' (Laurent,
Ann. 21,130; Rochleder, Ann. 41, 89),
and the latter gives benzylamine (with
toluene) by reduction in alcoholic solu-
tion with sodium (O. Fischer, Ber. 19,

748).

Benzoic aldehyde phenylhydrazone
reduces to benzylamine (and aniline)
with sodium amalgam and acetic acid
(Tafel, Ber. 19, 1928), or by electroly-
sis (Tafel and Pfeffermann, Ber. 35,
1510).

Benzoic aldehyde and glycin [Vol. II]
give benzylamine when heated to 130
(Curtius and Lederer, Ber. 19, 2463;
Erlenmeyer, junr., Ber. 30, 1528).

Benzylamine is among the products
formed by heating benzoic aldehyde with
ammonium formate [Vol. II] (Leuckart
and Bach, Ber. 19, 2128).

[C] Hippuric acid [Vol. II] gives
benzonitrile on heating per se or with
zinc chloride (Limpricht and Uslar, Ann.
88, 133; Gossmann, Ann. 100, 74).
Subsequent steps through benzylamine
and with carbon disulphide as before.

[D.] 'Prom phenylacetic acid [Vol. II]
through the bromo-acid (Radziszewski,
Ber. 2, 208), the phenylamino-acid as
above under B, and benzylamine with
carbon disulphide as before.

169 E-J.]

BENZYL ISOTHIOCYANATE

259

[E.] Styrene [7j gives phenylclilor-
aeetic acid and mandelic acid (see under
benzoic aldehyde [ll4; B]). Sub-
sequent steps through benzylamine
with carbon disulphide as above under B.

[P.] From phenol [60] and carbon
disulphide [160]. Phenol 2indi potassiicm
cyanide [172] give benzonitrile (see under
benzoic aldehyde [114 ; H]).

[Gr.] From cymene [6] and carbon di-
sulphide. Cymene gives aeetophenone
[114 ; K]. Then as above under A.

[H.] From benzene [8; I, &c.] or
toluene [54] and carbon disulphide [160].
All generators with these hydrocarbons
of aeetophenone or benzonitrile referred
to under benzoic aldehyde [114 ; A]
become generators of benzylamine and,
with carbon disulphide, of benzyl
mustard oil.

Aniline (from nitrobenzene) on dia-
zotisation with nitrous acid and inter-
action of the diazo-com pound with
nitromethane (see under hydrogen cyan-
ide [172 ; J, &c.]) gives, among other
products, phenylnitromethane = i^-
nitrotoluene (Bamberger, Schmidt, and
Levinstein, Ber. 33, 2053). The latter
reduces to benzylamine (Konowaloff,
Ber, 28, 1861). Toluene also on
nitration with nitric acid of i-i3 sp,
gr. at 100** yields phenylnitromethane
{Ibid. loc. cif.; Journ. Russ, Soc. 31,
254)-

Note : — For other methods of formation of
phenylnitromethane see Gabriel, Ber. 18, 1254 ;
Cohn, Ber. 24, 3867.

Benzylamine is obtained from benzyl
chloride and alcoholic ammonia (Canniz-
zaro, Ann. 134, 128 ; Suppl. 4, 24 ;
Mason, Trans. Ch. Soc. 63, 1313;
Limpricht, Ann. 144, 305 : see also
Seelig,Ber. 23, 2971 ; Dhommee, Comp.
Rend. 133,636); also from benzyl chlor-
ide andpotassium cyanide [l72] through
benzyl cyanide and hydrolysis of the
latter to phenylacetamide (Purgotti,
Gazz. 20, 173; 593)^ which gives
benzylamine by action of bromine in
presence of potassium hydroxide (Hof-
mann, Ber. 18, 2738 ; Hoogewerff and
Van Dorp, Rec. Trav. Ch. 5, 253).

Or benzyl chloride or iodide interacts
with silver nitrite to form phenylnitro-

methane (Holleman, Rec. Tr. Ch. 13,
405 ; Hantzsch and Schultze, Ber. 29,
700 ; Van Raalte, Rec. Tr. Ch. 18, 383),
which can be reduced to benzylamine as
above.

Or benzyl chloride or bromide and
silver cyanate give benzyl isocyanate
(Letts, Journ. Ch. Soc. 25, 446 ; Ber.
5, 91 ; Strakosch, Ber. 5, 692 ; Laden-
burg and Strnwe, Ibid. 10, 46). Silver
cyanate is obtained from potassium
cyanate by double decomposition
(Mendius, Jahresber. 1860, 17); the
potassium salt is obtained by the oxida-
tion oi potassium cyanide or ferrocyanide
[172] (Wohler, Berz. Jahresber. 3, 78;
4, 92; Pogg. Ann. 1, 117; Liebig,
Ann. 38, 108; 41, 289; Kolbe, Ann.
64, 237; Clemm, Ann. 66, 382; Wurtz,
Ann. Chim. [3] 42, 44 ; Lea, Jahresber.
1861, 789; Bell, Ch. News, 32, 100;
Gattermann, Ber. 23, 1224; Volhard,
Ann. 259, 378 ; H. Erdmann, Ber. 26,
2438 ; Reychler, Bull. Soc. [3] 9,
427).

Benzyl isocyanate gives benzylamine
on decomposition by caustic alkali
(Cannizzaro, Ann. 134, 128 ; Strakosch,
Ber. 6j 692 : see also Letts, Ibid. 91).

Benzylamine can be obtained also
from benzyl chloride and acetic acid
through benzylacetamide (Rudolph, Ber.
12, 1297), and decomposition of the
latter with alcoholic potash (Ibid.).

Or from benzyl chloride and jf'ormic
aldehyde [9l] through the aldehyde or
through ' trioxymethylene ' and the
base, hexamethylenamine, formed by the
action of ammonia on the aldehyde or
on trioxymethylene (Butleroff, Ann.
115, 322 ; Wohl, Ber. 19, 1843 ; Grassi-
Cristaldi and Motta, Gazz. 29, 43). The
compound of hexamethylenamine and
benzyl chloride gives benzylamine on de-
composition with alcoholic hydrochloric
acid (Delepine, Comp. Rend. 124, 292 ;
Bull. Soc. [3] 17, 294).

[I.] Naphthalene [l2] is a generator
of benzonitrile through phthalic acid
and phthalimide (see under benzoic
aldehyde [114 ; J]).

[J.] From ctimic aldehyde [II6]
through isopropylbenzene and aeeto-
phenone, &c. [114; K].

s 2

260

SULPHUR COMPOUNDS

[170-D.

170. Fhenylethyl Isothiocyanate,
Thiocarbimide, or Mustard Oil.

CeHg.CH^.CH^.NCS

Natural Sources.

Occurs in the ethereal oil of the
water- cress^ Nasturtium officinale, and
the winter-cress, Barharea prcBcox. The
glucoside (g-luconasturtiin) exists as
potassium salt in the seeds of these
plants (Gadamer, Ber. 32, 2339 ; Arch.
Pharm. 237, 507). According- to Ber-
tram and Walbaum (Journ. pr. Ch. [3]
50, ^Sl)^ ^l^is mustard oil is contained
in the ethereal oil from the roots of
Reseda.

Synthetical Processes.

[A.] From toluene [54; A, &c.] and
jiotassium cyanide [l72j through benzyl
cyanide (see under benzyl mustard oil
[169 ', H]) and carbon disulphide [I6O].
Benzyl cyanide on reduction gives w-
phenylethylamine (Spica and Colombo,
Gazz. 5, 134; Bernthsen, Ann. 184,304;
Spica, Jahresber. 1879, 440 ; Laden-
burg, Ber. 19, 783). The amine gives
the mustard oil by the general method
(Neuberfc, Ber. 19, 1825).

The nitrile of symmetrical triphenyl-
glutaric acid, obtained by the condensa-
tion of benzyl cyanide with benzoic
aldehyde [ll4] by means of sodium
ethylate (Meyer, Ann. 250, 156), gives
to-phenylethylamine on reduction with
sodium in alcoholic solution (Henze,
Ber. 31, 3065).

Or benzyl chloride can be combined
with the sodium compound of chlor-
malonic ester [Vol. II] (Conrad and
Bischoff, Ann. 209, 219) so as to give
^feenzyl chlormalonate (Conrad, loc. cit.
"' 343). The latter, on treatment with
potassium or barium hydroxide, gives
benzyl tar tronic acid {Ibid. 345), and
this yields phenyl- u-lactic acid on heat-
ing at 1 60-1 80° [Ibid. 347). Subsequent
steps as balow under D.

A\so ivova. benzene [6; I,&c.] through
ethylbenzene (see under phlorol [64 ;
a]). The compound of the latter with
chromium oxychloride is decomposed

by water with the formation of a-toluic
aldehyde (Etard, Ann. Chim. [5] 22,
348), the oxime of which (Dollfus,
Ber. 25, 191 7) gives phenylethylamine
on reduction (Bischler and Napieralski,
Ber. 26, 1905). Ethylbenzene also
yields a-toluic aldehyde among the pro-
ducts of its oxidation by potassium
persulphate (Moritz and Wolffenstein,
Ber. 32, 434).

Or from ethylbenzene through styr-
ene bromide (see under styrene [7 ; A]),
and then as below under B.

[B.] Styrene [7] gives ethylbenzene
(see under phlorol [64; B]), which, with
carbon disulphide [160], yields the mus-
tard oil as above under A.

Or styrene can be combined with
bromine, and the bromide converted
into the glycol (see under benzoic alde-
hyde [114; B]). The latter on heating
with 20 per cent, sulphuric acid gives
a-toluic aldehyde (Zincke, Ber. 11, 1402;
Ann. 216, 301 ; also Tiffeneau, Comp.
Rend. 134, 1505), which can be con-
verted into phenylethylamine as above
under A.

Or styrene, by the action of iodine in
presence of mercuric oxide, gives an
iodo-derivative, which yields a-toluic
aldehyde on treatment with silver nitrate
(Bougault, Comp. Rend. 131, 529).

[C] From tartaric or racemic acid
[Vol. II], and n-propyl alcohol [15],
and carbon disulphide [I6O], through
pyroracemic acid and propionic alde-
hyde, ethylisophthalic acid, ethylben-
zene, &c. (see under phlorol [64; J]).

Note : — Generators of pyroracemic acid are
given under benzyl alcohol [54 ; F ; I ; M, &c.].

[D.] From benzoic aldehyde [ll4],
alcohol [14], acetic acid [Vol. II], and
carbon disulphide [I6O]. Chloracetic
ester and benzoic aldehyde on treatment
with sodium in alcoholic solution give
the ester of /3-phenyloxyacrylic =
phenylglycidic acid (Erlenmeyer, Ann.
271, 153). The latter yields a-toluic
aldehyde on distillation with dilute
sulphuric acid (Baeyer, Ber. 13, 304 :
see also Glaser, Ann. 147, 100). Phenyl-
glycidic acid decomposes at ordinary
temperatures into a-toluic aldehyde and
carbon dioxide (Erlenmeyer, Ber. 13,
308).

170 D-171.]

PHENYLETHYL ISOTHIOCYANATE

261

Or phenylglycidic acid (ester) by the
action of sodium amalgam gives phenyl-
a-lactic acid (Plochl, Ber. 16, 2823), and
the latter yields a-toluic aldehyde on
heating per se at 130° or with dilute
sulphuric acid at 200° (Erlenmeyer,
Ber. 13, 304). Subsequent steps as
above under A.

Or from benzoic aldehyde and hydro-
gen cyanide [172] through the nitrile of
raandelic acid (see under benzyl mustard
oil [169; B]). This nitrile, according
to Fileti (Schiff, Ber. 12, 297 j 1700),
can be reduced to phenylethylamine.

[E.] From cinnamic acid [Vol. II]
and carbon disulphide [16 O]. Cinnamic
acid can be converted into phenyl-a-
chlorlactic acid by combination with
hypochlorous acid (Glaser, Ann. 147,
79 ; Erlenmeyer and Lipp, Ann. 219,
185). Phenyl-a-chlorlactic acid on
treatment with cold alcoholic potash
gives /3-phenyloxyacrylic acid (Glaser,
loc. cit. 98), which can be treated as
above under D. Or the phenyl-a-
chlorlactic acid yields a-toluic aldehyde
directly on distillation with sodium
carbonate solution (Forrer, Ber. 17,

Or cinnamic acid can be combined
with bromine, and the phenyldibrom-
propionic acid converted by boiling
with water into phenyl-a-bromlactic
acid (Glaser, loc. cit. 84 ; Erlenmeyer,
Ber. 13, 310). The latter gives fi-
phenylox^'acrylic acid on treatment with
alkali (Glaser, loc. cit. 98).

Or cinnamic acid on combination
with a hypobromite and treatment of the
product with alkali gives a-oxyphenyl-
propionic lactone, which, on heating in
a partial vacuum or with water, yields
a-toluic aldehyde (H. Erdmann, Eng.
Pat. 8248, April, 1899; Journ. Soc.
Ch. Ind. 19, 273).

Sodium cinnamate on treatment with
iodine chlorhydride gives phenyliodhydr-
acrylic = a-iodo-/3-pheny 1-/3 -hydroxy-
propionic acid, and this on heating with
water yields a-toluic aldehyde (Erlen-
meyer and Rosenhek, Ber. 19, 2464 ;
Erlenmeyer, Ann. 289, 276).

Or from cinnamic acid through
phenylgly eerie acid (see under benzoic
aldehyde [ll4 ; E]). The latter gives

phenyl-(8-chlorlactic acid or the corre-
sponding bromo-acid by treatment with
hydrochloric or hydrobromic acid(Lesch-
horn, Ann. 271, i.^'^ ; Lipp, Ber. 16,
1290). The phenyl-^-chlor- (or bromo-)
acid yields a-toluic aldehyde on distilla-
tion with dilute alkali (Erlenmeyer and
Lipp, Ann. 219, 182). Phenylglycerie
acid gives a-toluic aldehyde directly on
heating to 160° (Lipp, Ber. 16, 1288).

[P.] From benzoic and acetic acids
[Vol. II] through acetophenone (see
under benzoic aldehyde [114; A and
G]), dypnone, and ethylbenzene (see
under phlorol [64 ; K]), and then as
above under A.

[G.] Cymene [6] can be conveited
into acetophenone through cumic acid
and isopropylbenzene = cumene (see
under benzoic aldehyde [114; K]).

[H.J Yxoro. phenylacetic {a-toltnc) and
formic acids [Vol. II] by distilling
a mixture of the calcium salts (Canniz-
zaro, Ann. 119, 254), and treating the
a-toluic aldehyde thus formed as above
under A.

[I.] ^-Phenylpropionic acid [Vol. II]
is converted into its amide (Hofmann,
Ber. 18, 2740), and the latter into
CO- phenylethylamine by the action of
bromine in presence of potassium hydr-
oxide {Ibid. ; also Hoogewerf and Van
Dorp, Rec. Tr. Ch. 5, 254).

[J.] Phniylulanine [Vol. II] gives
<u-phenylethylamine on rapid heating
(Erlenmeyer and Lipp, Ann. 219, 202 :
see also Schulze and Barbieri, Journ.
pr. Ch. [2] 27, 346; Ber. 14, 1788;
16, 1713).

171. Parahydroxybenzyl Isothio-

cyanate, Thiocarbimide, or

Mustard Oil.

CH, . NCS

HO

Natuual Source.

Occurs in the oil of white mustard
from the seeds of Sinapis alba. The
glucoside contained in the seeds is sin-

263

SULPHUR COMPOUNDS

[171-172.

albin (Robiquet and Boufcron-Charlard,
Journ. Phai-m. [2] 17, 379; Will and
Laubenheimer, Ann. 199, 150 j Gada-
mer. Arch. Pharm. 235, 83 ; Ber. 30,

2327-2334).

Synthetical Processes.

[a.] From toluene [54] and carbon
dlsnlphide [I6O]. Paranitrobenzyl
chloride (see under p-hydroxybenzoic
aldehyde [119 ; E]) is converted into
a phthalimide derivative (see under
benzoic aldehyde [114 ; j]) by inter-
action with potassium phthalimide (Ga-
briel, Ber. 20, 3224), and this deriva-
tive converted into p-nitrobenzylamine
by heating with hydrochloric acid at

190-200°. The nitro-amine gives p-
aminobenzylamine on reduction, and
the latter p-hydroxybenzylamine by
the diazo-method. The mustard oil is
obtained from the base by the usual
method (Salkowski, Ber. 22, 2143).

p-Nitrobenzylamine can also be ob-
tained from henzylamine (see under
benzyl mustard oil [l69 ; A to end])
by acetylation, nitration of the benzyl-
acetamide, and reduction of the p-nitro-
derivative (Amsel and Hofmann, Ber.
19, 1284). The generators of henzyl-
amine, viz. benzoic acid and acetic alde-
liyde, liimmric and i:)]ienylacetic acids,
and styrene, thus become, with carbon
disulphide, generators of p-hydroxy-
benzyl mustard oil.

CYAlSrOGE]^ COMPOUNDS.

172. Hydrogen Cyanide ;

Hydrocyanic or Cyanhydric Acid ;

Frusstic Acid ; Formonitrile.

H.CN

Natural Sources.

Occurs to a considerable extent in
the free state or in very loose combina-
tion in all parts of Pangium edide, Java
(Greshoff, Ber. 23, 3549). Also in
Hydnocarpus inebrians = H. wightiana 1
and //. alj/mus {Ibid. 3550). The sweet
and bitter cassava contain hydrogen
cyanide, especially the skin (Francis,
' Analyst,'' 2, 4 ; Carmody, ' Bulletin of
Miscellaneous Information,^ Trinidad;
*^ Nature,' 63, 500 : for occurrence of
hydrogen cyanide in Pangium edule and
in bitter almonds see also Marco Soave,
Journ. Ch. Soc. 80, II, Abst. 332).

The hydrogen cyanide complex is
contained in the glucoside amygdalin
(for occurrence see under benzoic alde-
hyde [114]). The complex exists in
plants belonging to the Amygdalacese,
Asclepiads, Bixacese, Tiliacese, Sapo-
tacese, Sapindacese, Papilionacese, Con-
volvulaceae, Euphorbiacese, Linaceee,
and Aroideae (Greshoff). Traces of

free hydrogen cyanide have been found
among Saxifrages, in young shoots of
certain species of Bibes, viz. R. rvbrum,
P. nigrnm, and P. anreum. The seed
embryo of Eriobotyra japonica contains
•04 per cent, of hydrogen cyanide.

The complex exists in a compound
occurring in many wild Rosacese and in
an amygdalin-like compound found in
the young green parts of the Ranuncu-
laceous Aquilegia vulgaris. No hydro-
gen cyanide could be found in the
Aroidese, Arum maculatutn, A. italicmn,
Arisarnm vulgare, Amorphophallus rivieriy
or Piejfenbachia seguine (Hebert, Bull.
Soc. [3] 17, 664; 19, 310). R. Fischer,
contrary to the statement of GreshofP,
was unable to find hydrogen cyanide
in Mitchella repens (Pharm. Rev. 16,

9«)-

Amygdalin, or some glucoside yield-
ing hydrogen cyanide on hydrolysis, is
present in the leaves of Indigofera gale-
go'ides (Van Romburgh, SchimmeFs Ber.
Oct. 1894; April, 1896).

The distribution of hydrogen cyanide
in various parts of Prunus kmrocerasus
has been investigated by Van der
Ven (Ch. Centr. 1898, 2, 678).
The ojiening buds of Prunus lauro-

172-A.]

HYDROGEN CYANIDE

263

cerasMS and P. padus contain a g-lucoside
which yields hydrogen cyanide (Ver-
schaffelt, Proc. K. Akad. Wetensch.
Amsterdam^ 5, 3 1 ; Journ. Ch. Soc. 82,
II, Abst. 523).

The herb Spiraa amncus, the herb
and flowers of S. sorbifolia, and the
leaves of S. japonica give hydrogen
cyanide on distillation with water
(Wicke, Ann. 83, 175). Amygdalin,
or some similar compound yielding
hydrogen cyanide on hydrolysis, is pre-
sent in the seeds of many species of
Vicia, and absent in others (Bruyning
and Van Haarst, Rec. Tr. Ch. 18,
468).

Compounds containing the hydrogen
cyanide complex are present in the
flowers of peach, blackthorn, and moun-
tain ash, in the stem-bark and root of
the latter, in the stem-bark of Portugal
laurel, and in the root of Manihot
(Euphorbiacese) .

The glucoside lotusin contained in
Lotus arabicus from Egypt and N.
Africa gives hydrogen cyanide on
hydrolysis or zymolysis (Dunstan and
Henry, Proc. Roy. Soc. 67, 324; 68,
374 j Phil. Trans. B, 194, 515).
Cyanogenetic glucosides are contained
also in the young plants of Sorghum
vulgare, in Maniliot utillssima, Linwrn,
tisitatissimum, Lotus nustralis, and
Fhaseolns limatus, the Lima bean
(Dunstan and Henry, Proc. Roy. Soc.
70, 1^^; Phil. Trans. 1902, A, 399;
'Nature,' 68, 287; Briinnich, Trans.
Ch. Soc. 83, 788).

In the animal kingdom hydrogen
cyanide is said to have been obtained
from Chilognatha (Myriopods).

Synthetical Phocesses.

[A.] From carbon, hydrogen, and
nitrogen through acetylene [methane,
Ij a], which combines with nitrogen
under the influence of the electric spark
(Berthelot, Comp. Rend. 67, 1141 j
Ann. 150, 60 ; Dewar, Proc. Roy. Soc.
29, 188 j 30, 85). Hydrogen cyanide
is also formed from acetylene and nitro-
gen or ammonia in the electric furnace
(Hoyermann, Ch. Zeit. 26, 70). Acetyl-
ene and nitric oxide when mixed and

exploded by the electric spark give
hydrogen cyanide (Huntingdon, Germ.
Pat. 93852 of 1896; Ch. Centr. 1897,
2, 1166). Acetylene gives among the
products of its oxidation by fuming
nitric acid a crystalline compound
(CgH^OgN^), which yields hydrogen
C3'anide on heating above 120° (Bas-
chieri, Atti Real. Accad. Line. [5] 9,
391). Acetylene when exploded with
oxygen in the presence of nitrogen
gives hydrogen cyanide (Mixter, Sill.
Journ. [4] 9, 5 ; 10, 299).

Hydrogen cyanide is formed by heat-
ing wood charcoal with nitric acid
(Burls, Evans, and Desch, Ch. News,

68,75).

Ammonia (two molecules) and nitrous

oxide (one molecule), when mixed and
passed over heated carbon, give hydro-
gen cyanide (Roeder and Griinwald,
Germ. Pat. 132909 of 1901 ; Ch. Centr.
1902, 2, 235).

Cyanides or cyanamides are formed
by passing nitrogen, ammonia, or nitric
oxide and steam over the carbides of
the metals of the alkalis or alkaline
earths heated to a high temperature.
Calcium cyanamide is formed directly
from nitrogen by heating lime and
carbon in the electric furnace with
access of atmospheric air (Caro and
Frank, Germ. Pat. 88363 of 1895; Ber.
29, Ref. 816 j Ibid. No. 92587 of 1895;
Ch. Centr. 1 897, 2, 654; No. 95660
of 1896; Ch. Centr. 1898, 1, 813; No.
10897 1 of 1898; Ch. Centr. 1900,1,
JI20; Nos. 116087 and 1 16088 of
1898; Ch. Centr. 1900, 2, 1222; also
the patents of Erlwein and Frank and
of Bradley and Jacobs referred to
below).

Potassium cyanide is formed by the
combination of strongly heated carbon
and nitrogen in presence of potassium
carbonate or hydroxide (Desfosses, Ann.
Chim. 38, 158; Journ. Pharm. 12;
Fownes, 'Athenaeum,' 1^41^ P- 625;
Journ. pr. Ch. 26, 412; Lewis Thomp-
son, Berz. Jahresber. 21, 80; Bunsen
and Playfair, Rep. Brit. Assoc. 1845,
185 ; Journ. pr. Ch. 42, 397 ; Delbriick,
Ann. 64, 296 ; Journ. pr. Ch. 41, 161 ;
Wohler, Jahresber. 1850, 550 ; Rieken,
Ann. 79, 77; Marguerite and Sour-

264.

CYANOGEN COMPOUNDS

[172 A.

deval, Comp. Rend. 50, iioo; Hempel,
Ber. 23, 3390 ; De Lambilly, Journ.
Soc. Ch. Ind. 11, 604 ; ico6 ; Young-,
Eng. Pat. 24856 of 1893 : for technical
production of cyanides from atmosplierie
nitrogen or ammonia and carbon in
presence of fused alkali see also Pfleger's
Germ. Pats. 881 15 of 1894 and
89594 of 1895; Ber. 29, Ref. 748 and
1197 ; Stassfurter Ch. Fab., Eng. Pats.
9350, 9351, and 9352 of 1900 ; Journ.
Soc. Ch. Ind. 20, 77 : for production
of cyanides from atmospheric nitrogen
and fused alkali in presence of carbon
and iron see Victor Alder^s Germ. Pats.
12351 of 1880; Ber. 14, 1126; 18945
of 1881 ; Ber. 15, 1776; also Tauber,
Ber. 32, 3152 : for production of
barium cyanide from barium carbide
and atmospheric nitrogen in the electric
furnace see Bradleyand Jacobs, Eng. Pat.
7558of 1 900; for manufacture of calcium
cyanide and cyanamide by means of
the electric furnace from calcium carbide
and nitrogen see Erlwein and Frank,
Amer. Pat. 708333 of 1902 ; Journ. Soc.
Ch. Ind. 21, 1232; Erlwein, Zeit.
angew. Ch. 16, 533 : for production of
hydrogen cyanide from metallic cyan-
ides see Feld's Eng. Pat. 24904 of
1901 ; Journ. Soc. Ch. Ind. 21, 1553).

Potassium cyanide is formed by pass-
ing carbon monoxide and nitrogen over
a fused mixture of potassium carbonate
and carbon (Possoz and Boissiere, Wag-
ner's Jahresber. 1855, 83, from the
^London Journ. of Arts,' 1845, 380),
or by passing carbon monoxide and
ammonia through a fused mixture of
potassium hydroxide and carbon (Young
and Macfarlane, Eng. Pat. 3092 of
1892).

Sodamide gives sodium cyanide when
heated in an atmosphere of carbon
monoxide (Beilstein and Geuther, Ann.
108, 91 ; Conroy, Journ. Soc. Ch. Ind.
15,9).

Fused sodium in contact with carbon
gives sodium cyanide when heated in
an atmosphere of ammonia, sodamide
and cyanamide being formed as inter-
mediate products (Castner, Eng. Pats.
12218 and 1 22 1 9 of 1894: see also
D eutsch . Gold- u. S ilber- S cheide- Anstalt ,
&c., Germ. Pat. 126241 of 1900; Ch,

Centr. 1901, 2, 11 84; Eng. Pats.
21820 of 1900 and 3329 of 1901; Journ.
Soc. Ch. Ind. 20, 11 13 and 21, 345;
also Darling, Journ. Franklin Inst. Jan.
1902). Barium cyanide is formed by
passing carbon monoxide over heated
barium nitride (Maquenne, Comp. Rend.
114, 221).

Ammonium cyanide is formed when
ammonia is passed over heated carbon
(Kuhlmann, Ann. 38, 62 ; Journ. pr.
Ch. 16, 482; Lance, Comp. Rend. 124,
819; Lance and De Bourgade, Germ.
Pat. IC0775 of 1897; Ch. Centr. 1899,

1, 766; Eng, Pat. 26326 of 1897 : for
production of ammonium cyanide by
passing ammoniacal gases over heated
' contact ' surfaces see Besenfelder's
Germ. Pat. 120264 of 1900; Ch. Centr.
1901, 1, 1125; 122144 of 1900;
Mid. 2, 379 : for earlier work on
the production of cyanides from ammo-
nia and carbon see also Clouet, Ann.
Chim. 11, 30 ; Bonjour, Scherer's Journ.

2, 621 ; Schroder, Ibid. 626 ; 628 ;
Langlois, Journ. pr. Ch. 23, 232 ; Berz.
Jahresber. 22, 84 ; Ann. 38, 64 : for
historical summary to 1 842 see Erdmann
and Marchand, Journ. pr. Ch. 26, 411.
Scheele obtained potassium cyanide from
a fused mixture of 'tartar' and coal
or graphite and ammonium chloride,
' Sammtliche phys, u. chem. Werke,'
Ilermbstadt, Vol. II, p. 345).

Potassium cyanide is formed when
ammonia is passed into a heated mix-
ture of carbon and potassium carbonate
or hydroxide (Desfosses, loc. cit. ; Kuhl-
mann, loc. cit. ; Griineberg, Flemming,
and Siepermann, Eng, Pat, 13697 of
1889 ; Beilby, Eng. Pat. 4820 of 1891;
Siepermann, Eng, Pat, 13754 of ^^93)
Riepe, Germ, Pat, 1 05051 of 1898; Ch.
Centr. 1899, 2, 1080).

Sodium cyanide is formed by passing
ammonia over a heated mixture of
sodium carbonate and zinc with or with-
out carbon (Hood and Salamon, Eng.
Pat. 21239 of 1 893). Alkaline cyanides
are formed by passing ammonia over
a mixture of alkaline sulphide and
charcoal at a red heat (Grossmann, Eng.
Pat. 2401 1 of 1899; also Germ. Pat.
121555 of 1900; Ch. Centr. 1901, 2,
68). Ammonium chloride and borax

172 AC]

HYDROGEN CYANIDE

265

on ignition g-ive a boron nitride which,
on fusion with potassium carbonate and
carbon, yields potassium cyanide (Moise,
Germ. Pat. 91708 of 1895 ; Ch. Centr.
1897, 2, 156}.

Cyanog-en is formed on passing electric
sparks between carbon poles in an at-
mosphere of nitrogen (Morren, Comp.
Rend. 48, 342), and this combines with
hydrogen under the influence of the
silent electric discharge (Boillot, Comp.
Rend. 76, 1132)^ or on heating the
mixed gases to 500-550° (Berthelot,
Bull. Soc. [2] 33, 2 ; Ann. Chim. [5]
18, 380). An aqueous solution of
cjanogen is found to contain hydrogen
cyanide among other products after long
keeping (Wohler, Pogg. Ann. 15, 627).

Phospham (Gerhard t, Ann. Chim.
[3] 18, 188; 20, 225; Liebig and
Wohler, Ann. 11, 139 ; Pauli, Ann.
101, 41 ; Salzmann, Ber. 1, 494; Besson,
Comp. Rend. 114, 1264), on heating
with an alkaline carbonate and carbon
or iron, gives a cyanide or ferrocyanide
respectively (Vidal, Germ. Pat. 95340
of 1897 ; Ch. Centr. 1898, 1, 542).

[B.] Carbon disulplnde [I6O] and
ammonia combine to forai ammonium
thiocyanate (Zeise, Ann. 47, 36; Millon,
Jahresber. 1860, 237; Zeit. [i] 1861,
64 ; Gelis, Jahresber. 1861, 340 ; 1863,
746 ; Schwartz, Wagner^s Jahresber.
1869, 269 ; Schulze, Journ. pr. Ch.
[2] 47, 518; Claus, Ann. 179, II2:
for combination in presence of sul-
phites and hydrosulphites see Goldberg
and Siepermann, Germ. Pats. 83435
of 1895, and 87813 of 1896; Ber. 28,
Ref. 950 ; 29, Ref. 744 : for historical
summary and patented processes see
further N. Caro, Ch. Ind. 13, 244 ; 14,
287 ; Conroy, Journ. Soc. Ch. Ind. 15,
10 : for production of thiocyanates from
carbon disulphide and ammonia in pre-
sence of lime or magnesia see Hood and
Salamon, Germ. Pat. 72644 of 1892;
Ber. 27, Ref. 281 ; British Cyanides
Co., Germ. Pat. 81 116 of 1894; Ber.
28, Ref. 667; Albright and Hood,
Gei-m. Pat. 85492 of 1895; Ber. 29,
Ref. 314: for technical production of
thiocyanates see also Tscherniac and
Giinzburg, Ding. poly. Journ. 245,
214; Journ. Soc. Ch. Ind. 1, 150 ;

Nafzger, Journ, Soc. Ch. Ind. 5, 324;
Gasch, Ibid. 379 ; Crowther and Rossi-
ter. Ibid. 13, 887; Brock, &c.. Ibid.
1 1 95 J Albright and Hood, Ibid. 14,

657)..

Thiocyanates can by various pro-
cesses of oxidation or reduction be con-
verted into cyanides or ferrocyanides
(Pean, Jahresber. 1858, 585; Gelis,
Wagner^s Jahresber. 1862, 283 ; 1863,
321 ; Fleck, Ibid. 1863, 323; Alander,
Ding. poly. Journ. 226, 318; Tscherniak
and Giinsburg, Jahresber. 1878, 1123;
Wagner's Jahresber. 1878, 500 ; 1879,
471 ; 1880, 386; 1882, 510 ; Playfair,
Eng. Pat. 7764 of 1890 ; Journ. Soc.
Ch. Ind. 11, 14 ; Liittke, Germ. Pat.
89607 of 1895; Ber. 29, Ref. 1197;
United Alkali Co., Genu. Pat. 97896
of 1 895 J Ch. Centr. 1898, 2, 837:
for electrolytic oxidation see Parker,
Eng. Pats. 17447 of 1888 and 2383
of 1889 and also Journ. Soc. Ch.
Ind. 9, 67 ; 291 : for oxidation by hy-
drogen peroxide see Raudnitz, Zeit.
BioL, Jubelband, 42, 91 ; Ch, Centr.

1 901, 2, 1234: for historical summary
from the technological point of view see
Caro and Conroy as above ; also for
Raschen's process of oxidation by nitric
acid, Coni'oy, Journ. Soc. Ch. Ind. 18,
432 : see further Rasehen, &c., Journ.
Soc. Ch. Ind. 14, 1046 ; Goerlich and
Wichmann, Ibid. 657 ; Beringer, Eng.
Pat, 18565 of 1899; Rasehen, Norman,
and Luxton and the United Alkali Co.,
Eng. Pat. 12180 of 1900; Journ. Soc.
Ch. Ind. 20, 809 : for reduction of thio-
cyanates to cyanides by hydrogen see
Sestini and Funaro, Gazz. 12, 184;
Conroy, Heslop, and Shores, Journ. Soc.
Ch. Ind. 20, 320; British Cyanides Co.,
Germ. Pat. 132294 of 1901 ; Ch. Centr.

1902, 2, 80 : for reduction of copper
and other thiocyanates see Rossiter,
Crowther, and Albright, Eng. Pats.
4403 and 6226 of 1 901 ; Journ. Soc.
Ch. Ind. 21, 173; 345).

Cyanides are formed also from thio-
cyanates by heating the latter with
calcium carbide or in an atmosphere of
acetylene (Conroy, Heslop, and Shores,
loc. cif. ; Sandmann, Zeit. angew. Ch.

15, 543).

[C] From benzene [6 ; I, &c.], the

266

CYANOGEN COMPOUNDS

[172 C-J.

nitro-derivatives of which give hy-
drogen cyanide among the products
of the action of alkali (Hiibner and
Postj Ber. 5, 408). From benzene via
nitrobenzene, phenylhydroxylamine, and
nitrosobenzene. The latter gives hy-
drogen cyanide among the products of
the action of alkali (Bamberger, Ber.
33, 1939).

Or from benzene through trichlor-
phenomalic acid (see under carbon di-
sulphide [160; N]) and chloroform,
'and then as under E below.

Or from toluene [54 ; A, &e.] through
o-nitrofcolnene and o-toluidine, the latter
giving hydrogen cyanide by the action
of sodium hypochlorite (Meigen and
Normann, Ber. 33, 2714).

[D.] From phenol [6O], hydrogen
cyanide being among the products of
the action of alkali on the nitro-deriva-
tives (Hiibner and Post, as above : see
also Wedekind and Haussermann, Ber.
35, 1 133).

From phenol and ethyl alcohol
[14] through coumarone (see under
phlorol [64; Cl) and nitrocoumarone
(see under salicylic aldehyde [117; A]).
The latter gives hydrogen cyanide
among the products of its decomposition
by sodium ethylate (Stoermer and Kah-
lert, Ber. 35, 1640).

[E.] From ethyl alcohol [14] through
chloroform (see under methane [l; D]).
Hydrogen cyanide is foi-med by passing
ammonia and chloroform vapour through
a hot tube, or by heating chloroform and
alcoholic ammonia to 180-190" (Heintz,
Ann. 100, 369 ; Cloez, Jahresber. 1858,
345). Also by the action of caustic
potash on chloroform in presence of
aqueous ammonia (Hofmann, Ann. 144,
116).

Alcohol also gives hydrogen cyanide
among the products of its oxidation by
nitric acid, possibly through the forma-
ti( n of an oximido-compound (Gill and
Meusel, Zeit. [2] 5, 66 ; Hantzsch,
Ann. 222, 6$).

Or from alcohol through glyoxal by
oxidation with nitric acid (Debus, Ann.
102, 20; 107, 199; 110, 316; 118,
253). The oxime (glyoxime) gives
cyanogen on heating with acetic anhy-
dride (Lacli, Ber. 17, 1573), and- this

can be converted into hydrogen cyanide
as above under A.

Note : — The following compounds thus be-
come, through chloroform, generators of hydro-
gen cyanide (see under carbon disulphide [160 ;
D ; E ; F ; K ; L ; M]) :—

Acetone [106] ; aldehyde [92] ; acetic, gallic, or
salicylic acid [Vol. II] ; plisnol [60]. The last
three through trichlor-aa-glyceric acid and
chloroform.

[P.] From formic aldehyde [91], the
polymeric oxime of which gives hydro-
gen cyanide on sudden heating (Scholl,
Ber. 24, 577). Or formoxime yields
hydrogen cyanide on dehydration by
phosphorus pentoxide (Dunstan and
Bossi, Trans. Ch. Soc. 73, 360).

[G.] From isolutyric aldehyde [94]
through the a-brom-paraldehyde by
bromination (Franke, l^onats. 21, 205).
The latter gives an oxime which, by
the action of acetic anhydride, yields a
resinous nitrile which is decomposed by
sodimn carbonate into hydrogen cyanide
and acetone {Ibid. 210 : see also under
acetone [IO6 ; DDJ).

[H.] Dextrose, Icevnlose [154; 155],
and many sugars give hydrogen cyanide
among the products of their oxidation
by nitric acid (Hantzsch, Ann. 222,
65 : for production from saccharose see
Burls, Evans, andDesch, Ch. News. 68,

75)-

[I.] From formic acid [Vol. II] by

heating the dry ammonium salt (Peiouze
and Dobereiner, Ann. 2, 90), or by dis-
tilling this salt or formamide with phos-
phorus pentoxide (Lorin, Ann. 132,
255 ; Hofmann, Journ. pr. Ch. 91, 61 ;
Journ. Ch. Soc. 16, 74). By distilling
ammonium formate (or fonnamide) into
heated potash potassium cyanide is
formed (Glock, Germ. Pat. 108152 of
1899; Ch. Centr. 1900, 1, 1115).

Or phospham, when heated with for-
mic acid, gives at 150-200° hydrogen
cyanide (Vidal, Germ. Pat. 101391 of
1898; Ch. Centr. 1899, 1, 960 ; also
Eng. Pat. 4227 of 1898; Journ. Soc.
Ch. Ind. 18, 398).

[J.] From acdic acid [Vol. II], dry
sodium acetate giving the cyanide (15
p.c.) on heating with a nitrite (Warren,
Ch. News, 72, 40; Kerp, Ber. 30, 610 :
see also Roussin, Comp. Rend. 47, 875).

172 J-U.]

HYDROGEN CYANIDE

267

According- to Kerp {loc. cit. 6ii) free
hydrogen cyanide is also evolved.

Or potassium chloracetate, by the
action of a nitrite^ yields nitromethane
(Preibisch, Journ. pr. Ch. [2] 8^ 316).
The latter^ by the action of alkalis,
gives ' methazonic acid ' (Lecco, Ber.
9, 705 ; Dunstan and Goulding, Trans.
Ch. Soc. 77; 1262), which, on heating
with acids or alkalis or by oxidation
with potassium permanganate, yields
hydrogen cyanide (D. and G., loc. cit.
1264),

A solution of copper acetate heated
with ammonia gives cuprous cyanide
(Vittenet, Bull, Soc. [3] 21, 261).

Acetic acid and methyl alcohol [13]
give dimethylacetoacetic methyl ester,
which, on treatment with nitric acid,
yields a compound decomposable by al-
kali with the formation of hydrogen
cyanide among other products (W. H.
Perkin, junr., Proc. Ch. Soc. 17, 204).

[K.] From propionic acid [Vol, II]
by heating dry sodium propionate
with a nitrite as above (Kerp, loc. cit.
611).

[L.] From tartaric acid [Vol. II] as
above, potassium sodium tartrate or
neutral sodium tartrate being fused with
nitrite. Free hydrogen cyanide is also
evolved (Warren, loc. cit. ; Kei^), loc.
cit. 611).

Or indirectly from tartaric acid
through 'nitrotartaric acid' (Dessaignes,
Ann. 82, 362 ; Demole, Ber, 10, 17H9 ;
Kekule, Aim, 221, 245). The latter [or
the ' dioxy tartaric ' acid obtained from
it by the action of ethyl nitrite (Kekul^,
loc. cit. 247), or by decomposition by
aqueous sodium carbonate and acetate
(Thiele and Dralle, Ann. 302, 291,
note)] gives glyoxal on heating with
acid sodium sulphite in aqueous solution
(Hinsberg, Ber. 24, 3236). Subsequent
steps through glyoxime and cyanogen,
&c., as above under E.

Note : — Dioxytartaric acid can also be ob-
tained from tartaric acid through its oxidation
product, dihydroxymaleic acid (see under
furfural [126 ; E]), and further oxidation of
the latter by bromine and water (Fenton,
Trans. Ch, Soc, 67, 48 ; 73, 71).

[M.] From oxalic acid [Vol. II] by
beating the ammonium salt alone or

with phosphorus pentoxide, &c. (Dumas,
Ann. 10, 295 ; Bertagnini, Ann. 104,
176 ; Storch, Ber. 19, 2459). The
cyanogen thus fonned can be con-
verted into hydrogen cyanide as above
under A.

[N.] From lactic acid [Vol. II]
through ' nitrolactic acid ' (Henry, Ber.
3, 532), the latter undergoing spon-
taneous decomposition with evolution
of hydrogen cyanide (Ibid.).

[O.] Yvom acetic alde//^de [92 j through
glyoxal by oxidation with nitric acid
(Liubavin, Ber. 8, 768 ; Journ. Russ.
Soc. 7, 249 ; 13, 496 ; Ber. 10, 1366 ;
De Forcrand, Bull. Soc. [2] 41, 242 ;
Spiegel, Ch. Zeit. 19, 1423), and then
through the oxime and cyanogen as
above under E.

[P.] From catechol [69], which gives
dioxytartaric acid when acted upon by
nitrous gas in ethereal solution (Barth,
Monats. 1, 869). Subsequent steps as
above under L.

[Q,] Protocatechuic acid [Vol, II]
gives dioxytartaric acid when treated as
above (Gruber, Ber. 12, 514).

[R.] Quinone [142] gives hydrogen
cyanide when oxidised by nitric acid in
excess (Kerp, Ber, 30, 612).

[S,] From glycocoll [Vol. II], which
gives hydrogen cyanide when heated
with dilute sulphuric acid and manga-
nese dioxide (Watts's Diet., Morley and
Muir, II, 627). Or glycin ethyl ester,
by the action of nitrous acid, gives
ethyl diazoacetate (Curtius, Journ. pr.
Ch. [2] 38, 401). The latter, on treat-
ment with sodium ethylate, yields the
sodium derivative of ethyl isodiazoace-
tate. Free ethyl isodiazoacetate gives
hydrogen cyanide among the products
of its decomposition by heat (Hantzsch
and Lehmann, Ber, 34, 2506),

[T,] From wethylawine [Vol. II] by
the action of heat on the vapour (Wurtz,
Ann. Chim. [3] 30, 454), or by com-
bustion of the moist vapour (Tollens,
Zeit, [2] 2, 516). Hydrogen cyanide
is also among the products of oxidation
of methylamine by monopersulphuric
acid (Bamberger and Seligman, Ber.
35,4299).

[U.] Trirnethylamine [Vol. II], when
the vapour is passed through a red-hot

268

CYANOGEN COMPOUNDS

[172 U-174.

tube, gives hydrogen and ammonium
cyanides (Willm_, Bull. Soc. [2] 41,

449)-

[v.] From methane [l] and nitrogen,
which give ammonium cyanide under
the influence o£ the silent electric dis-
charge (Figuier, Bull. Soc. [2] 46, 61).

[W.] From succinic acid [Vol. II]
through acetylenedicarboxylic acid (see
under methane [l ; T]). The silver
salt of the latter on treatment with
strong nitric acid is decomposed with
the formation of silver cyanide.

[X.] From fumaric acid [Vol. II]
through dibromsuceinic acid and acety-
lenedicarboxylic acid (see under me-
thane [1 ; u]), and then as above.

[Y.] From methyl alcohol [13] through
methyl iodide and nitromethane (Bewad,
Journ. Buss. Soc. 24, 1 26 ; V. Meyer,
Ann. 171, 32). From the latter through
methazonic acid as above under J. Ni-
tromethane is also among the products
of interaction of dimethyl sulphate and
a nitrite (Kaufler and Pomeranz, Monats.
22, 492).

[Z.] From eihylamine [Vol. II],
hydrogen cyanide being among the
products of pyrogenic decomposition
(Muller, Bull. Soc. [2] 45, 438).

[AA.] From malonic acid [Vol. II]
and ethyl alcohol [14]. Ethyl malonate
on nitration gives a nitromalonic ester,
and this on heating with water at 160°
yields hydrogen cyanide among other
products (Wahl, Comp. Rend. 132,
1050).

[BB.] From glycerol [48] through
allyl alcohol (see under ethyl alcohol
(14 ; G]). The latter gives glyoxal by
' contact ■" oxidation over heated plati-
num (Trillat, Comp. Rend. 133, 82a).
From glyoxal as above under E.

[CC] From coumarin [Vol. 11'
through coumarone (see under phloro
[64 ; D]), and then through nitrocou-
marone as above under D.

[DD.] From salicylic aldehyde [117]
and acetic acid [Vol. II] through
coumarone (see under phlorol [64 ; E]),
and then as above under D.

[EE.] From cinnamic acid [Vol. II]
through coumarone (see under phlorol
[64; F]), and then as above.

[PF.] From lysine [Vol. II], hydrogen

cyanide being among the products of
oxidation by barium permanganate
(Zickgraf, Ber. 35, 3401).

[GG.] Urea [Vol. II] gives zinc
cyanide on heating with zinc dust
(Aufschlager, Monats. 13, 268).

Organic Cyanides.

Note: — The cyanides of ally], benzyl, and
phenylethyl which, chiefly on the authority of
Hofmann (Ber. 7, 518 ; 520 ; 1293), are included
among the products contained in the oils of
black and white mustard seed and of various
cresses, are now known not to occur as such in
the plants, but to result as secondary products
of decomposition of the corresponding mustard
oils (Gadamer, Arch. Pharm. 237, in ; Ber.
32, 2336 ; Ter Meulen, Eec. Tr. Ch. 19, 37).

173. Isocyanacetic Acid.
CN.CH2.COOH

Natural Source.

This acid, on the authority of Calmels
(Bull. Soc. [2] 42, 266), is said to have
been found in toads.

Synthetical Processes.

[A.] From acetic acid [Vol. II] by
the interaction of the bromo-acid and
silver cyanide [l72] (Calmels, loc. cit,).

[B.] From glycocoll [Vol. II] by the
action of chloroform [l ; D] in presence
of caustic potash {IIAd,).

174. Thiocyanic Acid;
Sulphocyanic Acid.

NC.SH

Natural Sources,

Allyl thiocyanate is possibly present
in traces with the isothiocyanate in
allyl mustard oil (see latter [I66] for
natural sources: also Schmidt, Ber.
10, 187 ; Gildemeister and Hoffmann,
'Die aetherischen Oele,' p. S3^)-

Potassium thiocyanate occurs in the
urine of man, dogs, horses, and cattle,
and also in saliva and gastric juice. (For
occurrence in urine see Munk, Virchow's

174-F.]

THIOCYANIC ACID

269

Arcli.;, 69, 354; Gscheidlen, Pfliiger's
Arch, 14, 401 : in saliva, submaxillary
and sublingual, Gscheidlen, loc. cit. ;
Oehl, Canstatt's Jahresber. d. Med. 1,
1 20; Kriiger, Zeit. Biol. 37, 6; Ch.
Centr. 1899, 1, ^^; Grober, Ch. Centr.
1901, 1, 839 : in g-astric juice, Kehling,
Zeit. physiol. Ch. 18, 397; Nencki,
Ber. 28, 1318; Nencki and Sieber,
Zeit. physiol. Ch. 32, 291 : in nasal and
conjunctival secretions. Muck, Ch. Centr.
1900, 2, 1 157 : for method of identifi-
cation in urine, blood, bile, &c., see
Bruylants, Journ. Pharm. [5] 18, 104 ;

^53-)

Synthetical Processes.

[A.] From carbon through cyanogen
(see under hydrogen cyanide [172 ; A]).
Cyanogen passed over heated potassium
polysulphide gives thiocyanate ( Wohler,
Pogg. Ann. 3, 181). Nitrogen passed
over a strongly ignited mixture of
potassium carbonate (containing sul-
phate) and charcoal gives a trace of
potassium thiocyanate (Erdmann and
Marchand, Journ. pr. Ch. 26, 414).
Or cyanogen chloride interacts with
ammonia to form cyanamide (Cloez and
Cannizzaro, Ann. 78, 229), which can
be treated as below under E. Nitro-
genous organic matter (such as urea)
fused with potassium polysulphide gives
potassium thiocyanate (Aufschlager,
Zeit. anal. Ch. 35, 315).

Or carbon dioxide passed over heated
sodamide gives cyanamide (Beilstein
and Geuther, Ann. 108, 93 ; Drechsel,
Journ. pr. Ch. [2] 16, 203). Ammonium
carbonate or carbamate heated with
sodium also yields cyanamide (Fenton,
Trans. Ch. Soc. 41, 26^). Subsequent
steps as below under E.

Ammonium thiocyanate is produced
by the electrolysis of a solution of
ammonium hydrosulphide with gas-
retort carbon electrodes (Millot, Comp.
Rend. 103, 153; Bull. Soc. [2] 46,
246).

[B.] From hydrogen cyanide [172] by

combination . with ammonium polysul-
phide (Liebig, Ann. 61, 126). Or
metallic cyanides or ferrocyanides [l72 ;
A] give thiocyanates on heating with
sulphur or alkaline sulphides (Porret,
Gilb. Ann. 53, 184; Berzelius, Berz.
Jahresber. 1, 48 ; Wiggers, Ann. 29,
319; Liebig, Ann. 50, 349; 51, 288;
61, 126; Henneberg, Ann. 73, 230;
Lowe, Jahresber. 1853, 407 ; Babcock,
Zeit. [2] 2, 666; Frohde, Pogg. Ann.
119, 317 : for production of potassium
thiocyanate by the fusion of carbon,
sulphur, and ammonium sulphate with
potassium hydroxide see Fleck, Ding,
poly. Journ. 169, 209 : for production
of potassium thiocyanate by the inter-
action of potassium thiosulphate and
cyanide see Dobbin, Ch. News, 77,

131)-

[C] From carbon disuljoJiide [I60]
and ammonia as under hydrogen cyanide
[172; B].

[D.] From ethyl alcohol [14] and
nitric acid, &c., through mercury ful-
minate (see under benzoic aldehyde
[114 ; A]). The latter gives ammonium
thiocyanate when acted upon by sul-
phuretted hydrogen (Ber. 8, 1 1 7 8).

[E.] Urea [Vol. II] on heating with
sodium or by distillation with quick-
lime gives cyanamide (Fenton, Trans.
Ch. Soc. 41, 262 ; Emich, Monats. 10,
332). The latter on treatment with
sulphuretted hydrogen or (better) am-
monium sulphide yields thiourea (Bau-
mann, Ber. 6, 1375 ; 8, 26), and this
on heating with water at 140° or /jer se
at 160-170° becomes converted into
ammonium thiocyanate (Haller, Bull.
Soc. [2] 45, 706).

[P.] Guanidine [Vol. II] is converted
into the nitroso-derivative (Thiele, Ann.
273, 133). The latter on heating with
water gives cyanamide {Ibid. 136),
which can be treated as above under E.

Note : — For the liberation of free thiocyanic
acid from its salts see "WOhler, Gilbert's Ann.
69, 271 ; Hermes, Zeit. [2] 2, 417 ; Journ. pr.
Ch. 97, 465 ; Zimmermann, Ann. 199, I ;
Klason, Journ, pr. Ch. [2] 35, 403.

APPENDIX

While the foregoing^ pages were passing through the press several additional
syntheses of natural products have been accomplished. In order to make the
present volume as complete as possible, these and other recent discoveries bearing
upon the synthetical processes dealt with in the text, together with a few
corrections, have been included in this appendix.

CAMPHOE AND TERPENE GROUP.

175. Camphor; 1 : 7 : 7-Triinethyl-
1:2: 2-Bic7Clo-2-Heptanone.

H,C

H,C

CH-

-CH,

0:0

CH,

Natural Sources.

Camphor (d-modification) is obtained
from C'mnamomum camphora = Laurus
camphora, which grows in the eastern
districts of Central China, in South
China, in the Malay Archipelago, in
the islands of Formosa and Hainan,
and in the S. Japan islands, Kiushiu
and Shikoku. 1-Camphor occurs in the
oil of Matricaria {Pyreihrum) par-
theniim,, common feverfew, which is
cultivated in Germany (Dessaignes and
Chautard, Journ. pr. Ch. 45, 45 ;
Chautard, Jahresber. 1863, ^^^. Oil
of tansy, from Tanacetum vulgare,
appears also to contain 1-camphor
(Schimmel & Co., as quoted by Gilde-
meister and Hoffmann, 'Die aetheri-
schen Oele/ p. 889 : see also Persoz,
Comp. Rend. 13, 436; Ann. 44, 313;
Journ. pr. Ch. 25, SS\ Vohl, Arch.
Pharm. 124, 16).

Ordinary (d-) camphor has been
found also in oil of spike from Lavan-
dula spica (Kane, Journ. pr. Ch. 15,
163 ; Dumas, Ann. 6, 248 ; Lalle-
mand, Ann. 114, 197; Bruylants,

Journ. Pharm. [4] 30, 139). Its
occurrence in oil of sage from Salvia
officinalis (Muir, Trans. Ch. Soc. 37,
678) could not be confirmed by Schim-
mel & Co. (Ber. Oct. 1895, p. 40). It
occurs in oil of sassafras bark to the
extent of 6-8 per cent. (Power and
Kleber, Pharm. Rev. 1896; Ch. Centr.
1 897, 2, 42), in oil of sweet basil from
Ocimtim hasilicmn (Bertram and Wal-
baum. Arch. Pharm. 235, 176), and in
Siam cardamom oil from Amommn car-
(lamomum (SchimmeFs Ber. Oct. 1897;
Ch. Centr. 1898, 1, 258). Small
quantities have been found also in the
oil of cinnamon root, Ceylon (Tromms-
dorff, ' Handb. d. Pharm.^ 1 827, p. 666 ;
Dumas and Peligot, Ann. 14, 50 ;
SchimmeFs Ber. Oct. 1892), and in
oil of rosemary from Rosmarinus offici-
nalis (Lallemand, Ann. 114, 197;
Montgolfier, Bull. Soc. [2] 25, 17 ;
Bruylants, Journ. Pharm. [4] 29, 508 ;
Pharm. Journ. [3] 10, 327 ; Jahresber.
1879, 944 ; Hailer, Comp. Rend. 108,
1308). The camphor from this last
source is a mixture of the d- and 1-
modifications (Montgolfier, loc. cif,.).

Note : — The oil from the leaves of the cam-
phor tree has been examined by Schimmel &
Co. (Ber. Oct. 1892) and by Hooper (Pharm.
Journ. 56, 2 1 ). For determination of camphor
in camphor oils see Lohr, Ch. Zeit, 25, 292.
For the mode of formation of camphor in the
plant see Tschirch and Shirasawa, Arch.
Pharm. 240, 257.

272

APPENDIX

[175 A-176.

Synthetical Processes.

[A.] From malonic and oxalic acids
[Vol. II], acetone [l06], and methyl and
ethyl alcohols [l3 ; 14]. Acetone is
converted into mesityl oxide (see under
acetone [l06 ; S, p. 179]), the latter
condensed with sodio-malonic ester in
alcoholic solution by means of sodium
ethoxide so as to form dimethylhydro-
resorcylic ester, and the ester decom-
posed by heating" with barium hydroxide
solution in order to obtain dimethyl-
hydroresorcinol (Komppa, Ber. 32,
£422 : see also Vorliinder, Ann. 294,
314). The latter, on oxidation by
sodium hypobromite, yields ^/3-di-
methylglutaric acid (K. loc. cit. 1423).
The dimethyl ester of this last acid and
oxalic ester condense under the influence
of sodium ethylate to form diketoapo-
camphoric ester {Ibid. 1424; 34, 2472).
By the action of sodium and methyl
iodide the latter is converted into di-
ketocamphoric ester, and this, on reduc-
tion in sodium carbonate solution by
means of sodium amalgam, gives the
corresponding dihydroxy camphoric acid,
which, on heating with a strong solu-
tion of hydriodic acid in presence of red
phosphorus, yields a racemic dehydro-
camphoric acid. The latter combines
with hydrogen bromide, when heated
with an acetic acid solution of the
hydracid, to form a saturated /3-brom-
camphoric acid. The bro mo-acid on
reduction with zinc dust and acetic acid
gives a syrupy mixture of acids, from
which, by the action of acetyl chloride,
camphoric anhydride is obtained, and
this, on solution in alkali and precipita-
tion by acid, yields racemic camphoric
acid {Ibid. 36, 4332-4335).

Camphoric anhydride on reduction
in alcoholic solution with sodium amal-
gam is converted into *campholide'

= C8Hi,<™2)0 (Haller, Comp. Rend.

122, 293), and this on heating with
a solution of potassium cyanide is
converted into ' cyancampholic acid '
(= homocamphoric nitrile), from which
homocamphoric acid can be obtained
by hydrolysis. The lead or calcium
salt of this acid on dry distillation

yields camphor {Ibid. 446 ; Bull. Soc.
[3] 15, 324 ; Haller and Blanc, Comp.
Rend. 130, ^']6 ; Bredt and Rosenberg,
Ann. 289, i).

Note: — )3;8-Dimethylglutaric acid has been
obtained also by the condensation of dimethyl-
acrylic ester (obtained from a-bromisovaleric
ester) and sodio-malonic ester and decomposi-
tion and hydrolysis of the dimethylpropane-
tricarboxylic ester thus obtained (Auwers, Ber.
28, 1130; W. H. Perkin, junr., and Goodwin,
Trans. Ch. Soc. 69, 1472).

[B.] Borneol [176] gives camphor on
oxidation by nitric acid (Pelouze, Ann.
40, 328 ; Montgolfier, Comp. Rend.
88, 915; Ann. Chim. [5] 14, 20.
1-Borneol gives ordinary (d-) camphor
(Montgolfier, Ann. Chim. [5] 14, 29 :
compare Pope and Harvey, Trans. Ch.
Soc. 79, 76).

[C] Camphene [177] gives camphor
on contact oxidation by heated spongy
platinum (Berthelot, Ann. 110, '^^f),
or by chromic acid mixture (Riban,
Bull. Soc. [2] 24, 19 ; Armstrong and
Tilden, Trans. Ch. Soc. 35, ^^6; Ber.
12, 1756).

176. Borneol.

H.O

H,C

CH,

(?)

CH.OH

CH,

Natural Sources.

d- Borneol occurs in the pith cavities
of the trunk of Bryobalanops camphora
(= aromatica) from Borneo, Sumatra,
Labuan and Jahore in the Straits
Settlements (Martius, Ann. 27, 6-^ ;
Pelouze, Comp. Rend. 11, ^6^ ; Ann.
40, 326; Gerhardt, Ann. 45, 38), in
oil of spike from Lavandula spica
(Bruylants, Journ. Pharm. [4] 30, 139;
Ch. Centr. 1879, 616 j Bouchardat,
Comp. Rend. 106, 551 ; 117, ^'^ ; 1094),
in oil of rosemary from Uosmarinus
officinalis (Bruylants, Journ. Pharm.
[4] 29, 50H; Pharm. Journ. [3] 10,
327; Jahresber. 1879, 944; Weber,
Ann. 238, 89 ; Gildemeister and Ste-
phan. Arch. Pharm. 235, 585 ; Schim-
meFs Ber. Oct. 1897 ; Ch. Centr. 1898,
1^ 258), in Siam cardamom oil from

176-177.]

APPENDIX

273

Amomum cardamomum (Schimmel's Ber.
loc. cit.), and in lavender oil {Ibid. April^
1903 ; Ch. Centr. 1903, 1, 1086; Chara-
bot, Bull. Soc. [3] 17, 380).

1-Borneol occurs in Chinese Ngai
camphor from Blumea balsamifera
(Plowman, Pharm. Journ. [3] 4, 710 ;
riiickiger. Ibid. Sijg ; Hanbury, Jahres-
ber. 1874, ^^'j ; SchimmeFs Ber. April,
1895), as ester of formic, acetic, buty-
ric, and isovaleric acids in the oil
of valerian (Gerhardt, Ann. 45, 34 ;
Bruylants, Ber. 11, 452 ; Haller, Ann.
Chim. [6] 27, 396 ; Oliviero, Comp.
Rend. 117, 1096; Bull. Soc. [3] 11,
150 ; 13, 917), as ester of acetic and
isovaleric acids in oil of kesso from
Valeriana officinalis var. angustifolia
(Bertram and Gildemeister, Arch.
Pharm. 228, 483), in citronella oil
from Andropogon nardtis (SchimmeFs
Ber. April, 1894), in oil of feverfew,
Matricaria {Vyrethrum) parthenium {Ibid.
Oct. 1 894), and in oil of Asarum cana-
dense (Power and Lees, Proc. Ch. Soc.
17, a 10).

1-Bornyl acetate is contained in the
oils from many Coniferse : — Abies cana-
densis (oil of hemlock), A. pectinata,
A. sibirica, Picea vulgaris, P. nigra (or
"^ alba, spruce oil), P. excelsa, Pimis
joumilio, P. montana (Bertram and Wal-
baum, Arch. Pharm. 231, 290 ; Schim-
meFs Ber. Oct. 1897 ; Ch. Centr. 1898,
1, 358 ; Hirschsohn, Pharm. Zeit. f.
Russland, 1892, No. 38; Kremers,
Pharm. Bund. 13, 135 ; Hunkel, Pharm.
Rev. 14, ^i^).

Borneols or their esters (chiefly ace-
tates) are found also in larch needle oil
from Larix decidua (Schimmel & Co.
loc. cit.), in Swedish oil from Pinus
sylvestris (Bertram and Walbaum, loc.
cit.), in Virginian snake-root oil from
Aristolockia serpentaria (Spica, Gazz.
17, 313), probably in the oil of Aristo-
lockia reticulata (Peacock, Am. Journ.
Pharm. 63, 257; Ch. Centr. 1891, 2,
379), in oil of g-olden rod from Soliclago
sp. (SchimmeFs Ber. Oct. 1891 ; April,
1894; April, 1897), in oil of thyme
from Thymus vulgaris {Ibid. Oct. 1 894),
and (d- and 1- modifications) in oil of
sage from Salvia officinalis {Ibid. Oct.
1895). Bornyl acetate is contained

also in the oil of Satureia tliymbra from
Spain {Ibid. Oct. 1889).

According to Jeanjean (Ann. 101,
95) the fusel oil of brandy obtained
from the spirit produced by the fer-
mentation of the sugar from the madder
root contains 1-borneol (see Beilstein^s
^Handbuch,^III, 471).

Synthetical Processes.

[A.] From camphor [175] by heating
with alcoholic potash (Berthelot, Ann.
Chim. [3] 56, 78). Camphor by the
action of sodium per se or by reduction
with sodium in alcoholic or moist ethe-
real solution gives borneol, the optically
isomeric camphors yielding to a pre-
ponderating extent the corresponding
borneols (Baurigny, Zeit. [2] 2, 408;
3, 71; 4, 208; 481; 687; Kachler,
Ann. 197, 99 ; Montgolfier, Ann. Chim.
[5] 14, 21; 38; Jackson and Menke,
Am. Ch. Journ. 5, 270 ; 6, 406 ;
Kachler and Spitzer, Monats. 5, 50 ;
Immendorff, Ber. 17, 1038; Wallach,
Ann. 230, 225 ; Haller, Comp. Rend.
105, 227 i Ann. Chim. [6] 27, 416;
Briihl, Ber. 24, 3384; Beckmann,
Germ. Pat. 42458 of 1887; Ber. 21,
Ref. 321; Ann. 250, 322; Ber. 22,
912 : for electrolytic reduction of cam-
phor to borneol see Tafel and Schmitz,
Zeit, Electroch. 8, 288). By the action
of sodium on camphor d- and isoborneol
are formed (Bertram and "Walbaum,
Journ. pr. Ch. [2] 49, 15 ; Beckmann,
Ibid. 55, ^S)'

[B.] From camphene [177] through
camphor [l75 ; C], and then as above
under A.

177. Campliene.

HC CH CH2

HC

(?)

CH,

Natural Sources.

1-Camphene is contained in citronella
oil from Andropogon nardus (SchimmeFs
Ber. Oct. 1893 ; Bertram and Walbaum,
Journ. pr. Ch. [2] 49, 16), in kesso oil

274

APPENDIX

[177-178.

from the Japanese Valeriana officinalis
var. angustifolia (B. and W. loc. cit. i8),
and in French oil of valerian (Oliviero,
Comp. Rend. 117^ 1096; Bull. Soc. [3]
\1, 150 ; 13, 917). d-Camphene is con-
tained in oil of ging-er (SchimmePs
Ber. Oct. 1893; B. and W. loc. cit.),
in oil of sweet orange (neroli oil from
flowers) (Theulier, Bull. Soc. [3] 27,
278 : see also Hesse and Zeitschel,
Journ. pr. Ch. [2] 66,481), in oil of
spike from Lavandula spica (Bouchardat,
Comp. Rend. 117, 1094), and in American
oil of turpentine (SchimmeFs Ber. Oct.
1897 : see also Armstrong and Tilden
as below).

i-Camphene occurs in oil of rosemary
(Gildemeister and Stephan, Arch.
Pharm. 235, 586; Schimmel's Ber.
Oct. 1897).

A eamphene is contained in Russian
oil of turpentine, probably from Abies
(Pinus) sibirica (Golubeff, Journ. Russ.
Soc. 20, 585; Ch. Centr. 1888, 2,
1632), in French turpentine oil, and
probably in other pinene-containing
oils from Coniferse (Armstrong and
Tilden, Ber. 12, 1753; Trans. Ch. Soc.
35, 742 ; Power and Kleber, Pharm.
Rund. 12, 16; Bouchardat and Lafont,
Comp. Rend. 113, 551; 125, iii).

Synthetical Peocesses.

[A.] From borneol [176] by heating
with hydrogen potassium sulphate to
200° (Wallach, Ann. 230,. 239), or with
dilute sulphuric acid to 60-100° (Kono-
waloff, Journ. Russ. Soc. 32, 76). Or
borneol can be converted into bornyl
chloride by heating with hydrochloric
acid (Berthelot, Ann. 112, 366), or with
phosphorus pentachloride (Wallach, loc.
cit. 23 1 ; Kachler, Ber. 11, 460 ; Ann.
197, 93). The chloride gives eamphene
on heating with alcoholic potash (Riban,
Ann. Chim. [5] 6, 383), with water and
magnesium oxide (Kachler, Ann. 197,
96), or with aniline (Wallach, loc. cit.
233; Ber. 25, 916). Water alone
decomposes the chloride with the forma-
tion of eamphene (Kachler and Spitzer,
Ann. 200, 342 ; Riban, loc. cit. 382).

[B.] Camphor [175] on heating with
ammonium formate gives formylbornyl-

amine (Leuckart and Bach, Ber. 20, 104 ;
Wallach and Griepenkerl, Ann. 289,
347), and this yields bornylamine on
hydrolysis with hydrochloric acid. The
amine or its formyl derivative gives
eamphene on heating to 200-210° with
acetic anhydride (W. and Gr. loc. cit.
349). Or camphor by the action of
phosphorus pentachloride at ordinary
temperatures gives camphor chloride,
CjoHigClg (Spitzer, Ann. 196, 26a),
and this on treatment with sodium in
ethereal solution yields a eamphene
(Kachler, Ann. 197, 127 ; K. and
Spitzer, Ann. 200, 341 ; Montgolfier,
Ann. Chim. [5] 14, 104).

Camphor oy the action of sodium
gives (with d-borneol) isoborneol (Ber-
tram and Walbaum, Journ. pr. Ch. [2]
49, 15), and this yields eamphene on
heating in benzene solution with zinc
chloride or on boiling with dilute sul-
phuric acid {Ibid. 8). Isoborneol also
gives eamphene by heating to 220°
with zinc dust (Semmler, Ber. 33,

Note : — Bornylamine is among the products
formed by the reduction of camphoroxime with
sodium in alcoholic solution (Leuckart and
Bach, Ber. 20, 104: for electrolytic reduction
of the oxime to bornylamine, see Bohringer
and SOhne, Germ. Pat. 141 346; Journ. Ch.
Soc. 84, I, 551).

Camphor may also be converted into
borneol [as under 176, A], and the
latter treated as above under A.

178. Menthene ;

Tetrahydro-p-Cymene ;

l-Meth7l-4-inetlioetli7l-

S-cyclohexene.

CH3
CH

H,C

CH,

H,C CH

\/

C
CH3.CH.CH3

Natural Source.

According to Labbe menthene is
contained in oil of thyme (Bull. Soc.

178-179 A.]

APPENDIX

275

[3] 19, loio : compare Gildemeister
and Hoffmann, op. cit. p. 818). A
menthene may occur in peppermint oil
(Andres and Andr^eff, Ber. 25, 609).

Synthetical Process.

[A.] From menthol [4l] by heating-
with sulphuric acid, phosphorus pent-
oxide, zinc chloride, anhydrous cuprie
sulphate, or acid potassium sulphate
(Walter, Ann. 32, 388; Beckmann,
Ann. 250, 358; Briihl, Ber. 25, 143;
Sicker and Kremers, Am. Ch. Journ.
14, 391 ; Urban and Kremers, Ihid. 16,
397 ; Helbing, Ibid. 18, 762 j Richt-

mann. Ibid. 763 ; Konowaloff, Journ.
Russ. Soc. 32, 76).

Or menthol may be converted into
menthyl chloride by heating with phos-
phorus pentachloride, and the menthyl
chloride heated with aniline or quinoline
(Wagner, Ber. 27, 1636; Tolloczko,
Journ. Russ. Soc. 29, 48 ; Slawinski,
Ibid. 118: see also Berkenheim, Ber.
25, 686 ; Kijner, Journ. Russ. Soc.
27, 473; Wallach, Ch. Centr. 1898,
1, ^']0; Masson and Reychler, Ber. 29,
1843 J Tschugaeff, Ber. 32, 3332).

Note : — Menthene would precede cymene [6,
p. 28] in the scheme of chemical classification.
It is conveniently introduced here on account
of its genetic relationship to the terpenes.

FLAYONE GROUP.

179. Fisetin;
3:3^: 4^-Trihydroxyflavonol.

HO;

0.

HO

C— OH

■\ /

OH

\/\co/

Natukal Sources.

The occurrence of fisetin in the wood
of (Quebracho Colorado and of Rhus
cotinus is referred to under catechol
[69, p. 139]. Fisetin and a glucoside
thereof (not fustin) is also contained
in the stem of the yellow cedar, Rhus
rhodanthema, from N. S. Wales (A. G.
PerkiUj Trans. Ch. Soc. 71, 1194).

Synthetical Process.

[A,] From resorcinol [70], vanillin
[121], acetic acid [Vol. IIj, methyl and
ethi/t alcohols [13 ; 14]. Resorcinol and
acetic acid are converted into resaceto-
phenone (see under pseonol [133 ; A,

p. 231], and the latter into its ethyl
ether by ethylation. Vanillin is methy-
lated so as to form the methyl ether
(veratric aldehyde), and the latter con-
densed with the resacetophenone ether
by the action of alkali in alcoholic
solution so as to form 2^-hydroxy-4^-
ethoxy-3 : 4-dimethoxychalkone : —

[i]CH.C„H3(OCH3),[3:4]

(Kostanecki and R6zycki, Ber. 32,
2257)- ^^^^ unsaturated ketone on
boiling with an alcoholic solution of
dilute sulphuric acid is converted into
3 - ethoxy- 3^ : 4^ - dimethoxyflavanone,
which by interaction with amyl nitrite
forms isonitroso-3-ethoxy-3^ : 4^-di-
methoxyflavanone. The latter on heat-
ing with dilute sulphuric acid in acetic
acid solution gives 3-ethoxy-3^ : 4^-di-
methoxyflavonol, which on boiling with
strong hydriodic acid is completely
de-alkylated with the formation of
fisetin (Kostanecki, Lampe,and Tambor,
Ber. 37, 784).

T 2

276

APPENDIX

[180-181 A.

180. Quercetin ;
1:3:3^: 4^-Tetrahydroxyflavonol.

HO

OH

C.OH

>0H

HO

CO

/

Natural Sources.

The sources of quercetin are given
under catechol [69, pp. t^8, 139]. To
these must be added Prunus spinosa,
Viola odorata, and Trifolium repens,
white clover, in which the colouring-
matter has been found (A. G. Perkin
and Phipps, Trans. Ch. Soc. 85, ^6).
Globulariacitrin, a glucoso-rhamnoside
of quercetin, is contained in Globularia
alypum (Tiemann, Arch. Pbarm. 241,
»89).

Synthetical Process.

[A.] From pJiloroglticinol\SQ\,vamllin
[121], acetic acid [Vol. 11], and methyl
alcohol [13]. Phloroglucinol dimethyl
ether (see under hydrocotoin [134; A.,
p. 231]) is condensed with acetyl
chloride so as to form phloroaceto-
phenone dimethyl ether (see under
chrysin [138; A, p. 233]), and the
latter by condensation with vanillin
methyl ether (veratric aldehyde) con-
verted into 2^-hydroxy-4i : 6^ : 3 : 4-
tetramethoxychalkone : —

into quercetin by heating with strong
hydriodic acid (Kostanecki, Lampe, and
Tambor, Ber. 37, 1402).

181. Eampherol;
1:3: 4^-Trilxydroxyflavoiiol.

HoC.O'^ ^OH

CO.CH :CH[i] ,CsH3(OCH3)j[3: 4]
0 . CH3

The latter on heating with alcoholic
hydrochloric acid is converted into 7 :
3:3^: 4^-tetramethoxyflavanone, from
which the isonitroso-derivative is ob-
tained by the action of amyl nitrite.
On heating with dilute sulphuric acid
in acetic acid the isonitroso-derivative
forms I : 3 : 3^ : 4^-tetramethoxyflavonol,
which is demethylated and converted

HO

HO

Ov

CO

C.OH

)0H

Natural Sources.

Natural sources of kampherol are
given under phloroglucinol [86, p. 161,
and this appendix, p. 287].

Synthetical Process.

[A.] From phloroglucinol [86], anisic
aldehyde [120], acetic acid [Vol. II],
and methyl alcohol [13]. Phloraceto-
phenone dimethyl ether (see under
chrysin [l38; A, p. 233]) and anisic
aldehyde condense in alcoholic solution
in presence of sodiimi hydroxide to form
2^- hydroxy- 4I : 6^ : 4 -trimethoxy chalk-

one ;-

H.C,

o/\

OH

CO . CH : CH[i] . C6H,(OCH3)[4]
O.CH3

(Kostanecki and Tambor, Ber. Zl, 792).
The latter, on boiling its alcoholic solu-
tion with dilute sulphuric acid, is con-
verted into 1:3: 4^-trimethoxyflavanone,
which by the action of nitrous acid
(amyl nitrite) yields isonitroso-i : 3 : 4^-
trimethoxyflavanone. On heating with
dilute mineral acids the isonitroso-
derivative gives 1:3: 4^-trimethoxy-
flavonol, and this, on demethylation by
heating with strong hydriodic acid,
yields kampherol (Kostanecki, Lampe,
and Tambor, Ber. 37, 2096).

Note :— Fisetin, quercetin, and kampherol
belong to the same group as chrysin [138,
p. 233], tectochrysin [139, p. 234], apigenin
[140, p. 234], and lutoolin [141, p. 234].

APPENDIX

or THE

yNJYERSITY

277

The following modes of occurrence and methods of production are supple-
mentary to those recorded in the preceding pages : —

1. Methane (p. 3i).

Methane is among the products of
decomposition of egg-meat mixture by
Bacillus coli communis (Rettger^ Am.
Journ. Physiol. 8, 284). A ferment
(' pseudosarcine ') which produces meth-
ane has been obtained by Maze from
dead leaves. According to this author
the ferment produces methane from the
products formed by the butyric ferments
(Comp. Rend. 137, 887).

To be added to synthetical pro-
cesses : —

[D, p. 23.] From ethyl alcohol [l4],
methane being among the products
formed by passing the vapour over
heated carbon, aluminium, or magnesium
(Ehrenfeld, Journ. pr. Ch, [2] 67, 49,
&c.). With aluminium ethylene (see
note, p. 23) is also produced. Methane
is likewise formed by ' contact ' decom-
position of the vapour by finely divided
heated copper, nickel, cobalt, and
platinum (Sabatier and Senderens,
Comp. Rend. 136, 738).

Ethylene and methane are also formed
by the catalytic action of heated alumina
or fire-clay on alcohol vapour (IpatiefP,
Ber. 36, 1990; 2003).

[E, p. 24.] Isopropi/l alcohol [16]
gives methane among the products of
decomposition by finely divided heated
copper (210°) (Sabatier and Senderens,
loc. oil. 983).

[J^ p. 24.] Acetone [IO6] in aqueous
solution yields methane (and acetic
acid) by photochemical decomposition
(Ciamician and Silber, Ber. 36, i575)-

For the electrolytic preparation of
iodoform from acetone see Howe Abbott,
Journ. Physical Ch. 19O3, pp. 84-91.

[S, p. 25.] Malonic acid [Vol. II] in
glycerol or ethylene glycol gives meth-
ane among the products of decomposi-
tion on heating in a sealed tube (CE. de
Coninck and Raynaud, Comp. Rend.
135, 1351).

[BB, p. 26.] Malic acid [Vol. II]
gives methane among other products
under the above conditions [Ifjid.).

[CC, p. 26.] Citric acid [Vol. II]

when heated in glycerol solution gives
methane among other products {Ibid.).

[II, p. 26.] Tartaric acid [Vol. II]
when heated in glycol solution with sul-
phuric acid gives methane anaong other
products {Ibid.).

[J J, p. 26.] Camphor [175] gives
methane among the products of decom-
position by heating with zinc chloride
(Montgolfier, Ann. Chim. [5] 14, 87). Or
on heating with strong hydriodic acid
at 200° methyl iodide is formed among
other products (Markownikoff and Gor-
benko, Ber. 30, 1216), and this can be
converted into methane by reduction,
as under C, p. 22. Or on heating at
200° with iodine chloride, chlorinated
camphor yields among other products
carbon tetrachloride (Ruoff, Ber. 9,
1048 ; 1483 ; I499)^and this can be con-
verted into methane as under L, p. 25.

5. Heutriacontane (p. 28).

A hydrocarbon of the above composi-
tion (? normal) has been obtained from
the East Indian ko-sam seeds from
Brucea sumatrana (Power and Lees,
Pharm. Journ. [4] 17, 183).

6. Cymene (p. 28).
To be added to synthetical processes

(P- 33) :— . .

[N.] ' Terpinene is readily converted
into cymene by the oxidising influence
of sulphuric acid '' (Heusler's 'Chemistry
of the Terpenes/ Pond, p. 113).

[O.] From camjjhor [175] by heating
with zinc chloride (?), phosphoius pent-
oxide, pentachloride or pentasulphide,
or strong hydrochloric acid (Gerhardt,
Ann. 48, 234; Dumas and Delalande,
Ann. 38, 342; Pott, Ber. 2, 121 ;
Fittig, Kobrich, and Jilke, Ann. 146,
129; Wright, Journ. Ch. Soc. 26,
686 ; Beckett and Wright, Ibid. 29, 1 ;
Renter, Ber. 16, 694 ; Armstrong and
Miller, Ber. 16, 2259 ; Alexejeff, Journ.
Russ. Soc. 12, ] 87 : according to Bredt,
Rochussen, and Monheim, Ann. 314,
369, carvenone is an intermediate
product).

278

APPENDIX

[P.] Camphene [l77] when heated
with phosphorus pentoxide gives an
oily product, which may contain cymene
(Heusler's ' Chemistry "of the Terpenes/
Pond, p. 59).

[Q.] From mentliene [178] by heating
with anhydrous cuprie sulphate at 250°
(Briihl, Ber. 25, 151).

7. Styrene (p. '>,'^.

To be added to synthetical pro-
cesses : —

[A, p. 33.] The formation of styrene
from nascent acetylene and benzene in
presence of aluminium chloride is con-
firmed by Parone (Journ. Ch. Soc. 86,
I, a6; from L'Orosi, 25, 148).

9. Dipentene and Limonene (p. ^(>).

The presence of this hydrocarbon in
neroli oil is confirmed by Hesse and
Zeitschel (Journ. pr. Ch. [3] 66, 481)
and by Walbaum and Hiithig {Ibid.
67, 315)- ^^he last-named authors {loc.
cit.) confirm also the presence of di-
pentene in petit-grain oil from Para-
guay. For further reference to the
occurrence of 1-limonene in verbena oil
from Verbena iriphylla see Theulier, Bull.
Soc. [3] 27, 1 1 13.

13. Methyl Alcohol (p. 40).

The cohobation water of oil of savin
from Juniperus sabina and the distilla-
tion water from the oil of W. Indian
sandal- wood contain methyl alcohol
(SchimmePs Ber. April, 1903; Ch.
Centr. 1903, 1, 1086). The presence
of methyl salicylate and benzoate in
ylang-ylang oil is confirmed [Ibid.),
and the occurrence of methyl anthrani-
late in this same oil recorded [Ibid.).
Methyl salicylate is a constituent of
the oil of cassia flowers from Acacia
cavenia and A. farnesiana (Walbaum,
Journ. pr. Ch. [2] 68, 235), and methyl
anthranilate a constituent of the essen-
tial oil of tuberose blossoms. This last
oil, when obtained by ' enfleurage '
instead of by extraction with petro-
leum, contain^ also methyl salicylate
(Hesse, Ber. 36, 1459). Methyl an-
thranilate has been found in petit-grain

oil from Paraguay (Walbaum and
Hiithig, Journ. pr. Ch. [2] 67, ^i^'-
for estimates of the quantities of
methyl anthranilate and other con-
stituents of average oil of neroli see
further Hesse and Zeitschel, Ibid. 66,
481).

To be added to synthetical pro-
cesses : —

[D, p. 44.] Formic aldehy^de gives
methyl alcohol by catalytic reduction
by hydrogen in presence of finely
divided heated nickel at 90° (Sabatier
and Senderens, Comp. Rend. 137, 301).

[P, p. 44.] For the industrial pro-
duction of methyl alcohol (and formic
aldehyde) by the electrolysis of sodium
acetate in presence of sodium chlorate
see Moest^s Germ. Pat. 138442 ; Journ.
Ch. Soc. 84, I, 546.

[L, p. 44.] Camphor [175] gives
methyl iodide among other products
when heated with strong hydriodic
acid at 200° (Markownikoff and Gor-
benko, Ber. 30, 12 16). From methyl
iodide through methyl acetate followed
by hydrolysis, or by any of the visual
methods.

14. Ethyl Alcohol (p. 44).

Further researches on anaerobic, intrar
molecular alcoholic fermentation in
sugar-beet have been published by
Stoklasa, Jelinek, and Vitek (Beit. ch.
Physiol, u. Path. 3, 460 ; Zeit. Zucker-
Ind. Bohm. 27, 633), and in peas in
potassium nitrate solution with dextrose
or peptone by Nabokich (Ber. deutsch.
bot. GeselL, 21, 398; Ch. Centr. 1903,
2, 1 01 2). Further studies of the en-
zymes from the cells of the higher
animals and plants which produce this
fermentation have been undertaken by
Stoklasa and Czerny (Ber. 36, 4058).
According to Cohnheim (Centr. Physiol.
17, No. 17) and to Batelli (Comp. Bend.
137, 1079) this alcoholic fermentation
by^ supposed animal enzymes is due to
micro-organisms.

With reference to selective fermenta-
tive action in connexion with stereo-
chemical configuration (pp. 46-47),
Schizo-Saccharomi/ces octosporus of Beye-
rinck and Miicor alternaus ferment mal-

APPENDIX

279

tose and methyl-d-glueoside, but not
cane-sugar or a-methyl-d-fructoside.
The enzymes extracted from cultivated
As])ergillus niger resolve amygdalin and
the iS-d-glucosides, but not lactose or
methyl-d-galactosides. Duclaux, Kay-
ser, and Adametz's milk-sugar ferment-
ing yeasts ferment milk-sugar and
/3-methyl-d-galactoside, and give an
enzyme which acts on the two galacto-
sides (Pottevin, Comp. Rend. 136^ 169).

With respect to ' zymase ' (p. 48) the
velocity of decomposition of dextrose
and Isevulose by the commercial product
has been determined by Herzog^ and
found to agree with ordinary ' catalytic^
actions (Zeit. physiol. Ch. 37, 149)-
The velocity of the fermentative de-
composition of dextrose by yeast has
been determined by Aberson (Rec. Tr.
Ch. 22, 78). Further experiments on
the fermentative properties of yeast-
extract have been made by Meisen-
heimer (Zeit. physiol. Ch. 37, 518).

The ' acclimatisation'' of yeasts (p. 50)
to solutions containing sodium fluoride
and the fermentation of the must of
Indian figs by such yeasts have been
investigated by Ulpiani and Sarcoli
(Atti Real. Accad. [5] 11, II, 173).
The species investigated were S. pa-s'to-
rianus II and S. cerevisice.

The mould, O'idium lactis (p. 50),
when grown upon media containing
Isevulose causes alcoholic fermentation
of this sugar (Teichert, Milch-Zeit. 31,
801 ; Journ. Ch. Soc. 84, II, 229).
The butyric ferment, Clostridiwn pasto-
rianum, from the soil of St. Peters-
burg, forms alcohol (small quantity)
among the products of fermentation of
dextrose in presence of appropriate
nitrogenous nourishment (Winograd-
sky, Centr. Bakter. II, 9, 4354, 107-
112). An organism isolated from milk,
Eiiterococcus, decomposes sugars with
the production of alcohol (traces) among
other products (Tissier and Gasching,
Ann. Inst. Past. 17, 540). Alcohol
has been found in milk which has
undergone natural curdling (Kozai,
Bied. Centr. 32, 273). The bacteria
which are capable of decomposing bone
produce alcohol when sugar is added
to the nutrient solution (Stoklasa,

Duchacek, and Pitra, Beit. ch. Physiol,
u. Path. 3, 322). The bacteria capable
of fermenting sugar belong to the type
of Bacillus coll comtminis of Escherich,
and produce alcohol from dextrose to
the extent of 1-2 to 2-0 per cent, by
weight (Konig, Spieckermann, and
Olig, Abst. in Journ. Ch, Soc. 84, II,
386). Alcohol is a product of glyco-
lysis by the minced pancreas, liver, &c.,
or the juices expressed from these
organs (Feinschmidt, Beit. ch. Physiol,
u. Path. 4, 511).

To be added to synthetical pro-

cesses

[D, p. 54.] Alcohol is among the
products of oxidation of ethane by
ozone (Bone and Drugman, Proc. Ch.
Soc. 20, 127).

[H, p. ^^."l Acetic aldehyde [02],
when the vapour mixed with hydrogen
is passed over finely divided nickel
heated to 140°, gives an almost quanti-
tative yield of alcohol (Sabatier and
Senderens, Comp. Rend. 137, 301).

[S, p. ^6."] The amyl ester of acetic
acid gives ethyl alcohol when reduced
with sodium in amyl alcohol solution
(Bouveault and Blanc, Comp. Rend.
137, 60).

[MM, p. 58.] Isopropyl alcohol [I6]
gives ethane among other products by
the catalytic action of finely divided,
reduced copper at 210° (Sabatier and
Senderens, Comp. Rend. 136, 983).
From ethane as under D, p. 54.

[NN, p. 58.] Gli/col [45] gives ethyl
iodide on heating with strong aqueous
hydriodic acid. From ethyl iodide the
alcohol can be obtained by any of the
ordinary processes. Or from glycol
through glycol chlorhydrin = chlorethyl
alcohol (see under n-propyl alcohol [15 ;
A, p. 59] and under isopropyl alcohol
[le ; C, p. 66]), the latter giving ethyl
alcohol on reduction with sodium amal-
gam (Louren90, Ann. 120, 92).

Note : — Ethylene is also a direct generator
of glycol chlorhydrin [15 ; A, p. 59, and 16 ;
C, p. 66].

[00, p. 58.] Camphor [175] gives
methyl iodide (see under methane [l;
Appendix, JJ, p. 277]). From the latter
through ethane, as under D, p. 54-

280

APPENDIX

15. Normal Propyl Alcohol (p. 58). 17. Normal Butyl Alcohol (p- 69).

Propyl alcohol is among' the products
o£ the butyric fermentation of dextrose
by Clostridium pastoriamim (Winograd-
sky, Centr. Bakter. 11^ Q, 4354 ; 107-
113).

To be added to synthetical pro-
cesses : —

[E, p. 59.] Or allyl bromide in
ethereal solution is acted upon by
carbon dioxide in presence of magne-
sium with the formation of vinylacetic
acid (Houben^ Ber. 30^ 3897). From
the latter through crotonic acid, as
under W, p. 6^, and I, p. 60, &c.

KoTE : — This synthesis of vinylacetic acid
from glycerol via allyl bromide relates also
to formic aldehyde [91 ; GG, p. 174], acetic aldehyde
[92 ; Z, p. 180], and to hexoic aldehyde [96 ; C,
p. 186].

[N, p. 61.] Propionic aldehyde is
reduced to the alcohol by hydrogen
under the contact influence of finely
divided nickel at 102-145° (Sabatier
and Senderens, Comp. Rend. 137, 301).

16. Isopropyl Alcohol (p. 64).

To be added to synthetical pro-
cesses : —

[A, p. 6^."] Acetone vapour mixed
with hydrogen and passed over finely
divided nickel heated to 115-125° gives
isopropyl alcohol (Sabatier and Sen-
derens, loc. cit,).

[B, p. 65.] The vapour of n-propyl
alcohol is decomposed at 560° by the
'contact ^action of alumina into propyl-
ene and water almost quantitatively
(IpatiefF, Ber. 36, 1990).

[O, p. 67.] Acetyl carbinol (acetol)
gives isopropyl alcohol among other pro-
ducts by direct reduction with sodium
amalgam in alkaline solution (Kling,
Comp. Rend. 135, 970 ; Bull. Soc. [3]
29, 92 : see also under A, p. 6^).

[QQ, p. 69.] From camphor [l75],
which gives isopropyl iodide among
other products on heating with strong
aqueous hydriodic acid at 200° (Mar-
kownikoff and Gorbenko, Ber. 30,
1 21 6). From the iodide as under B,
p. 65.

[A, p. 70.] From ethyl alcohol
through ethylene oxide (see under
acetic aldehyde [92 ; A, p. 175]). The
latter interacts with magnesium ethyl
bromide in ethereal solution at - 15° to
form a product which yields n-butyl
alcohol on distillation in steam (Gri-
gnard, Comp. Rend. 136, 1260).

[L, p. 7 !•] Methyl butyrate on reduc-
tion with sodium in alcoholic solution
gives n-butyl alcohol (Bouveault and
Blanc, Comp. Rend. 137, 60).

18. Isobutyl Alcohol (p. 72).

For occurrence of butyl (? isobutyl)
alcohol in Roman oil of chamomile see
further Blaise, Bull. Soc. [3] 29, 327.
Isobutyl alcohol is among the j)roducts
of butyric fermentation of dextrose by
Clodridium, pastoriamim (Winogradsky,
Centr. Bakter. II, 9, 4354; 1 07-1 12).

To be added to synthetical pro-
cesses : —

[A, p. 72.] Tertiary butyl alcohol
also gives isobutylene by catalytic de-
composition on passing the vapour over
finely divided copper heated to 280-
400° (Sabatier and Senderens, Comp.
Rend. 136, 983).

[D, p. 73.] Or from acetone through
diacetonamine or mesityl oxide (see
under acetic aldehyde [92; S, p. 179]).
Diacetonamine by the action of nitrous
acid is transformed into diacetone alco-
hol = dimethylacetonyl carbinol (Heintz,
Ann. 178, 342 : see also Ann. 169, 1 14).
The latter is oxidised by bromine in
presence of aqueous alkali to /3-hydroxy-
isovaleric acid (Kohn, Monats. 24, 765).
From the latter through /3-dimethyl-
acrylic acid and isobutylene as under
^i P' !?>' ^^ mesityl oxide, on oxida-
tion with bromine in presence of alkali,
gives ^-dimethylacrylic acid directly
(Kohn, loc. cit.).

Note : — This synthesis affects also tertiary
butyl alcohol [19 ; D, p. 75] and isobutyric
aldehyde [94 ; E, p. 182].

[E, p. 73.] The vapour of isobutyric
aldehyde mixed with hydrogen and
passed over finely divided nickel at

APPENDIX

281

135-160° gives isobutyl alcohol by
catalytic reduction (Sabatier and Sen-
derens, Comp. Rend. 137, 30i)«

19. Tertiary Butyl Alcohol (p. 73).

[B, p. 74.] Isobutyl alcohol gives
isobutylene as the only olefine by pyro-
genic 'contact-' decomposition of its
vapour by heated alumina (Ipatieff,
Ber. 36, 2003). Isobutylene is absorbed
at 0° by aqueous hydrobromic acid with
the formation of tertiary butyl bromide,
which can be converted into the alcohol
by the usual processes (Ipatieff and
Ogonowsky, i^/i/. 1988; Journ. Russ.
Soc. 35, 452).

[K, p. 76.] From methyl alcohol [l3]
2iQ& phosgene, formed by the combina-
tion of carbon monoxide and chlorine.
Magnesium methiodide and phosgene
interact with the formation of trimethyl
carbinol (Grignard, Comp. Rend. 136,

21. Methylpropyl Carbinol (p. 77).

To be added to synthetical pro-
cesses : —

[B, p. 77.] Butyramide and magne-
sium methiodide interact to form a com-
pound which is decomposed by water
into methylpropyl ketone (B^is, Comp.
Rend. 137, 5^s)-

[E, p. 78.] Propionic acid and ethyl
alcohol [14] also yield diethyl ketone
by the interaction of propionamide and
magnesium ethobromide, and decom-
position of the product with water
(Beis, lac. cit.).

when mixed with hydrogen and passed
over reduced nickel at 135-165°, gives
isoamyl alcohol by catalytic reduction
(Sabatier and Senderens, Comp. Rend.
137, 301).

[C, p. 80.] From methyl and ethyl
alcohols [13; 14] and tartaric acid
[Vol. II]. The latter is converted into
pyroracemie (pyruvic) acid (see under
benzyl alcohol [54; W, p. 114]), and
the ethyl ester of the latter allowed to
interact with magnesium methiodide,
when isoamyl a-hydroxyisobutyrate is
formed (Grignard, Comp. Rend. 135,
627). The alcohol could be obtained
from its ester by hydrolysis.

Note : — Generators of pyroracemie acid other
than tartaric acid are available for this
synthesis.

24. IsoHezyl Alcohol (p. 82).

To be added to synthetical pro-
cesses : —

[C, p. 82.] From ethyl and isobutyl
alcohols [14 ; 18] and aceioacetic ester
[Vol. IIJ. Ethyl isobutyl-acetoacetate
on reduction in alcoholic solution with
sodium gives isohexyl alcohol (Bou-
veault and Blanc, Comp. Rend. 137,
338).

25. Active Hexyl Alcohol (p. 83).

Further confirmation of the presence
of this alcohol in Roman oil of chamo-
mile is given by Blaise, Bull. Soc. [3]
29, 327.

22. Isoamyl Alcohol (p. 79).

For occurrence of isoamyl alcohol in
Roman oil of chamomile see further
Blaise, Bull. Soc. [3] 29, 327. An
amyl alcohol (probably isoamyl) has
been found in oil of lavender (Schim-
mel's Ber. April, 1903; Ch. Centr.
1903, 1, 1086).

To be added to synthetical pro-
cesses :—

[A, p. 80.] Isovaleric aldehyde vapour.

27. Isoheptyl Alcohol (p. 83).

To be added to synthetical pro-
cesses : —

[A, p. 83.] Or from ethyl alcohol
through ethylene oxide [92; A, p. 175]
and isoamyl magnesium bromide. The
latter interacts with ethylene oxide in
ethereal solution to form a compound
which gives isoheptyl alcohol on steam
distillation (Grignard, Comp. Rend.
136, 1260).

282

APPENDIX

.28. Normal Primary Octyl
Alcohol (p. 84).

To be added to synthetical pro-
cesses : —

[C^ p. 84.] From n-ocfoic acid [Vol.
II], the methyl ester of which gives
n-octyl alcohol on reduction with
sodium in alcoholic solution (Bouveault
and Blanc, Comp. Kend. 136, 1676).

29. Secondary Nonyl Alcohol
= Methyl-n-heptyl Carbinol (p. 85).

For further details concerning- the
production of this alcohol by the reduc-
tion of the ketone see Thoms and
Mannich, Ber. 36, 2544.

30. Secondary Hendecatyl Alcohol
= Methyl-n-nonyl Carbinol (p. 85).

See further Thoms and Mannich as
above for the production of this alcohol
from the ketone.

35. Dimethylheptenol (p. 86).

[B, p. 86.] Barbier^s synthesis of this
alcohol from methylheptenone and
magnesium methiodide has been re-
peated by Harries and Weil (Ber. 37,
«45).

36. Geraniol (p. 87).

Further observations on the occur-
rence of geraniol and geranyl acetate in
neroli oil are given by Hesse and Zeit-
schel (Journ. pr. Ch. [2] 66, 481 :
compare Walbaum and Hiithig, Ibid.
67, 315)^ in lavender oil by Schimmel
& Co. (Sch. Ber. April, 1903 ; Ch.
Centr. 1903, 1, 1086), Geranyl capro-
ate is also present in this last oil (^Ibid.).
The presence of geraniol and geranyl
acetate in petit-grain oil from Para-
guay is confirmed by Walbaum and
Hiithig {loc. cit.). The influence of
season, temperature, &c., upon the com-
position of petit-grain oil has been
studied by Jeancard and Satie (Bull.
Soc. [3] 29, 1088).

37. Linalool (p. 88).

The quantity of linalyl acetate in
neroli has been estimated by Hesse and
Zeitschel (Journ. pr. Ch. [2] 66, 481).
The presence of 1-linalool and its ester
in this oil and in petit-gi*ain oil from
Paraguay is recorded also by Walbaum
and Hiithig {Thid. 67, 315)- Linalool
has been found in the oil from the
bark of Cinnamomum pedatinervium from
Fiji (Goulding, Trans. Ch. Soc. 83,
1099).

38. Citronellol (p. 89).

d-Citronellol is the alcohol corre-
sponding to d-citronellal (p. 192), and
its formula is accordingly : —

CH2.CH2.OH

CH2:C(CH3)[CH2]3.CH(CH3).
CH^.CF

2 : 6-Dimethyl-i-octenol-8.

For occurrence in Reunion geranium
oil see further Tiemann and Schmidt,
Ber. 30, 36.

The formula given on p. 89 is that
of the 1-alcohol contained in the plant
oils there referred to, and is the ^rho-
dinol ' of Barbier and Bouveault. Since
1-citronellol and d-citronellol are now
proved to be structurally isomeric the
former name is inappropriate.

Note : — The synthetical process A on p. 89
gives d-citronellol and not rhodinol. d-Rho-
dinol may be contained in pelargonium oil
(Monnet and Barbier, Comp. Kend. 117, 1092 ;
Barbier and Bouveault, Ibid. 122, 530 ; 673 ;
Bouveault, Bull. Soc. [3] 23, 458 ; 465).

39. Terpineol = l-Methyl-4-metho-
ethylol-4^-cyclohexene-l (p. 90).

d-Terpineol is contained in neroli oil
and in the oil mixed with the aqueous
distillate from orange flowers (Hesse
and Zeitschel, Journ. pr. Ch. [2] 66,
497 : for occurrence in neroli oil and in
petit-grain oil from Paraguay see also
Walbaum and Hiithig, Ibid. 67, 315).
1-Terpineol is present in distilled oil of
limes (Burgess and Page, Trans. Ch.
Soc. 85, 414).

APPENDIX

283

To be added to synthetical pro-
cesses : —

[D, p. 9T.] From methyl and ethyl
alcohols [l3 ; 14], glycerol [48], potas-
sium cyanide [l72], and acetic acid
[Vol. II]. Ethyl chloracetate is con-
verted into ethyl cyanacetate by inter-
action with potassium cyanide and
glycerol into /3-iodopropionic acid and
ester (see under resorcinol [70 ; I",
p. 1 14] and, for preparation of )Q-iodo-
propionic ester, also W. H. Perkin,
junr.^ Trans. Ch. Soc. 85, 422, note).
Cyanacetic and /3-iodopropionic esters
condense under the influence of sodium
ethoxide to form ethyl y-cyanopentane-
aye-tricarboxylate : the latter on hydro-
lysis by hydrochloric acid yields pent-
ane-aye-tricarboxylic acid {JMd. 423).
The tricarboxylic acid when digested
with acetic anhydride gives 8-keto-
hexahydrobenzoic acid, the ester of
which interacts with magnesium meth-
iodide to form among other products
cis-h- hydroxy hexahydro - p - toluic acid
(W. H. P., junr., Proc. Ch. Soc. 20,
86 : see also Stephan and Helle, Ber.
35, 3153). The latter acid (or its
lactone formed by the action of heat)
combines with hydrogen bromide to
form 8-bromhexahydro-p-toluic acid,
and this on debromination by the
action of pyridine or sodium carbonate
is converted into A^-tetrahydro-p-toluic
acid, the ester of which interacts in
ethereal solution with magnesium meth-
iodide to form a product which yields
inactive terpineol on decomposition by
hydrochloric acid (W. H. P., junr.,
loc. cit.).

Note : — Succinic acid is also a generator of
/3-iodopropionic acid (see under resorcinol [70 ;
F, p. 145]). Cyanacetic acid is also obtainable
from oxalacetic ester (see under n-propyl
alcohol [15 ; Z, p. 63]).

stituent of the oil of Calif ornian laurel
from Umhellularia californica (Power
and Lees, Proc. Ch. Soc. 20, 88).

41. Menthol (p. 93).

For variation in composition of
peppermint oil from Mentha piperita
according to climate, cultivation, &c.,
see Charabot and Hebert, Ann. Agro-
nom. 28, 595. For quantities of
menthol in Italian peppermint oils see
Zay, Staz. sper. agrar. 35, 816 j Ch.
Centr. 1903, 1, 331.

To be added to synthetical pro-
cesses : —

[B, p. 93.] For reduction of menth-
one to menthol see further Beckmann's
Germ. Pat. 42458 of 1887; Ber. 21,
Ref. 321.

42. Isopulegol (p. 93).

The relationship of this compound
to d-citronellal [l05] and the modifica-
tion of the formula of the latter (see
this appendix under citronellol [38,
above]) makes the formula of iso-
pulegol : —

CH3

CH

HjC CH2

HjC CH(OH)

CH
HoC . C r CHo

For transformation of d-citronellal into
isopulegol by the action of dilute sul-
phuric acid see Barbier and Leser, Comp.
Rend. 124, 1309.

40. Cineole (p. 91).

Cineole (eucalyptole) is always present
in peppermint oil from Mentha piperita
(Charabot and Hebert, Ann. Agronom.
28, 595). The presence of cineole in
lavender oil has been confirmed (Schim-
mePs Ber. April, 1903; Ch. Centr.
1903, 1, 1086). Cineole is a con-

44. Methylacetyl CarMnol (p. 94).

To be added to synthetical pro-
cesses : —

[D, p. 94, note.] Magnesium ethiodide or
bromide and acetamide interact to form a com-
pound which on decomposition by water yields
methyl ethyl ketone (Beis, Comp. Rend. 137,

.575)-

284

APPENDIX

48. Glycerol (p. 96).

Glycerol is formed during the an-
aerobic (intramolecular) respiration of
the sugar beet (Stoklasa, Jelinek, and
Vitek, Zeit. Zucker-Ind. Bohm. 27,

633)'

According to Nicloux, glycerol

(traces) is normally present in the

blood of dogs and rabbits (Comp. Rend.

136,764; 1576: compare Mouneyrat,

Comp, Rend. Soc. Biol. 55, 1207 ; Ni-

cloux, Idid. 1329).

51. Mannitol (p. 104).

The ferment of sour wine forms
mannitol in presence of Isevulose, Re-
ducing bacteria which liberate hydro-
gen and the amylo-baeteria cultivated
in invert sugar solution in presence
of chalk are incapable of producing
mannitol from Isevulose (Maze and
Perrier, Ann. Inst. Past. 17, 597)-

54. Benzyl Alcohol (p. 107).

Benzyl alcohol and ester are present
in the oil obtained from tuberose
blossoms by distillation or by enfleur-
age (Hesse, Ber, 36, 1459). Benzyl
alcohol (with its acetic and benzoic
esters) is contained in ylang-ylang oil
(SchimmePs Ber. April, 1903; Ch.
Centr. 1903, 1^ 1086).

To be added to synthetical pro-
cesses : —

[A, p. 108.] Benzene can be con-
verted into toluene by the interaction
of phenyl magnesium bromide and
dimethyl sulphate in ethereal solution
(Werner and Zilkens, Ber. 36, 2116 ;
Houben, Mid. 3083 ; Werner, Ibid.
3618).

[R, p. 1 1 5-] Phthalic acid can be
obtained from the naphthols, nitro-
naphthalene, the naphthylamines, nitro-
naphthols, naphthalene sulphonic acids,
&c., by oxidising with metallic oxides
in presence of heated alkaline hydr-
oxides (Basler, Ch. Fab. Germ. Pats.
138790; 139956; 140999; Journ. Ch.
Soc. 84,1,487; 561).

[DD, p. 1 1 6.] Sodium ethyl succinate

on electrolysis gives, among other pro-
ducts, a small quantity of ethyl acryl-
ate (Bouveault^ Bull. Soc. [3] 29,
1043). From acrylic acid as under I,
p. Ill, &c.

[KK, p. 116.] CampJior [l75] gives
toluene among the products of its
decomposition by heating with zinc
chloride (Fittig^ Kobrich, and Jilke,
Ann. 145, 129 ; Renter, Ber. 16, 694),
or with zinc dust (Schrotter, Ber. 13,
1621).

55. Saligenin (p. 116).

The quantity of salicin in buds,
leaves_, and bark of 8alix ptirimrea at
various periods of growth has been
determined by Weevers (Proc. k. Akad.
Wetensch. Amsterdam, 6, 295).

57. Phenylethyl Alcohol (p. 118).

For occurrence of this alcohol in
n6roli oil see further Walbaum and
Hiithig, Journ. pr. Ch. [2] 67, 315 :
also SchimmeFs Ber. April, 1903 ; Ch.
Centr. 1903, \, 1086.

To be added to synthetical pro-
cesses : —

[A, p. 118.] Phenylacetic ethyl ester
is reduced to phenylethyl alcohol by
sodium in alcoholic solution (Bouveault
and Blanc, Comp. Rend. 137, 60).

Note : — The alcohol obtained by Grignard
and Tissier (Comp. Rend. 134, 107) by the
condensation of trioxymethylene and magne-
sium benzyl chloride is not, as at first supposed,
benzyl carbinol, but the isomeric o-toluyl car-
binol (Tiffeneau and Delange, Comp. Rend.
137, 573).

58. Methylphenyl Carbinol (p. 118).

The alcohol has been found in the
steam-distilled oil of orange blossoms
(Hesse and Zeitschel, Journ. pr. Ch. [2]
66, 481).

59. Phenylpropyl Alcohol (p. 119).

To be added to synthetical pro-
cesses : —

[B^ p. 119.] From cinnamic acid
[Vol. II], the ethyl ester of which
a-ives the above alcohol on reduction

APPENDIX

285

with sodium in alcoholic solution (Bou-
veault and Blanc, Comp. Eend. 137,
328).

60. Phenol (p. 119).

Phenol is among- the products of the
decomposition of fodder bj micro-
organisms (Konig, Spieckermann, and
Olig, Journ. Ch. Soc. 84, 11, 447).

To be added to synthetical pro-
cesses : —

[A, p. 130.] Haloid derivatives of
benzene, e. g. brombenzene, interact
with magnesium in ethereal solution
to form a phenyl-magnesium halide,
which is oxidised by air with the
formation of a product which yields
phenol (18 per cent.) on treatment with
aqueous alkali (Bodroux Bull. Soc. [■:(]
31. 33)'

[tr, p. 124, note.] For preparation of gluta-
conic ester from acetonedicarboxylic acid via
^-hydroxyglutaric acid see further Blaise, Bull.
Soc. [3] 29, 1012.

61. Orthocresol (p. 124).

To be added to synthetical pro-
cesses : —

[A, p. 124.] Also from toluene
through o-bromtoluene, o-bromtoluyl
magnesium bromide, and oxidation, &c.,
of latter as under phenol (60 ; A, above ;
Bodroux, loc. cit.).

[J, p. 127.] Dihydrocarveol by oxida-
tion is converted into tri hydroxy hexa-
hydrocymene, which by further oxida-
tion with sulphuric and chromic acids
gives I -methyl-4-ethylonecyclohexanol-
2, and this by the action of sodium
hypobromite yields i-methylcyclohexa-
nol-2-carboxylic-4-acid. By the action
of bromine at 190° the latter is con-
verted into 2-hydroxy-p-toluic acid
(Tiemann and Semmler, Ber. 28, 2144 :
see also Einhorn and Willstatter, Ann.
280, 88), which gives o-cresol as under
A, p. 125.

[L, p. 128.] From camphor [175]
through cymene and then as under C,
p. 127. According to Renter (Ber. 16,
694); o-cresol is among the products
obtained by heating camphor with zinc
chloride. Pseudocumene is also among

the products of decomposition of cam-
phor by this last process {Ibid.) and
possibly among the products obtained
by heating camphor with zinc dust
(Schrotter, Ber. 13, 162 1). From
pseudocumene through m-xylene, &c.,
as under B, p. 126.

62. Metacresol (p. 128).

To be added to synthetical pro-
cesses : —

[A, p. 129.] p-Xylene can be obtained
also from toluene or benzene by the
interaction of p-toluyl magnesium brom-
ide and dimethyl sulphate (Werner and
Zilkens, Ber. 36, 2 116), or of p-brom-
phenyl magnesium bromide and di-
methyl sulphate in ethereal solution
(Houben, Ibid. 3083).

[C, p. 129.] Or the ethyl ester of
m-hydroxyuvitic (= a-coccinic) acid is
decomposed on heating with the forma-
tion of 5-hydroxy-o-toluic acid (Claisen,
Ann. 297, 46). From the latter as
under A, p. 128.

Note :— m-Hydroxyuvitic ester has been ob-
tained also from ethoxymethylene-acetoacetic
ester (from acetoacetic and orthoformic ethyl
esters condensed by means of acetic anhydride,
Claisen, Ber. 26, 2731) and acetonedicarboxylic
ester (see under orcinol [75 ; C, p. 154]). The
two esters condense in presence of sodium
ethylate to form methylhydroxytrimesic tri-
ethyl ester, the sodium derivative of vrhich is
converted into the diethyl ester on boiling with
water. ^The diethyl ester on distillation at
220-230° under 60 mm. pressure gives m-
hydroxyuvitic acid (Errera, Ber. 32, 2785 ; for
production of the ethyl ester of m-hydroxy-
uvitic acid from methenylbisacetoacetic ester
see further Claisen, Ann. 297, 43).

[K, p. 130.] From camphor [175],
p-xylene being among the products
formed by heating this compound with
zinc dust (Schrotter, Ber. 13, 1621).
From p-xylene as under A, p. 1 29.

63. Faracresol (p. 130).

To be added to synthetical pro-
cesses : —

[A, p. 131.] Or from toluene through
p-bromtoluene, p-bromtoluyl magne-
sium bromide, and oxidation, &c., of
the latter as under phenol (60; A,
above in this appendix ; Bodroux, Bull,
Soc. [3] 31, '>,^),

386

APPENDIX

[G^ p. 133.] From jpTienylacetic acid
[Vol. II] through the a : 4-dinitro-aci(i
and 2 : 4-dinitrotoluene (see under o-
cresol [61 ; H^ p. 1 27]). From the latter
as under A, p. 131.

64. Fhlorol (p. 133).

To be added to synthetical pro-
cesses : —

[A, p. 133.] Ethylbenzene can be
obtained from toluene by the interaction
of benzyl magnesium chloride and di-
methyl sulphate in ethereal solution
(Houben^ Ber, 36, 3083). Also by
the action of nascent acetylene on benz-
ene in presence of aluminium chloride
(Parone, Journ. Ch. Soc. 86, \, 26).

66. Carvacrol (p. 135).

To be added to synthetical pro-
cesses : —

[C, p. 136.] Camphor [175] gives
carvacrol when heated with iodine
(Kekule and Fleischer, Ber. Q, 1088 :
see also Clans, Journ. pr. Ch. 25, 264 ;
Schweizer, Ihid. 26, 118; Ann. 40,
329 ; Armstrong and Miller, Ber. 16,
2259). Carvacrol is among the pro-
ducts formed by heating camphor or
bromcamphor with zinc chloride (Arm-
strong and Miller, loc. cit. 2255 ;
R. Schife, Ber. 13, 1408).

69. Catechol (p. 137).

The catechol (protocatechuic acid)
complex is apparently contained in the
colouring-matter of the Japanese 'fu-
kugi ' (A. Gr. Perkin and Phipps, Trans.
Ch. Soc. 85, 60). The catechol com-
plex may be contained in epinephrine
= adrenalin = suprarenin, the active
principle of the suprarenal glands
(Jowett, Proc. Ch. Soc. 20, 18). The
cerebrospinal fluid from a case of hydro-
cephalus examined by Coriat did not
contain catechol (Am. Journ. Physiol.
10, III: compare Halliburton as quoted,
p. 140).

To be added to synthetical pro-
cesses : —

[A, p. 140.] Phenol-p-sulphonic acid
on chlorination at 50° gives 2-chlor-
phenol-p-sulphonic acid. The latter.

on heating the sodium salt with acid
or water at 180-200°, yields o-chlor-
phenol, which can be converted into
catechol as on p. 140 (Hazard-Flamand,
Germ. Pat. 141 751 j Journ. Ch. Soc.
84, I, 622).

70. Resorcinol (p. 142).

The resorcinol complex is apparently
contained in ononin, a glucoside obtained
from the root of rest-harrow. Ononis
spijiosa (v. Hemmelmayr, Monats. 24,
132)-

71. Quinol (p. 146).

Quinol and arbutin are contained in
the leaves and quinol in the flowers of
cranberry (Kanger, Arch. exp. Path.
50, 46; Ch. Centr. 1903, 2, 893).

75. Orcinol (p. 152).

Protocetraric acid, which is contained
in the lichens Ramalma ceruchis, Bendro-
grapka leucophaa, Cetraria islandica and
vars. vulgaris, platyna, crispa, subtubu-
losa, &c., C. complicata = C. laureri =
Platysma complicatiim, Sticta palmonaria,
Cladonia rangiferina var. vulgaris, C. sil-
vatica, C.Jimbriata var. chordalis, Par-
melia saxatilis vars. sulcata, pjanyiiformis,
and retirnga (Hesse, Journ. pr. Ch. [2]
57, 2S5; 272; 295; 441; 58, 467;
469; 62, 321 J 430; 68, I; Zopf,
Ann. 324, 39), gives rise to cetraric
acid by hydrolysis {Ibid. [2] 57, 300) :
the latter, and therefore its generator,
contains the orcinol complex (Simon,
Arch. Pharm. 240, 521). Cetraric acid
itself may exist ready formed in the
\\c\iGnBPertusaria amara, Cladonia rangi-
ferina, C. silvatica, and Citraria fah-
luensis (Hesse, Journ. pr. Ch. [2] 58,
502 ; 62, 477 ; Zopf, Ann. 300, 323 ;
328 J 352 : compare Hesse, loc. cit. 62,
477), and also in Cetraria islandica
(Simon, loc. cit.).

77. /3-Orcinol (p. 156).

To be added to synthetical pro-
cesses : —

[B, p. 156.] From camphor [175]
through p-xylene as under m-cresol

APPENDIX

287

[62;, in tliis appendix, p. 385]. From
p-xylene as under A., p. 156.

79. Isoeugenol (p. 157).

For occurrence of isoeugenol in ylang-
ylang oil see further SchimmeFs Ber.
April, 1903; Ch. Centr. 1903, 1, io85.

81. Methyleugenol = Engenol
Methyl Ether (p. 157).

This ether has also been found in
ylang-ylang oil (Schimmel & Co. as
above) and probably in the volatile oil
of the bark of Cinnamomum pedati-
nervium from Fiji (Goulding, Trans.
Ch. Soc. 83, 1097). Has been found
also in the essential oil of Californian
laurel from Umbellularia califoruica
(Power and Lees, Proc. Ch. Soc. 20,
88).

84. PyrogaUol (p. 159).

The pyrogallol (gallic acid) complex
is contained in glucogallin and tetrarin,
two glucotannoids from Chinese rhu-
barb (Gilson, Comp. Rend. 136, 385).

86. Phloroglucinol (p. 160).

The phloroglucinol complex appears
to be contained in catechin (Clauser,
Ber. 36, loi) and in the Japanese dye-
stuff, ' fukugi ' (A. G. Perkin and
Phipps, Trans. Ch. Soc. 85, 60). Kam-
pherol, which contains the phloro-
glucinol complex (p. 161, ante), has
been obtained from the flowers of the
blackthorn, Prmiiis spinosa [Ibid. ^y).

87. Antiarol (p. 163).

To be added to synthetical pro-
cesses : —

[A, p. 163.] Pyrogallol can be con-
verted into its trimethyl ether by
agitating with dimethyl sulphate in
presence of alkali (Ullmann, Ann. 327,
104).

90. a-Hydrojuglone (p. 165).

Syntheses of Naphthalene.

[A, p. 166.] Naphthalene is among
the products of decomposition of the

vapour of ethyl alcohol at 500° (Ber-
thelot, 'Traite de Chimie Organique,'
187a, p. 164).

91. Formic Aldehyde (p. 169).

To be added to synthetical pro-
cesses : —

[C, p. 169.] Methyl alcohol gives
formic aldehyde on oxidation by ozone
(Harries, Ber. 36, 1933). '^^® vapour
of methyl alcohol mixed with air and
passed over a platinum spiral gives at
200° chiefly methylal ; at a dark red
heat formic aldehyde is also produced
(TriUat, Bull. Soc. [3] 29, ^^'. for
technical process depending on the
oxidation of the alcohol by air in
a heated coppered tube see also this
author's Germ. Pat. 55176 of 1889;
Ber. 24, Eef. 434).

[D, p. 170.] Methylene iodide from
ethyl alcohol via iodoform gives methyl-
ene bromide by the action of bromine
(Butleroff, Ann. Ill, 251). The brom-
ide, on heating with water or with lead
oxide and water at 150°, gives in the
latter case a quantitative yield of
formic aldehyde (Kloss, Monats. 24,

783)-

The conversion of trioxymethylene
into the monomolecular aldehyde can
be effected by the action of a methyl
alcoholic solution of hydrogen chloride
on the polymeride in presence of con-
densing agents so as to form chlor-
methyl methyl ether, ClCHg. O . CH3.
The latter is decomposed by water with
the formation of the monomolecular
aldehyde (Wedekind,Germ. Pat, 1353 10
of 1901; Ch. Centr. 1902, 2, 1164;
Pharm. Zeit. 47, 836; Ch. Centr. 1902,
2, 1301).

[H, p. 171.] For electrolytic prepara-
tion of formic aldehyde from sodium
acetate in presence of sodium chlorate
see also Moest's Germ. Pat. 138442 of
1902; Journ. Ch. Soc. 84, I, 546).

92. Acetic Aldehyde (p. 174).

The bacteria which cause the decom-
position of vegetable foods, and which
belong to the type of Bacillus coli
communis, produce aldehyde among

288

APPENDIX

other compounds in a solution o£ dex-
trose (Konig, Spieckermann, and Olig,
Journ. Ch. Soc. 84, II, 386). The
presence of acetic aldehyde in oil of
peppermint has been confirmed by
Charabot and Hebert (Ann. Agronom.
28, 595).

To be added to synthetical pro-
cesses : —

[A, p. 175.3 Ethylene oxide is com-
pletely converted into acetic aldehyde
by the ' contact ' action of alumina on
the vapour at 200° (Ipatieff and Leonto-
witsch, Ber. 36, 2016).

[B, p. 175.] Acetic aldehyde is among
the products of oxidation of ethane by
ozone (Bone and Drugman, Proc. Ch.
Soc. 20, 127).

[C, p. 175-3 For further study of the
oxidation of alcohol to aldehyde from
the electrochemical point of view see
paper by Slaboszewicz, Zeit. physik.
Ch. 42, 343. The production of alde-
hyde from alcohol vapour by pyrogenic
decomposition at 500° is referred to by
Berthelot, 'Traite de Ch. Org.' 1872,
p. 164. For further researches on the
pyrogenic ' contact ' conversion of alco-
hol into aldehyde, &c., by heated metals
and metallic oxides see paper by Ipatieff ,
Ber. 36, 1990.

94. Butyric Aldehyde (p. 181).

To be added to synthetical pro-
cesses : —

[D, p. 182.3 ^^^ production of iso-
butyric aldehyde from isobutylene oxide
, by the ' contact ' action of alumina on
the vapour at 200° see paper by Ipatieff
and Leontowitsch, Ber. 36, 2016.

95. Valeric Aldehyde (p. 183).

A valeric aldehyde occurs in pepper-
mint oil from Mentha piperita (Charabot
and Hebert, Ann. Agronom. 28, 595).
A valeric aldehyde is possibly present
in lavender oil (SchimmeFs Ber. April,
1903; Ch. Centr. 1903, 1, 1086).

96. Eexoic Aldehyde (p. 185).

Methylpropylacetaldehyde.

To be added to synthetical pro-
cesses : — ■

[A, p. 185.3 Propylene oxide, when

the vapour is passed through a tube
containing aluminium oxide heated to
200°, is resolved chiefly into propionic
aldehyde (Ipatieff and Leontowitsch,
Ber. 36, 2016).

100. Decoic Aldehyde (p. 189).

The occurrence of this aldehyde in
neroli oil is recorded by Walbaum and
Hiithig (Journ. pr. Ch. [2] 67, 315 :
see also Hesse and Zeitschel, Ibid. 66,
481). The aldehyde has been found in
the oil of cassia flowers from Acacia
cavenia (Walbaum, Ibid. 68, 235).

101. Acrolein (p. 190).

To be added to synthetical pro-
cesses : —

[A, p. 190.3 Glycerol gives acrolein
when heated with succinic acid, with
d-tartaric acid, or with malic acid (CE.
de Coninck and Raynaud, Comp. Rend.
135, 1351).

102. Crotonic Aldehyde (p. 190).

Solanin, a gluco-alkaloid found in
the berries of Solatium nigrum, S. dulca-
mara, S. verbascifolium , in stalks and
leaves of S. lycopersicum, and in shoots
of the potato, apparently contains the
crotonic aldehyde complex (Hilger and
Merkens, Ber. 36, 3204).

To be added to synthetical pro-
cesses : —

[J, p. 190.3 From glycol [45], cro-
tonic aldehyde being among the pro-
ducts of decomposition of this com-
pound by zinc chloride at 250° (Bauer,
' Repertoire de Chimie Pure,' 2 [18603,
344)-

104. Citral (p. 191).

For occurrence of citral in verbena
oil from Verbena triphylla see paper by
Theulier, Bull. Soc. [3] 27, 1113.

Note : — Since the rhodinal of Bouveault (see
under citronellal [105, p. 192]) is the aldehyde
derived from 1-citronellol = rhodinol [38, p. 89 ;
A, note, and this appendix, p. 282] and is not
identical with citral, the synonyms rhodinal
and licareal given for the latter (p. 191) must
be deleted. Rhodinal has not yet been shown
to be a natural product.

APPENDIX

289

105. Citronellal (p. 192).

The formula assigned to this com-
pound on p. 192 has been confirmed
(Barbier and Leser, Comp. Rend. 124,
1308; Harries and Roder, Ber. 32,
3363 : see also the note on p. 192). It
is therefore 2 : 6-dimethyl-i-oetenal-8,
and is the aldehyde of d-eitronellol [38,
p. 89, and this appendix]. For occui*-
rence in oil of lemon and of lemon-grass
see further Tiemann, Ber. 32, 812;
834 : compare also Stiehl, Journ. pr.
Ch. [2] 58, 62.

To be added to synthetical pro-
cesses : —

[B, p. 192.] From d-citronellol [38]
by oxidation with chromic acid mixture
(Tiemann and Schmidt, Ber. 30, 34).

106. Acetone (p. 192).

Acetone is said to be present in
normal horse urine (Kiesel, Pfliiger^s
Arch. 97, 480). Acetone occurs in the
expired air and in the urine of man
only in grave cases of diabetes (Le
Goff, Comp. Rend. 137, 216). Acetone
has been found in the fluid from a pan-
creatic cyst (Alay and Rispal, Journ.
Pharm. [6] 17, 319).

To be added to synthetical pro-
cesses : —

[B, p. 193.] Isopropyl alcohol is
readily converted into acetone by pass-
ing the vapour over reduced copper
heated to 250-430°. At 300° platinum
sponge acts in a similar way. Reduced
nickel is less effective (Sabatier and
Senderens, Comp. Rend. 136, 983).

A small quantity of acetone is
formed when the vapour of propylene
oxide is passed over aluminium oxide
heated to 200° (Ipatieff and Leonto-
witsch, Ber. 36, 2016).

[K, p. 196.] A solution of sodium
isobutyrate gives acetone when electro-
lysed in presence of sodium chlorate
(Moest, Germ. Pat. 138442 of 1902;
Journ. Ch. Soc. 84, I, 546).

[V, p. 199.] Methylheptenone gives
acetone among other products on oxida-
tion by ozone (Harries, Ber. 36, 1933).

113. Diacetyl (p. 203).

To be added to synthetical pro-
cesses : —

[B, p. 203.] Oxalic ester and magne-
sium methiodide interact in ethereal
solution to form a small quantity of
diacetyl (Gattermann and Maffezzoli,
Ber. 36, 4152).

114. Beuzoic Aldehyde (p. 205).

To be added to synthetical pro-
cesses : —

[A, p. 205.] Toluene, on passing the
vapour over heated lead oxide, gives
stilbene = symmetrical diphenylethylene
(Behr and Van Dorp, Ber. 6, 754 ;
Lorenz, Ber. 7, 1096; 8, 1455), or
benzal chloride gives stilbene on treat-
ment with sodium or zinc dust in
appropriate solvents (Limpricht, Ann.
139, 318; Lippmann and Hawliczek,
Jahresber. 1877, 405). Stilbene gives
benzoic aldehyde among other products
on oxidation with chromic acid mixture.
By photochemical oxidation stilbene
yields benzoic aldehyde as an inter-
mediate product (Ciamician and Silber,
Ber. 36, 4266).

Benzene and formic acid [Vol. II]
give benzoic aldehyde by the inter-
action of phenyl magnesium bromide
(from brombenzene and magnesium)
and formic ester in ethereal solution
(Gattermann and Maffezzoli, Ber. 36,
4152}.

[B, p. 208.] By the action of nitrous
gas on styrene in ethereal solution
a ' pseudonitrosite ^ is formed. This
gives benzoic aldehyde among the pro-
ducts of decomposition by hot aqueous
alkali or by sodium ethoxide solution
(Wieland, Ber. 36, 2558).

[C, p. 209.] Benzamide and magne-
sium methiodide interact to form a
compound which is decomposed by
water with the formation of aceto-
phenone (B^is, Comp. Rend. 137, ^"J^'

Note : — This synthesis affects all products
of which acetophenone is a generator, e. g.
methylphenyl carbinol [58 ; C, p. 118.]

[D, p. 209.] For production of benzoic
aldehyde by the electrolysis of a solu-

290

APPENDIX

tion of sodium plienylacetate in pre-
sence of sodium chlorate see Moest^s
Germ. Pat. 138442 of 1903; Journ.
Ch. Soc. 84, I, 546.

[E, p. 209.] Cinnamic acid yields
benzoic aldehyde (with glyoxylic acid)
when oxidised by ozone (Harries, Ber.
36, 1933).

The phenyl-a/3-dibrompropionic acid
or ester obtained by the combination of
cinnamic acid or ester with bromine
(see p. 209), on treatment with hot
alcoholic potash, gives two isomeric
a-bromcinnamic acids or esters (Glaser,
Ann. 143, 325 ; Sudborough and
Thompson, Trans. Ch. Soc. 83, 666).
Both these, which are stereo-isomerides,
yield benzoic aldehyde on oxidation by
potassium permanganate (Erlenmeyer,
Ber. 23, 2130).

[L, p. 211.] Benzyl alcohol gives
benzoic aldehyde and hydrogen when
the vapour is passed over reduced
copper heated to 300° (Sabatier and
Senderens, Comp. Rend. 136, 983).

[N, p. 211.] Frora formic and ci?t-
namic aldehydes [91; 123], a mixture
of these aldehydes giving benzoic alde-
hyde when allowed to stand in contact
with lime or baryta and water at 30-50°
for 1-2 days (Van Marie and Tollens,
Ber. 36, 1347).

119. Farahydroxybenzoic
Aldehyde (p. 215).

To be added to synthetical pro-
cesses : —

[A, p. 215.] The condensation of
phenol with hydrogen cyanide by
means of hydrogen chloride may take
place without the use of aluminium or
zinc chloride (Farb. vorm. F. Bayer
& Co., Germ. Pat. 106508 of 1898;
Ch. Centr. 1900, 1, 742).

[B and E, p. 216.] p-Nitrobenzoic
aldehyde is best reduced to the amino-
aldehyde by acid sodium sulphite (Cohn
and Sprinoer, Monats. 24, 87).

[G, p. 219.] Faraliydroxyhenzoic acid
[Vol. II] when heated with chloroform
m presence of alkali gives parahydroxy-
benzoic aldehyde (Reimer and Tiemann,
Ber. 9, 1268).

120. Anisic Aldehyde (p. 218).

To be added to synthetical pro-
cesses : —

[B, p. 218.] Or from anisole and
formic ester [Vol. II] through p-brom-
anisole and p-methoxyphenyl magne-
sium bromide, the latter interacting
with formic ester in ethereal solution
to form anisic aldehyde (Gattermann
and Maffezzoli, Ber. 36, 4153).

127. Carvone (p. 226).

The formula given in the text is
erroneous. The relationship of this
compound to limonene (see under 9 ;
E, p. 38) indicates for carvone the
formula : —

CH3

HC 0:0

I I

H^C.CrCHj

For literature relating to constitution
see Wagner, Ber. 27, 1653; 2270;
Wallach, Ber. 28, 1773; Tiemann and
Semmler, Ihld. 1778.

128. Pulegone (p. 226).

The ethereal oil, ^ marjolaine,'' of
Calamintha nepeta contains pulegone
(Genvresse and Chablay, Comp. Rend.
136, 387). The botanical source is
erroneously given as Origanum majorana
on p. 226.

129. Meuthoue (p. 227).

The variation in the composition of
peppermint oil from Mentha piperita
containing menthone, according to con-
ditions of climate, mode of cultiva-
tion, &c., has been studied by Ch^rabot
and Hebert (Ann. Agronom. 28, 595).

To be added to synthetical pro-
cesses : —

[A, p. 227.] For details of method
of oxidising menthol to menthone by
potassium dichromate and sulphuric
acid see further Flatau and Labbe,
Bull. Soc. [3] 19, 788.

APPENDIX

291

144. MetahydroxyauthraoLuinone

(p. 236).

Syntheses of Anthracene.

Nascent acetylene acts on benzene in
presence of aluminium chloride with
the formation of anthracene among
other products (Parone^ Journ. Ch.
Soc. 86, I, 26 ; from L'Orosi, 25,

148). , . ^

To be added to synthetical pro-
cesses : —

[C, p. 238.] Anthraquinone is oxi-
dised by ammonium persulphate in sul-
phuric acid solution with the formation
of m-hydroxyanthraquinone (Wacker,
Journ. pr. Ch. [2] 54, 89).

145. Alizarin (p. 238).

To be added to synthetical pro-
cesses : —

[A, p. 238.] For synthesis of alizarin
from catechol and phthalic anhydride
see further Liebermann and Hohenem-
ser, Ber. 35, 1779).

[B, p. 239.] Anthraquinonesulphonic
acid on extreme reduction by hydriodic
acid and phosphorus or by sodium
amalgam or ammonia and zinc dust
gives 2-anthracenesulphonic acid (Lie-
bermann, Ann. 212, 48 ; 57 ; Bischof
and Liebermann, Ber. 13, 47 ; 15, 852 :
according to Heffter, Ber. 28, 2262,
this sulphonic acid is also formed by
the direct sulphonation of anthracene
by dilute sulphuric acid). By alkaline
fusion this sulphonic acid yields 2-
anthrol (Liebermann, Ann. 212, 49).
By the action of sodium nitrite and
zinc chloride in alcoholic solution the
latter forms a nitroso-derivative, which
reduces to an amino-derivative. The
latter is oxidised by chromic and sul-
phuric acids to I : 2-anthraquinone, and
this is reduced by zinc dust and acetic
acid to I : 2-anthraquinol. The anthra-
quinol diacetate is oxidised by chromic
acid in acetic acid solution to alizarin
diacetate, and this yields alizarin on
hydrolysis (Lagodzinski, Ber. 27, 1438;
28, 116; 1422; 1427; 1533; 36,
4020).

Anthraquinone is directly oxidised to

alizarin by ammonium persulphate in
sulphuric acid solution (Wacker, Journ.
pr. Ch. [2] 54, 90).

148. Authragallol (p. 240).

To be added to synthetical pro-
cesses : —

[D, p. 240.] From m-hydroxyanthra"
qumone [144] through the i : 3-dinitro-
derivative by nitration (Simon, Ber.
14, 464). The latter, on reduction in
strongly alkaline solution, or by heat-
ing the corresponding i : 3-diamino-
derivative with aqueous hydrochloric
acid under pressure, or by the diazo-
method from the diamino-compound,
yields authragallol {Ibid. Germ. Pat.
I19755 of 1898; Ch. Centr. 1901,1,

979)-

149. Purpurin (p. 240).

To be added to synthetical pro-
cesses : —

[A, p. 24 1 .] Or quinizarin on bromina-
tion yields a 2-bromo-derivative (Lie-
bermann and Riiber, Ber. 33, 1658;
Farb. vorm. F. Bayer & Co., Germ.
Pat. 114199 of 1899; Ch. Centr. 1900,
2, 884). The latter, or the correspond-
ing chlorquinizarin, gives purpurin on
alkaline fusion (B. & Co., loc. cit.).
Quinizarin also gives purpurin on heat-
ing with sulphuric and nitrous acids in
presence of boric acid {Ibid, as below
under P).

[C, p. 241.] Alizarin gives purpurin
also on oxidation by ammonium per-
sulphate in sulphuric acid solution
(Wacker, Journ. pr. Ch. [2] 54, 90).

[P, p. 241.] From m-hydroxyanthra-
quinone [144], which, on treatment
with nitrous acid in the presence of
strong sulphuric and boric acids, yields
quinizarin (Farb. vorm. F. Bayer & Co.,
Germ. Pat. 81245 of 1893; Ber. 28,
Kef. 703; 86630 of 1895; Ber. 29,
Ref. 470). From quinizarin as under
A, p. 241, and above in this appendix.

Note : — Anthraquinone gives first quinizarin
and then purpurin on heating with sulphuric
acid in presence of boric acid (B. & Co.
Germ. Pat. 81960 of 1893 ; Ber. 28, Ref. 806).

u a

292

APPENDIX

151. Dihydrozyacetone (p. 24.2).

An oxidising Bacterium obtained
from wine vinegar produces dihydroxy-
acetone from glycerol (Sazerac, Comp.
Rend. 137, 90).

154. Dextrose (p. 244)-

In place of the constitutional formula
given in the text a ' lactone "* (alkylene
oxide) formula was proposed by Tollens
in 1883 (Ber. 16, 923) : —

HO HO HO H HO

H.C-

-C-

I
H

-C-

I
H

-CHo.OH

Further evidence in support of this
formula has recently been advanced, so
the literature is now given: — Sorokin,
Journ. pr. Ch. [2] 37, 312 j Erwig and
Koenigs, Ber. 22, 2207 ; 23, 672 ;
Skraup, Monats. 10, 401 ; Wohl, Ber.
23, 2098 ; E. F. Armstrong, Trans.
Ch. Soc. 83, 1305; Lowry, Ibid. 1314.
Dextrose is present in small quantity
in all the organs and tissues of the dog
and horse in the normal state (Cadeac
and Maignon, Comp. Rend. 136, 1682).
Human cerebrospinal fluid drawn by
lumbar puncture contains dextrose
(Rossi, Zeit. physiol. Ch. 39, 183:
see also Donath, Ibid. 526). The
globulins of blood on decomposition by
hydrobromic acid yield dextrose among
other carbohydrates, and may therefore
contain the dextrose complex (Lang-
stein, Ch. Centr. 1903, 1, 239). Grly-
collic aldehyde administered to rabbits
appears as dextrose in the urine (Paul
Mayer, Zeit. physiol. Ch. 38, 135).
Dextrose is present in human cephalo-
rachid liquid (Grimbert and Coulaud,
Comp. Rend. 136, 391).

155. Lavulose (p. 247).

Further researches on the relationship
between the soluble ferments and the
polysaccharides which they hydrolyse
(gentianose, &c.) have been published
by Bourquelot (Comp. Rend. 136, 762).

Stachyose, a sugar obtained from the

tubercles of StacJiys tuherifera, contains
the galactose, dextrose, and laevulose
complexes (v. Planta and Schulze, Ber.

23, 1692; 24, 2705; Landw. Versuchs.
Sta. 35, 473). According to Tanret
this tetrose is identical with the manneo-
tetrose (p. 248) of manna (Comp. Rend.
136, 1569).

Lsevulose is among the carbohydrates
resulting from the decomposition of the
globulins from horse blood serum by
hydrobromic acid (Langstein, Monats.

24, 445)-

156. Maunose (p. 248).

Salep mucilage (p. 248) has been
shown by analysis to be a tetrasacchar-
ide of d-mannose, and it is converted
quantitatively into the latter sugar on
hydrolysis (Hilger, Ber. 36, 3199).
A manno-galactan has been obtained
from Melilotus leucantha (Herissey,
Comp. Rend. Soc. Biol. 54, 11 74).

161. Methyl Mercaptau (p. 252).

Egg-meat mixture is rapidly decom-
posed by Bacillus coli communis with
the formation of mercaptan (? methyl)
among other products (Rettger, Am.
Journ. Physiol. 8, 284).

165. Secondary Butyl Isothio-
cyanate (p. 254).

To be added to synthetical pro-
cesses : —

[A, p. 254.] The vapour of n-butyl
alcohol passed over alumina heated to
500-520° gives 25-30 per cent, n-
butylene (Ipatieff, Ber, 36, 1999).

169. Benzyl Isothiocyanate (p. 257).

To be added to synthetical pro-
cesses : —

[A, p. 258.] Benzamide in pyridine
solution is converted into benzonitrile
by the action of carbonyl chloride (Ein-
horn and Mettler, Ber. 35, 3647).

[B, p. 258.] For electrolytic reduc-
tion of benzaldoxime to benzy lamina
see Germ. Pat. 141 346, Bohringer and
Sohne ; Journ. Ch. Soc. 84, I, 550.

APPENDIX

293

[E, p. 259.] By the action of nitrous
gas on styrene In ethereal solution
a ' pseudonitrosite ' is formed, which on
boiling with water is transformed into
y3-styrene nitrosite = a-nitroacetophen-
one-oxime. The latter, on boiling with
strong hydrochloric acid, yields (with
benzoic acid) benzonltrile (Wieland,
Ber. 36, 2558 : see also Sommer, Ber.

170. Fhenylethyl Isothiocyauate

(p. 260),

To be added to synthetical pro-
cesses : —

[A, p. 260.] Or benzyl magnesium
bromide (from benzyl bromide and
magnesium) Interacts In ethereal solu-
tion with formic ester [Vol. II] to
form phenylacetic = a-toJuic aldehyde
(Gattermann and Maffezzoli, Ber. 36,

4153)-

172. Hydrogen Cyanide (p. 262).

The presence of hydrogen cyanide in
sorghum has been confirmed and the
quantity estimated by Slade (Journ.
Am. Ch. Soe. 25, 55). Experiments
on the formation and determinations of
the quantity of hydrogen cyanide in
sorghum and other fodder-plants have

been undertaken by the Queensland
Department of Agriculture at the Bris-
bane Botanic Garden, and are described
In the paper referred to on p. 263
(Briinnich, Trans. Ch. Soc. 83, 788).
A cyanogenetic glucoslde, gynocardin,
has been obtained from the seeds of
Gynocardia oclorata (Power and Gornall,
Proc. Ch. Soe. 20, 137).

To be added to synthetical pro-
cesses : —

[A, p. 263.] Hydrogen cyanide is
formed by passing electric sparks
through a mixture of hydrogen, nitro-
gen, and carbon monoxide (Gruszkie-
wlcz, Zeit. Elektroch. 9, 83). Further
experiments on the production of
cyanides from nitrogen in presence of
strongly heated carbon and alkaline
carbonates, hydroxides, iron, &c., have
been carried out by Tauber (Ch. Ind.
26, 26; Ch. Centr. 1903, 1, 434).

[HH, p. 268.] From benzoic and acetic
acids [Vol. II] through acetophenone
and its nitroso- (Isonitroso-) derivative
(see under benzoic aldehyde [114 ; G,
p. 210]). The sodium compound of
isonltrosoacetophenone on heating,
or by the action of strong acid or
excess of aqueous alkali. Is resolved
Into benzoic acid and hydrogen cyanide
(Claisen and Manasse, Ber. 20, 2194 ;
Sluiter, Proc. Akad. Wetensch. Am-
sterdam, Jan. 30, 1904).

INDEX

The numhers refer to pages only. The chief reference to natural products is printed in thick type.

Abies alba, 37.
,, canadensis, 273.
,, pectinata, 161, 273.
,, sibirica, 273, 274.
Acacetin, 161, 234.
Acacia catechu, 138, 139, 160.
,, cavenia, 278, 288.
,, farnesiana, 108, 278.
,, sp. containing methyl salicylate, 41.
Acaroid resin, 33, 142, 215, atg.
Acarospora chlorophana, 45.
Acclimatisation of yeasts, 50.
Acetal, 181.

,, for erythrose, 243.
,, for formic aldehyde, 173.
,, for furfural, 225.
,, for mannitol, 106.
Acetalmalonic acid, 31.
Acetamide, 71.

„ and magnesium ethiodide for me-

thylacetyl carbinol, 283.
4-Acetamino-2-cresol, 156.
Acetanilide, 150, 215, 229.
Acetchlorglucose, 250, 251.
Acetferulaic acid, 141.

Acetic acid and ethyl alcohol for n-butyl al-
cohol, 71.
,, ,, ,, for erythritol, loi.

,, „ „ for glycerol, 98.

,, and hydrogen cyanide for quinol, 151.

,, and methyl alcohol for tertiary butyl

alcohol, 74.
,, and silver cyanide for isocyanacetic

acid, 268.
,, &c. , for acetaldehyde, 176.

,, &c., for formic aldehyde, 171, 287.

,, ethyl alcohol, and acetone for me-

thylheptenone, 203.
,, for acetol, 94.

„ for acetone, 193.

,, for carbon disulphide, 251.

,, for chloroform, 25.

,, for ethyl alcohol, 56, 279.

, , for hydrogen cyanide, 266.

,, for isopropyl alcohol, 68.

,, for methane, 25.

,, for methyl alcohol, 44, 278.

,, for n-primary amyl alcohol, 76.

,, glycerol, and ethyl alcohol for eryth-

ritol, 102.
Acetic aldehyde, 174, 287.

,, ,, and carbon disulphide for sec.

butyl isothiocyanate, 254.
,, ,, andethylalcoholforacetal,i8r.

,, ,, for acetone, 196.

,, ,, for n-butyl alcohol, 71.

,, ,, for carbon disulphide, 251.

,, ,, for chloral, 24.

,, ,, for crotonic aldehyde, 71, 190.

„ ,, for diacetyl, 204.

Acetic aldehyde for ethyl alcohol, 55, 279.

for formic aldehyde, 170.

for n-hexyl alcohol, 82.

for hydrogen cyanide, 267.

for iodoform, 24.

for isopropyl alcohol, 67.

for methane, 24.

for methyl alcohol, 44.

formethylpropylacetaldehyde,
188.

for phenol, 124.

for n-propyl alcohol, 60.

for toluene, no.

from acetylene, 53.
Acetic and benzoic acids for acetophenone and
benzaldehyde, 210.
„ „ „ for hydrogen cyanide,

293-
Acetic and butyric acids for methylacetyl

carbinol, 95.
«, ,, „ for n-secondary

amyl alcohol, 77.
Acetic and decoic acids for methyl-n-nonyl

ketone, 202.
Acetic and formic esters for crotonic aldehyde,

71, 190.
Acetic and lauric acids for methyl-n-decyl ke-
tone, 202.
Acetic and n-octoic acids for methyl-n-heptyl

ketone, eoi.
Acetic and oxalic acids and alcohol for diacetyl,
204.
„ „ „ for glycerol, 97.

Acetic and propionic acids and potassium

cyanide for methylpropylacetaldehyde, 187.
Acetic and propionic acids for methylacetyl
carbinol, 95.
„ ,, aldehydes for tiglicalde-

hyde, 191.
„ ,, esters and hydrogen

cyanide for citraconic
acid, 113.
Acetic benzyl ester, occurrence, 108.
Acetic ester and glycerol for quinol, 150.

„ ,, and methylheptenone for citral,

191.
„ ,, ,, ,, for citron-

ellal, 192.
Acetic ethyl ester, occurrence, 45.
Acetoacetic acid and benzene for phlorol, 134.
,, ,, and hydrogen cyanide for

quinol, 151.
Acetoacetic ester and acetaldehyde for resor-
cinol, 145.
,, ,, and amylene bromide for

methylheptenone, 203.
,, ,, and benzoic acid for o-hydr-

oxyacetophenone, 228.
,, ,, and glycerol for resorcinol,

144.

296

INDEX

Acetoacetic ester and hydrogen cyanide for
citraconic acid, 113.

„ ,, and hydrogen cyanide, &c., for

methylpropylacetaldehyde,
186.

f, ,, and lactic acid for resorcinol,

145-

„ ,, and methyl alcohol for di-

acetyl, 204.

„ ,, and methyl alcohol for methyl-

acetyl carbinol, 95.

„ ,, and succinic acid for resor-

cinol, 145.

„ ,, &c., for m-cresol, 129,

„ „ for acetaldehyde, 178.

„ , , for acetol, 94.

„ „ for acetone, 196.

„ ,, for acrolein, 98, 190.

„ ,, for allylene and acetone, 194.

„ ,, for formic aldehyde, 172.

,f ,, for isopropyl alcohol, 69.

„ „ for orcinol, 155.

„ ,, for phloroglucinol, 162.

„ ,, for n-jpropyl alcohol, 63.

„ y, for quinol, 148.

f, ., for n-secondary amyl alcohol,

77-
y, „ for toluene, iii.

,, „ methyl alcohol, and carbon

disulphide for sec. butyl
isothiocyanate, 255.
7-Acetobutyric = 5-hexanonic acid, 144, 145.
Acetoglutaric ester, 144, 145.
Acetol = acetyl carbinol, 93.
Acetol for methylpropylacetaldehyde, 188.
Acetone, 192, 289.

„ and ethyl acetate for diacetyl, 204.
,, and glycerol, &c., for isobutyl alcohol,

73-

„ „ „ for isobutyric alde-

hyde, 182, 183.

„ „ ,, for tertiary butyl

alcohol, 75.

,, dibromide, 98, 190.

„ &c,, for n-primary amyl alcohol, 76.

,, &c., for n-secondary amyl alcohol,

77-

5, for acetaldehyde, 179.

„ for acetol, 94.

,, for acrolein, 98, 106, 190.

,, for active hexyl alcohol, 83.

„ for allylene, 114.

,, for benzene, 30.

„ for bromoform, 25.

„ for carbon disulphide, 251.

„ for chloroform, 24.

,, for m-cresol, 129.

,, for o-cresol, 126.

„ for p-cresol, 132.

„ for dextrose, 246.

,, for ethyl alcohol, 56.

,, for formic aldehyde, 170.

., for glycerol, 98.

„ for n-hexyl alcohol via pinacone, 82.

,, for iodoform, 24.

,, for isobutyl alcohol, 280.

„ for isopropyl alcohol, 65, 280.

„ for mannitol, 106.

,, for methane, 24, 277.

„ for phenol, 123.

,, for n-propyl alcohol, 60.

., for quinol, 149.

„ for toluene, 109.

Acetone, furfural, and phloroglucinol foreuxan-
thone, 233.
,, furfural, and resorcinol for euxan-

thone, 233.
,, malonic and oxalic acids, &c., for
camphor, 272.
Acetone-chloroform, 73, 75, 179.
Acetonedicarboxylie acid, 63, 99, 124, 145,
i54> i55> 162, 174, 180, 186, 196, 198, 242, 285.
Acetonedicarboxylie ester, for n-secondary

amyl alcohol, 77, 78.
Acetonedicarboxylmethenylmalonic ester, 145.
Acetoneoxalic ester = acetylpyroracemic ester,

129.
Acetoneoxime, 65.
Acetonephenylhydrazone, 65.
Acetonetricarboxylic ester, 162, 199.
Acetonitrile = methyl cyanide, 54, 71, 199, 206,

207, 209, 211.
Acetophenone, &c., for benzaldehyde, 207,
208-211, 289.
,, &c., for piceol, 229.

,, for hydrogen cyanide, 293.

,, for benzylamine, 258, 259.

,, for ethylbenzene, &c., 261.

,, foro-hydroxyacetophenone, 228,

229.
„ for methylphenyl carbinol, 119.

,, for phenylethyl alcohol, 118.

„ for phlorol, 135.

„ for salicylic aldehyde, 213-215.

,, for styrene, 34.

,, from benzene, 34.

„ from benzoic acid, &c., 35.

,, from benzoylacetoacetic ester,

35-
,, from isopropylbenzene, 34.

Acetophenonecyanhydrin, 229.
Acetopropyl alcohol, 203.
Acetosuccinic ester, 63, loi, 112, 149, 186, 196,

204.
p-Acettoluidide, 154, 228.
Acetvanillic acid, 141.
Acetvanillin, 239.
Acetyl carbinol for acetone, 200.

,, ,, for isopropyl alcohol, 65, 67,

68, 69, 280.
,, chloride, 207.

,, cyanide = pyroracemienitrile, 6 1,63, no,
III, 112, 116, 151, 171, 176, 186, 187.
Acetylacetone, 60, 76, 77, 94, 102, 149, 202, 204.
p-Acetylanisole, 229.
Acetylbutyl alcohol, 145.
/3-Acetylbutyric acids, n- & Iso-, 112.
Acetyl-/37-dibrompropylamine, 98.
Acetylene and benzene for anthracene, 291.
,, ,, for ethylbenzene, 286.

,, ,, for styrene, 278.

,, and nitrogen, &c., for hydrogen

cyanide, 263.
,, for aldehyde, 174, 179.

,, for anthracene, 237.

,, for benzene, 29.

,, for benzyl alcohol, 108.

,, for o-cresol, 128.

,, for crotonic aldehyde, 71, 190.

,, for erythritol, 100.

,, for ethyl alcohol, 53.

,, for formic aldehyde, 169.

,, for methane, 22.

,, for naphthalene, 166.

,, for phenol, 120.

,, for phloroglucinol, i6a.

INDEX

297

Acetylene for styrene, 33.

„ from acrolein, 26, 32, 58.

,, from carbides, 22.

„ from carbon tetrachloride, 54.

,, from chloroform, bromoform, and

iodoform, 29, 54, 56.
,, from fumaric acid, 26, 31, 57.

,, from hydrogen cyanide, 56.

„ from iodoform, 55.

,, from maleic acid, 26, 31, 57.

,, from salicylic acid, 57.

,, from succinic acid, 26, 57.

Acetylenedicarboxylic acid, 26, 31, 57, 177,

183, 268.
Acetylenetetracarboxylic ester = s-ethanetetra-

carboxylic ester, 166.
Acetyl-o-hydroxy-oi-acetophenone bromide,

213, 230.
Acetylmenthone, 228.
Acetylmethylcyclohexanone, 228.
/3-Acetylpropionic acid, see under laovulic =

4-pentanonic acid.
Acetyl-propionyl = 2 : 3-pentadione, 188.
Acetylpropyl alcohol, loi.

Acetyltrimethylene = ethanoylcyclopropane,77.
Acetyltrjmethylenecarboxylic acid, 77.
Acolium, tigillare, 45.
Aconitic acid for acetone, 200.

„ for isopropyl alcohol, 69.

„ for methylpropylacetaldehyde,

188.
„ for n-propyl alcohol, 63.

„ for toluene and benzyl alcohol,

Aconitum ferox, 140.

,, napellus, 104.
Acorus calamus, 40, 164, 224.
n-Acritol = i-mannitol, 105.
Acrolein, 190, 288.

,, and hydrogen cyanide for methyl-
propylacetaldehyde, 186.
„ diethylacetal, 243.
,, for acetaldehyde, 177, 179.
,, for acetone, 193, 200.
„ for benzene, 31.
„ for dextrose, 246.
,, for erythrose, 243.
,, for ethyl alcohol, 56, 58.
„ for formic aldehyde, 172, 173.
„ for glycerol, 98.
,, for isopropyl alcohol, 67.
„ for mannitol, 106.
,, for methane, 24, 26.
„ for n-propyl alcohol, 59, 60.
,, for quinol, 151.
,, for toluene, 109, no, 116.
„ from glycerol, 31.
a-Acrosazone, 105, 246, 250.
a-Acrose, 105, 106, 225, 246, 250.
a-Acrosone, 105, 225, 246, 250.
Acrylic acid for acetaldehyde, 176-179.
„ for acetone, 199, 200.

„ for benzyl alcohol, in, 284.

„ for formic aldehyde, 170, 173.

„ forisopropylalcohol, 65,67, 68,69.

„ for methylpropylacetaldehyde,

187.
„ for n-propyl alcohol, 58, 60, 62,

64.
„ for quinol, 151.

„ for toluene, 109-114, 116.

Acrylic and acetoacetic esters for resorcinol,
145-

Aciinobakter polymorphus, lactose ferment, 52.
Adenocrepis javanica, 41.
Adipic acid for n-butyl alcohol, 72.
,, for cetyl alcohol, 86.

,, for n-hexane, 79.

,, for n-hexyl alcohol, 81.

,, for n-primary amyl alcohol, 76.

,, for valeric aldehyde, 184.

Agaricus campestris, 105.
Agyneia muUiJlora, 41.
Ailanthus glandulosa, 138.
Alanine for acetaldehyde, 180.
,, for ethyl alcohol, 57.
,, for isopropyl alcohol, 69.
„ for n-propyl alcohol, 64.
,, for toluene and benzyl alcohol, 116.
Albumin, anaerobic putrefaction of, 252.
,, bacterial fermentation, 51, 80.
„ culture, quinone formed in, by Strepto-

thrix, 235.
,, intestinal decomposition of, 252.
,, methane fermentation of, 21.
Alcoholic fermentation by Mucor, 49.

,, „ by Mycoderma, 48.

,, „ by Torula, 48.

„ „ by yeasts, 45.

Aldehyde-ammonia for methane, 24.
Aldehydephenylhydrazone, 208, 214.
Aldehydoguaiacolcarboxylic acid, 220.
o-Aldehydophenoxyacetic = aldehydophenyl-

glycollic acid, 134, 230.
Aldehydopropionic acid, 31.
Aldol=i8- hydroxy butyric aldehyde, 71.
Alectoria ochroleuca, 156.
Algae, mannitol in, 104, 105.
Alizarin, 140, 238, 291.

,, for anthragallol, 240.
„ for m-hydroxyanthraquinone, 238.
,, for purpurin, 241, 291.
a-Alizarinamide, 238.
Allamanda hendersoni, 41.
Allene for acetone, 195.
Allium cepa, 249,

,, ursinum, 253.
Alloxan, 217.

,, and anisidine for vanillin, 220.
Allyl alcohol for acetone, 195.
,, ,, for ethyl alcohol, 55.
„ ,, for formic aldehyde, 172.
„ „ for glycerol, 98, 99.
,, ,, for glyoxal and hydrogen cyanide ,

268.
,, ,, for isopropyl alcohol, 67.
,, ,, for methylpropylacetaldehyde,

185.
,, ,, for n-propyl alcohol, 59.
,, bromide, 59, 67, 95, 145, 195, 212, 280.
,, carbonimide, 98.
„ chloride, 38, 60, 102, 109, 185, 195.
„ cyanide, 39, 64, 69, 109, 112, 172, 177,

185, 187.
„ iodide, 67, 70, 73, 81, 94, 98, 109, 158,

195, 254, 256.
„ isothiocyanate, 256.
„ ,, for acetaldehyde, 179.

,, ,, for allylene and acetone,

194.
,, ,, for carbon disulphide,

252.
,, „ for formic aldehyde, 173.

,, ,, for isopropyl alcohol, 69,

,, ,, for methylpropylacetal-

dehyde, 187.

298

INDEX

AUyl isothiocyanate for n-propyl alcohol, 64.
,, ,, for toluene, 112,

,, mercaptai), 256.
,, sulphide, 253.
,, Ihiocyanate from sinigrin, 256.
,, „ in mustard oil, 268.

Allylacetic acid, 102.
Allylacetoacetic ester, 102.
AUylacetone, 102, 149, 204.
Allylamine, 98, 102.

^-Allylbenzene = methovinylbenzene, 32.
AUylene dichloride, 60, iii, 145.

„ for acetol, 94.

,, for acetone, 193-200.

,, for benzene, 30.

„ for toluene, 108-116.

,, from ethyl alcohol, 199.

„ pyrogenic generators, 114.
Allylmalonic acid, 102.
Alpinia malaccensis, 42.

,, offidnarum, 91, 161.
Altingia excelsa, 205, 223,
Amanita, mannitol in, 105.
Ambrette seeds, oil, 224.
American bean, 249.

,, storax, 33, 119, 219.
o-Aminoacetophenone, 2 13, 214, 215, 228, 229.
p-Aminoacetophenone, 215, 230.
a-Aminoalizarin, 241.
/3-Aminoalizarin, 240.
2-Aminoanthraquinone, 238.
a-Aminoanthraquinonesulphonic acid, 239,
Aminoanthrol, 291,
m-Aminobenzoic acid, 121, 122, 236.
o-Aminobenzoic = anthranilic acid, 147, 148.
m-Aminobenzoic aldehyde, 215, 220.
p-Aminobenzoic aldehyde, 216, 217, 290.
o-Aminobenzyl alcohol, 117.
p-Aminobenzylamine, 262.
p-Aminobenzylideneaniline and sulphonic

acid, 217.
6- Aniino-3-brombenzoic =3 5- brom- 2- amino-
benzoic acid, 147.
2-Aminobutane, 254.
2-Amino-4-cresol, 155.
4-Amino-2-cresol, 155, 156.
5-Amino-2-cresol, 151.
5-Amino-3-cresol, 154.
3-Amino-p-cyanotoluene, 228.
2-Aminocymene, 136.
3-Amino-p-cymene = cymidine, 127, 136.
3-Amino-p-cymene-6-sulphonic acid, 127,
o-Aminoethylbenzene, 133.
p-Aminohydratropic acid, 229.
m-Amino-p-hydroxybenzaldehyde, 221.
a-Aminoisobutyric acid, 180. V
Aminomesitol, 157.
4-Aminomesitylenic acid, 132.
p- Amino-m-methoxy ben zaldehyde, 220.
1 : 4-Aminonaphthol, 168.
I : 8-Aminonaphthol, 167.
1 : 3-Aminonaphthol and sulpho-acid, 115.
m-Aminophenol, 143.
o-Aminophenol, 140, 142.
p-Aminophenol, 144, 146, 147, 150, 235.
o-Aminophenylacetylene, 214, 228.
o-Aminophenylpropiolic acid, 228.
3-Aminophthalic acid, 122.
4-Aminophthalic ester, 122.
7-Amino-a)3-propylene glycol, 98.
3-Aminosalicylic acid, 141.
5-Aminosalicylic acid, 147, 232, 233.
Aminotercphthalic acid, 123.

4-Aminotoluene-2'Sulphonic acid= p4oluidine-

o-sulphonic acid, 143.
2-Amino-m-toluic acid, 126.
4-Amino-m-toluic acid, 131,
6-Amino-m-toluic acid, 126, 127.
5-Amino-o-toluic acid, 128, 130.
6-Amino-o-toluic acid, 122.
2'-Amino-p-toluic acid, 125.
3-Amino-p-toluic = homoanthranilic acid, 129,

228.
5-Amino-i : 2 : 4-trimethylbenzene = pseudo-

cumidine, 149.
o-Aminoveratric acid, 239.
5-Amino-p-xylenol-3, 156.
Amomum, see under Elettaria.
Amomum danielli, 91.

Amorphophallus konjac = rivieri, 248, 249, 262.
Ampelopsis hederacea, 138.
Amygdalin, 205, 262, 263.
Amygdalus communis var. amara, 205.

,, nana, 205.

Amyl acetate, a product of fermentation, 80.

,, ,, for ethyl alcohol, 279.

Amyl alcohol, inactive, of fermentation, 79.
,, n-primary, 76.
„ n-secondary, 77.
,, for allylene, 114.
,, for cymene, 32.
,, for erythritol, 100.
,, for pontine, 32.
,, iso-, for acetaldehyde, 180.
,, ,, for acetone, 194.

,, ,, for formic aldehyde, 173.

,, ,, &c., for tertiary butyl al-

cohol, 75.
,, n-primary for n-secondary, 78.
,, tertiary, for acetaldehyde, 176.
,, ,, for acetone, 194, 196,

197, 200.
,, ,, for formic aldehyde,

172, 173.
,, ,, &c., for methylhepte-

none, 202.
alcohols for glycerol, 97.

,, for isopropyl alcohol, 66.
,, for propylene, 97.
iodide, tertiary, 176.
valerate from albumin by BadUus, 80.
n-Amylamine, 76.
Amyl-)3-chloracrylic ester, 201.
n-Amylene, 79.

Amylene, from fusel oil amyl alcohols, 78, 79.
„ see isopropyl- and trimethylethylene.
Amylene = sym. methylethylethylene = 3-

pentene, 77, 78.
Amylene bromides =1:3- and 2 : 3-dibrom-

3-methylbutane, 194, 195, 202, 203.
Amylenes for valeric aldehydes, 184.
Amylobakter wihylicum, alcohol producer, 53.
,, ,, butyl alcohol producer,

70.
,, „ n-propyl alcohol pro-

ducer, 58.
,, hutylicum, alcohol producer, 53.

,, „ butyl alcohol producer,

70.
„ ,, n-propyl alcohol pro-

ducer, 58.
Amylomyces, alcoholic ferments, 49, 51.

,, industrial use, 51.

Amyloxalyl chloride, 221.
Amylpropiolic ester and acid, 201.
Anaptychia dliaris, 42.

INDEX

299

Andromeda japonica, 138.

„ leschenaultii, 40.

Andropogon annuJaius, 104.

„ citratus, 28, 36, 87, igr.

,, muricatus, 40, 204, 224.

,, nardus, 36, 37, 87, 191, 192, 273.

,, sch(£nanthus,'^6, 87.

Anethole, 137.

,, for anisic aldehyde, 218. .
,, for p-cresol, 132.
„ for piceol, 229.
Angelic acid and carbon disulphide for sec.

butyl isothiocyanate, 255.
Angelic hexyl ester in Roman oil of chamomile,

83.
Angelic isoamyl ester, occun-ence, 79.

,, isobutyl ester in Roman oil of cliamo'-
mile, 72.
Angelyl isothiocyanate, 257.
Angelylamine, 257.

Aniline and acetic acid, &c., for piceol, 230.
,, and carbon disulphide for methyl

mercaptan, 253.
,, and nitromethane for benzylamine,

259-
,, &c., for anisole and anisic aldehyde,

219.
,, &c., for salicylic aldehyde, 214.
,, for benzonitrile, 207.
,, for catechol, 142.
,, for phenol, 120, 123.
,, for phloroglucinol, 163.
,, for quinol, 150.
,, for quinone, 235.
,, from indigo, 123.
Animal tissues, alcohol in, 53.
Anisamide, 218.
Anise-bark oil, 137.
Aniseed oil, 137, 174, 218.
Anisic acid for catechol, 141.
,, ,, for iretol, 164.
,, ,, for phenol, 121.
,, ,, phloroglucinol, acetic acid, &c., for

apigenin, 234.
,, aldehyde, 218, 290.
„ ,, &c., for anethole, 137.

,, „ &c., for piceol, 229.

„ ,, phloroglucinol, acetic acid,

&c., for kampherol, 276.
,, and formic acids for anisic aldehyde,
218, 219.
o-Anisidine, 140, 141, 142, 165, 220.
Anisole, 137, 141. 164, 229.

,, and carbonyl chloride for anisic alde-
hyde, 218.
,, and formic ester for anisic aldehyde,

290.
,, from aniline, 219.
Anisoleglyoxylic ester and acid, 218.
Anisyl ( = p-m.ethoxybenzyl) alcohol, 218, 219.
Anihemis nobilis, 72, 79, 83, 280, 281.
Anthracene for alizarin, 238.

,, or anthraquinone for m-hydroxy-

anthraquinone, 238, 291.
,, syntheses, 236, 237, 291.

2-Antliracenesulphonic acid, 291.
Anthrachrysone, 239.
Anthragallol, 240, 291.

„ dimethyl ether, 159.

Anthranilic = o-aminobenzoic acid, 147, 148.
Anthranilic acid for phenol, 121, 124.

,, „ and phloroglucinol for gcnti-

sin, 233.

Anthranilic acid andresorcinol for euzanthone,
23a.
,, methyl ester, occurrence, 41, 42.

1 : 2-Anthraquinol, 291.
Anthraquinone for alizarin, 239, 291.
,, for purpurin, 241, 291.

,, for quinizarin, 291.

,, from anthracene, 238.

,, syntheses, 237, 238,

I : 2-Anthraquinone, 291.

Anthraquinone-2'Sulphonic acid, 238, 239, 291.
Anthrax, symptomatic. Bacillus of, 53.
AnthriscuH cerefolium, 40, 45.
2-Anthrol, 291.
Antiaris toxicaria, 163.
Antiarol, 163, 287.
Antidesma diandrurn, 41.
Apigenin, 234.

,, for piceol, 230.
,, phenol complex in, 119.
,, phloroglucinol complex in, 160.
Apiin, 160, 234,
Apium graveolens, 37, 104.

,, petroselinum, 160, 234.
Apple leaves, 138.

Aqueous extract of liver, dextrose in, 246.
„ humour of eye, dextrose in, 246.
Aguilegia vidgaris, 262.

Arabinose, bacterial fermentation, 51, 52, 53, 70.
d'Ai-abinose, 103, 243.

,, for erythrose, 243.

,, for furfural, 225.

1-Arabinose and oxime, 243.
d-Arabonic acid, 243.
1-Arabonic acid, 243.
Arbutin, 146, 286.

Arctostaphylos uva-ursi &nd glmica, 138, 146, 251.
Areca catechu, 42, 249,
Arecoline, 42.
Arisarum lulgare, 262.
Arisiolochia reticulata, 273.

,, serpentaria, 273.

Arnica montana, 135, 158.
Aromadendral, 213.
Arrhenatherurn hulbosum, 248.
Artemisia dracunculus, 137.
,, maritima, 91.
„ vulgaris, 91.
Artocarpus integrifolia, 142, 155, 160.
Arum italicum, 262.

,, maculatum, 262.
Asarone, 164.
Asafoetida, 142, 219.
Asarone for asaryl aldehyde, 224.
Asarum arifolium, 157, 158, 164.

,, canadense, 87, 89, 90, 157, 273.
,, europwum, 157, 164.
Asaryl aldehyde, 224.

,, „ and propionic acid for asarone,

165.
Ascitic fluid, laevulose in, 248.
Ash leaves, 138,
Asparagus, 219.

,, coniferin in, 139.

Asparagus officinalis, 249.
Asparagus seeds, 249.

Aspergillus, alcoholic fermentation by, 49, 50.
„ luchuensis, starch saccharification by,

245-
,, niger, decomposes salicin and popu-

lin, 117.
„ „ enzyme of, 279.

,, „ gentianose hydrolyser, 245.

300

INDEX

Aspergillus niger, inulase in, 247.

„ „ inversion of raffinose by, 247.

„ „ melezitose hydrolyser, 245.

„ ,, raffinose hydrolyser, 245.

„ „ resolution of saccharose by,

244.

„ „ trehalose hydrolyser, 245.

„ „ and glaucus, decompose arbu-

tin, 146.

,, oryzcBf decomposes salicin, 117.

,, „ salicylic aldehyde producer,

213.
A^icilia calcarea, 153.
Aspidiumfilix mas, 80, 84, 160, 161.

,, spinulosum, 161.
Astrocaryum vulgare, 249.
Athyrium filix foemina, 161.
Atlas cedar, 192.

Atranorin = atranoric acid, 42, 156.
Atraric acid = ceratophyllin = physcianin, 42,

156-
Aucuba japonica, 249.
Awamori, Japanese, 46, 49, 245.
Azelaic acid for erythritol, 103.

,, ,, for ethyl alcohol, 57.

„ , , for ethylene, 26.

„ ,, for heptane, 27.

, , „ for isopropyl alcohol, 69.

„ „ for methane, 26.

„ „ for propylene and glycerol, 98.

,, ,, for suberic acid, 81.

Baccaurea sp., 41.

Bacillus acidi lactici, alcohol producer, 52.

„ „ IcBvolactici, glycerol ferment, 51.

„ „ „ lactose ferment, 52.

„ amylobakter = Clostridium butyricum, 70.

„ amylozymicus, starch ferment, 52, 80.

,, anthracis, starch hydrolyser, 246.

,, boocopricus, 43, 52.

„ butylicus, 51, 95.

„ ,, alcohol producer, 51.

„ ,, n-butyl alcohol producer, 69.

„ „ n-propyl alcohol producer, 58.

,, butyricum, butyl alcohol producer, 70.

,, coli communis, 21.

,, „ „ alcohol producer, 52.

,, ,, „ mercaptan producer, 292.

„ „ „ methane producer, 277.

,, esterificans, mercaptan producer, 252.

,, ethaceUcus, glycerol ferment, 51.

,, ethacetosuccinicus, alcohol producer, 51,

„ fermentationis cdlulosce, 21.

„ fervitosus, alcohol producer, 52.

„ fitzianus, 51.

,, Jluorescens liquefaciens, saccharose in-
verter, 244.

,, Jluorescens liquefaciens, starch hydrolyser,
246.

„ „ „ trehalose hydro-

lyser, 245.

,, gummosus, mannitol producer, 105.
Bacillus {= PneumobaciUus) lactis aerogenes, alcohol

producer, 52.
Bacillus levani/ormans, saccharose inverter, 244.

„ liquefaciens, methyl mercaptan producer,
252.

,, magnus, methyl mercaptan producer,
252.

,, megatherium, saccharose inverter, 244,

„ of malignant oedema, 5a, 53, 58, 119.

,, „ ,, mercaptan pro-

ducer, 352.

Bacillus of symptomatic anthrax, 53, 69, iig.
„ „ ,, mercaptan pro-

ducer, 252.
„ orthobutylicus, butyl alcohol producer,

70.
„ „ isobutyl alcohol producer,

7a.
,, prcepollens, albumin ferment, 80.
,, „ mercaptan producer, 252.

, , putrificus, alcohol or phenol producer, 53,

119.
,, ,, mercaptan producer, 252,

,, roseus vini, glucose ferment, 242.
,, spinosus, methyl mercaptan producer,

252.
„ suaveolens, aldehyde producer, 174.
,, ,, starch ferment, 52, 174.

,, „ starch hydrolyser, 246.

,, tartricus, 94.

,, typhosus, alcohol producer, 52.
Backhousia citriodora, 191.
Bacteria, alcohol producers, 51, 279.
,, aldehyde producers, 287.
,, lactic, milk-sugar hydrolysers, 245.
,, of blue pus, 69.
,, saccharose inverters, 244.
,, sugar, 244.
Bacterium aceti, laevulose from mannitol by, 247.
,, brassicce acidce, 21.

,, icteroides, alcohol producer, 52.

,, kictzingianum, mannitol oxidiser, 247.

,, lactis acidi, 51.

,, lactis aerogenes = B. aceticum, 21.

„ „ ,, „ acetone

producer, 193.
,, sorbose = £. xylinum, 93, 107, 242.

,, vermiforme, 51.
,, xylinum, see sorbose bacterium.
Badger, Philippine, 253.
Badiana oil, 92.
Balanophora sp., 96.
Balm mint oil, 87, 88, 192.
Balsam, Peru, 219.
Barbarea prcecox, 260.
Barbatic acid, 156.
Barosma betulina, 37, 227.

,, serratifolia, 37, 227.
Basacantha spinosa \ar.ferox, 104.
Bassia latifolia, 244, 247.
Bay oil, 36, 40, 157, 191, 204, 224.
Bebeerine, 124.
Beer, furfural in, 224.
Beesw^ax, 27, 28.
Beet, coniferin in, 139.
Beet-sugar, catechol in, 138.

„ molasses, mannitol in, 105.

,, ,, sorbitol in, 106.

,, vanillin in, 219.

Benzacetodinitrile = iminobenzoylmethyl cyan-
ide, 206, 209, 211,
Benzal bromide, 205.

,, chloride, see under benzylidene chloride.
Benzalbenzoylhydrazine, 209.
Benzaldehyde-cyanhydrin, 258.
Benzaldoxime, 108, 258, 292.
Benzamide, 258, 292.

,, and magnesium methiodide for ace-

tophenone, 289.
Benzene and acetyl chloride for acetophenone,
119.
,, and acetylene for anthracene, 291.
,, ,, for ethylbenzene, 286.

,, „ for styrene, 278.

INDEX

301

Benzene and acetylene dibromide, &c., for an-
thracene, 236.

,, and carbon disulphide for benzyl
isothiocyanate, 259.

, , and carbon disulphide for methyl mer-
captan, 253.

,, and dimethyl sulphate for p-xylene,
285.

,, and ethyl alcohol for methylphenyl
carbinol, 118.

, , and formic ester for benzaldehyde, 289.

„ and glycerol for hydrocinnamic alde-
hyde, 212.

„ and hydrogen cyanide, &c., for ben-
zaldehyde, 206.

,, and isobutyl alcohol for naphthalene,

165.

, , and n-propyl alcohol for hydrocinna-
mic aldehyde, an.

,, and trimethylene glycol ether for
phenylpropyl alcohol, 119.

,, &c., for anisic aldehyde, 219.

,, &c., for o-hydroxyacetophenone, 229.

,, &c., for p-hydroxybenzaldehyde, 216.

,, &c., for phenylethyl alcohol, 118.

,, &c., for piceol, 230.

,, &c., for salicylic aldehyde, 214.

,, for antiarol, 164.

,, for benzoic aldehyde, 205, 206.

,, for benzyl alcohol, 108.

,, for carbon disulphide, 252.

,, for catechol, 14a.

,, for hydrogen cyanide, 265.

,, for methane, 26.

,, for phenol, 120, 285.

,, for phloroglucinol, 163.

,, for quinol, 150.

,, for quinone, 235.

,, for resorcinol, 143.

,, for styrene, 33.

,, hexachloride, 142.

,, syntheses, 29.
Benzeneazoresorcinol dimethyl ether, 165.
Benzeneazosalicylic acid, 147,
Benzenedisulphonic acids, 143.
Benzenesulphonic acid, 120.
I • 3 • 5-Benzenetrisulphonic acid, 163.
Benzenylmethylimido-chloride, 207, 258.
Benzenyloxyamidoxime, 258.
Benzhydrazide, 209.
Benzhydroximic chloride, 258.
Benzimidoethyl ether, 209, 257.
Benzoic acid and acetoacetic ester for salicylic
aldehyde, 214.

,, „ and carbon disulphide for benzyl
isothiocyanate, 257.

,, ,, and phloroglucinol for gentisin,

233-

,, „ and resorcinol for euxanthone,

232.
,, ,, and toluene for anthracene, 237.
„ ,, for anthraquinone, 237.
,, „ for benzyl alcohol, 109.
,, ,, for catechol, 141.
,, ,, for m - hydroxyanthraquinone,

236.
,, ,, for m-hydroxy benzaldehyde, 215.
,, „ for phenol, 121.
,, ,, for purpuroxanthin, 239.
,, ,, for quinol, 147.
„ ,, for resorcinol, 144.
,, and acetic acids for hydi'ogen cyanide,
293-

Benzoic and acetic acids for o-hydroxyaceto-
phenone, 228.
„ „ „ for methylphenyl

carbinol, 118.
„ „ ,, for phenylethyl al-

cohol, 118,
„ „ „ and carbon disul-

phide for phenyl-
ethyl isothiocy-
anate, 261.
,, and formic acids, &c., for benzaldehyde,

208.
,, and gallic acids for anthragallol, 240.
„ and p-toluic acids for methylpui"puro -

xanthin, 241.
,, aldehyde, 205, 289.
,, ,, and acetic acid for phlorol, 134.

,, ,, acetic acid, alcohol, and car-

bon disulphide for phenyl-
ethyl isothiocyanate, 260.
,, ,, and ethyl alcohol for hydro-

cinnamic aldehyde, 212.
,, ,, and hydrogen cyanide, &c., for

phenylethyl isothiocyanate,
261.
, , , , and methyl alcohol for methyl-

phenyl carbinol, 119.
„ ,, and succinic acid for a-naph-

thol and hydrojuglone, 168.
„ ,, &c., and carbon disulphide for

benzyl isothiocyanate, 258.
,, ,, &c., for p-hydroxybenzalde-

hyde, 216.
,, ,, &c., for phenylethyl alcohol,

118.
,, ,, for benzyl alcohol, 108.

,, ,, for m-cresol, 130.

„ ,, for m-hydroxybenzaldehyde,

215-
,, ,, for phenol, 121.

,, ,, for quinol, 147.

,, ,, for toluene, 108.

„ ,, for vanillin, 220.

,, ,, phenylhydrazone, 258.

,, and acetic aldehydes for cinnamic alde-
hyde, 223.
,, benzyl ester, occurrence, 107.
,, methyl ester, 42.
Benzoin, 237.

,, Siam, 219.
Benzonitrile = cyanobenzene, 206, 207, 209, 21 r,

257, 258, 259, 292, 293.
Benzoyl chloride, 109, 208, 231, 258.

,, cyanide, 208, 210.
Benzoylacetaldehyde and oxime, 211.
Benzoylacetic acid and ester, 210, 211,

,, ester for benzaldehyde, 206, 208,

209, 210.
„ j> for styrene, 35.

Benzoylacetiminoethyl ether, 206, 209, 211.
Benzoylacetoacetic ester for acetophenone, 35.
„ ,, for benzaldehyde, 209.

o-Benzoylbenzoic acid, 237.
Benzoylformaldehyde = phenylglyoxal, 210.
Benzoylformic acid, see under phenylglyoxylic

acid.
Benzoylpyroracemic acid, 211.
Benzyl alcohol, 107, 284.

,, for benzaldehyde, 211, 290.

,, for toluene and quinol, 148.

carbinol, see phenylethyl alcohol, 118.
chloride, 34, 108, 205, 206.

„ and cyanide for piceol, 229.

302

INDEX

Benzyl chloride, &c., for naphthalene, 165.

„ ,, for anthracene, 236.

„ „ for benzaldehyde, 205.

,, „ for benzyl alcohol, 108.

,, ,, for benzylamine, 259.

,, ,, for p-hydroxy benzaldehyde,

217.

,, chlormalonate, 260.

„ cyanide, 34.

,, ,, &c., and carbon disulphide for

phenylethyl isothiocyanate,
260.

,, ,, for benzylamine, 259.

,, ethyl ether, 236.

,, isocyanate for benzylamine, 259.

,, isothiocyanate, 257, 293.

„ magnesium bromide, 293.

,, ,, chloride, 386.

,', trichloracetate, 236.
Benzylacetamide, 263.

,, for benzylamine, 259.

Benzylamine and carbon disulphide for benzyl
isothiocyanate, 257, 258, 259.
,, and generators and carbon disul-

phide for p-hydroxybenzyl iso-
thiocyanate, 263, 292.
,, for benzoic aldehyde, 206.

,, for benzyl alcohol, 108.

Benzylaniline, 306.
Benzylidene chloride for benzoic aldehyde, 205,

206, 289.
Benzylideneaniline, 206.
p-Benzylphenol, 236, 237.
Benzyltartronic acid, 260.
Berberine, 140.
Berieris vulgaris, 140.

Bergamot oil, 36, 37, 42, 88, 135, 136, 158, 335.
Betula lenta, 40.
Biatora lucida, 45.
Bile, thiocyanate in, 269.
Birch, sweet, 40.
Bishop's- weed oil, 136, 213.
Bisnitrosyl-p-nitrobenzyl, 217.
Bitter orange, oil from flowers, 41.
Blackthorn, 287.

,, flowers, 263.
Blastenia arenaria var., 42.

,, ,, var. teicholytum, 153.

Blood, acetone in, 192.

,, dextrose in, 246.

,, globulins of, 292.

,, glycerol in, 284.

,, leucaemic, 99.

,, thiocyanate in, 269.
Blumea balsamifera, 273.
Boletus, mannitol in, 105.
Borneol, 272.

,, for camphene, 274.
,, for camphor, 272.
Bornyl chloride, 274.
Bornylamine, 274.
Boswellia carteri, 37.
Botany Bay resin, 33, 215, 219.
Box myrtle, 159.
Brandy, furfural in, 224.
Brassica dichotoma, 256.

,, glauca, 256.

„ napus, 256, 257.

,, oleracea, 256.

„ rapa, 256.
Brazil wood, 139, 142.
Brazilin, 139, 142.
Broach leaves, 138.

Bromacetal, 225.

Bromacetaldehyde, 225.

Bromacetic ester, 191.

7-Bromaeetoacetic ester, 64, 149, 186.

Bromacotone, 94.

Bromacetylene, 162.

5(3)-Brom-2(6)-aminobenzoicacid, 147, 233.

Bromamylene, 184.

i8-Bromangelic acid, 31.

p-Bromanisole, 290.

Bromanthragallol and sulphonic acid, 240.

3-Bromanthraquinone, 238.

Brombenzene for phenol, 285.

m-(3'-Brombenzoic acid, 144, 147, 233.

o-Brombenzyl bromide, 236.

a-Brom-)3-butyleno bromide = crotonyl bromide,

257.
Brombutylmethyl ketone, 102.
a-Brombutyric acid, 60, 61, 64, 67, 112, 113,

188,
a-Brom-n-butyryl bromide, 197.
^-Bromcamphoric acid, 272.
Bromcarveol methyl ether, 226.
a-Bromcinnamic acids, 390.
i^-Bromcinnamic ester, 210.
5-Brom-3-cresol, 154.
3-Bromcymene, 137.
Bromcymenesulphonic acid, 137.
3-Brom-p-cymene-6-sulphonic acid, 127.
Brom-2 : 4-dinitrobenzene, 134.
Bromethylacetoacetic ester, loi, 203.
I'-Bromethylbenzene, 34, n8.
Bromethyl bromacetate, 181.
a-Bromheptoic acid, 82.
5-Bromhexahydro-p-toluic acid, 283.
i^-Bromhydrocinnamic = phenyl-)3-brompropio-

nic acid, 209.
Bromhydro- ethyl crotonic = bromhexoic acid,

188.
3-Brom-p-hydroxybenzaldehyde, 221.
4-Brom-m-hydroxy benzaldehyde, 22 1 .
)3-Brom-a-hydroxybutyric acid, 172, 188.
Bromhydroxyphenylcrotonic acid, 212.
a-Bromisobutyric acid, 178, 197.
a-Bromisobutyric aldehyde, 200.
a-Bromisobutyric paraldehyde and oxime, 266.
a-Bromisovaleric acid and ester, 73, 182, 197,

272.
7-Brom-methylacetoacetic ester, 149, 204.
Brom - methylethylacetic = 3 - brombutane - 2-

carboxylic acid, 255.
3-Brom-6-nitrobenzoic acid, 147, 233.
3-Brom-6-nitrocymene, 127,
Bromnitromethane, 98.
3-Brom-5-nitrotoluene, 154.
4-Brom-2-nitrotoluene, 131.
3-Brom-6-nitro-p-toluic acid, 125, 127.
3-Brom-5-nitro-p-toluidine, 154.
Bromoform and zinc ethyl for propylene, 98.
for acetylene, 29,
for methane, 23.
from acetone, 25.
from citric acid, 26, 57.
from ethyl alcohol, 23.
from malic acid, 26, 57.
o-Bromphenol, 140, 220.
p-Bromphenol, 144.

p-Bromphenyl magnesium bromide, 285.
a-Brompropionic acid and ester, 75, 76, 102,

112, 113, 176, 186, 196, 198.
Brompropionyl bromide, 76, 196.
Brompropiophenone, 212.
Brompropylacetoacetic ester, 145.

INDEX

303

S-Brompyromucic acid, i8o.
a-Bromquinizarin, 291.
5-Bromsalicylic acid, 146, 147, 23a.
Bromsebacic acid, 8r.
i^-Bromstyrenc, 208.
i^-(cu)-Bromstyrene, 117, 208, 210, ai6.
3-Brom-5-sulphobenzoic acid, 144.
Bromterephthalic acid, 123.
o-Bromtoluene, 236, 285.
p-Bromtoluene, 125, 285.
3-Bi-omtoluene-5-sulphonic acid, 154.
3-Brom-o-toluic acid, ia8.
5-Brom-m-toluic acid, 131, 13a.
6-Brom-m-toIuic acid, 126.
a-Brom-p-toluic acid, 125.
3-Brom-p-toluic nitrile and acid, 125.
3-Brom-p-toIuidine, 125.
5-Brom-m-toluidine, 154.
3-Brom-2-toluidine-5-sulphonic acid, 154.
o- and p-Bromtoluyl magnesium bromide, 285.
p-Bromtoluyl-m-methyl ketone, 131.
6-Brom-m-xylene, 126.
Broom (Spartium), 234.
Brucea sumatrana, 277.
Bucco-leaf oil, 37, 227.
Buckwlieat, 138.

Bursera delpechiana or aloexylon, 87.
I : 3-Butadi6ne = diviny], fee, 100.
Butadioneoxime = isonitrosomethylethyl ke-
tone, 149, 204.
Butane from adipic acid, 7a.

,, from butyric acid, 7a.

,, from ethyl alcohol, 70.

,, from glycerol, 70.

,, from isoamyl iodide, 70.

,, from mannitol, 71.

,, from propionic acid, 71.

,, from succinic acid, 72.
a-Butanol, see secondary butyl alcohol,
Butea frondosa, 138.
Butinic acid, see tetrolic acid.
Butter, rancid, butyl alcohol in, 70.

,, ,, ethyl alcohol in, 53.

n-Butyl alcohol, 69, a8o.

,, „ and carbon disulphide for

secondary butyl isothiocya-
nate, a54.

,, ,, for n-hexyl alcohol, 83.

,, ,, for iodoform, 24.

,, ,, for methane, 24.

„ ,, for isopropyl alcohol, 66.

,, ,, for n-propyl alcohol, 59.

,, ,, for the mercaptan, 253.

Butyl alcohol, secondary, and carbon disulphide
for sec. butyl iso-
thiocyanate, 254, 355.

,, „ „ for diacetyl, 304.

,, ,, ,, for methylethyl ke-

tone, 95.

,, ,, tertiaiy, 73, 281.

,, ,, „ and carbon disulphide

for crotonyl isothio-
cyanate, 257.

„ ,, ,, for acetone, 194.

„ ,, ,, for isobutyl alcohol, 72,

280.

,, ,, ,, for isobutylene glycol,

96.

„ „ „ for isobutyric aldehyde,

182.

,, ,, J, for isopropyl alcohol, 66.

,, ,, ,, for n-propyl alcohol, 59.

,, alcohols for ethyl alcohol, 55.

Butyl alcohols for formic aldehyde, 173.

,, ,, for toluene and benzyl alcohol,

116.
„ ,, iso- and tertiary, for acetalde-

hyde, 181.
„ ,, ,, „ for glycerol,

99-

,, ,, n- and iso-, for benzene, 30.

,, bromide, tertiary, 281.
n- Butyl chloride, 70.
Butyl chloride, tertiary, 75.
,, cyanide, tertiary, 173.
,, ether, sec, 254.
n-Butyl iodide, 354.

Butyl iodide, sec. = a-iodobutane, 254, 355.
„ „ tertiary, 59, 66, 173.
,, secondary, isothiocyanate, 254, 393.
n-Butyl mercaptan, 253.

,, sulphide, 353.
Butyl, secondary, thiocyanate for the isothio-
cyanate, 355.
n-Butylamine for n-butyl alcohol, 70.
n-Butylene for secondai-y butyl isothiocyanate,
354, 293.
,, from n-butyl alcohol, 59, 354, aga.

/3-Butylene glycol, 71, 73.

,, ,, for crotonic aldehyde, 190.

Butylenes from n-hexane, 355.
Butyramide, 61.

„ and magnesium methiodide for

methylpropyl ketone, a8i.
Butyric acid and methyl alcohol for acetone,
197.
,, ,, for allylene and acetone, 194.

,, ,, for n-butyl alcohol, 71, 380.

,, ,, for dipropyl ketone, 85.

,, ,, for ethyl alcohol, 57.

,, ,, for formic aldehyde, 171,

,, ,, for n-hexane, 79.

,, ,, for n-hexyl alcohol, 83.

, , , , for isopropyl alcohol, 68.

,, „ for methylpropylacetaldehyde,

188.
„ ,, for n-propyl alcohol, 61.

,, „ for toluene, 113.

,, acids for aldehyde, 178.
,, ,, for propylene and glycerol, 98.

„ and formic acids for butyric aldehyde,

183.
,, aldehyde, 181, 388.
,, ,, for n-butyl alcohol, 71.

„ ,, for ethyl alcohol, 56,

,, „ for iodoform, 35.

„ ,, for methane, 35.

,, ,, for octoic aldehyde, 189.

,, ethyl ester, occurrence, 45.
Butyrochloral = 3:3: 3-trichlorbutanal, 60, 67,

no, 145, 196.
Butyrone, 63, 85, 188.
Butyronitrile = propyl cyanide, 70, 73.
Butyryl chloride, 71, 113, 182.

,, ,, for dipropyl ketone, 85.

Buxus sempervirens, 124.
Bysfropogon origani/olius, 38, 226, 227.

Cactus opuntia, 104.

Ccesalpinia brasiliensis and crista, 139, 142.

,, sapan, 142.

Caffeic acid, 140.

„ ,, for catechol, 142.

Cajeput oil, 90, 91, 181, 183, 205.
Calamintha nepeta, 290.
Calcium glycerate, fermentation, 43.

304

INDEX

Californian bay, 36, 90.

„ laurel, 283, 287.

CaUopisma vitelUnum, 45, 104.
Callopismic acid = vulpic ethyl ester, 45.
Calluna vulgaris, 139, 146.
Calycium flavum, 43.

„ sp, yielding vulpic acid, 43,
Camellia lanceolata, 41.
Camphene, 273.

„ for borneol, 273.

„ for camphor, 272.

„ for cymene, 278.

Campholide, 272.
Camphor, 271.

„ chloride, 274.

„ for borneol, 273.

,, for camphene, 274.

,, for carvacrol, 286.

,, for m-cresol, 285.

,, for o-cresol, 285.

,, for cymene, 277.

„ for ethyl alcohol, 279.

„ for isopropyl iodide, 280.

,, for methane, 277.

„ for methyl alcohol, 278.

,, for /3-orcinol, 286.

„ for toluene and benzyl alcohol, 284.

„ Ngai, Chinese, 273.

„ oil, 36, 37, 90, 91, 136, 174.

Camphoric anhydride and acid, 272.
Camphoroxime, 274.
Canadian golden-rod oil, 36.
Cananga odorata, 41, 87, 131.
Canarium sp., 36, 39, 41.
Candelaria concolor, 45.
Canella alba, 92, 104.
Canthium sp., 41.
Caperatic acid, 43.
Capparis spinosa, 138.
n-Caproic = hexoic aldehyde, 185.
n-Caproic (= hexoic) and formic acids for the

aldehyde, 185.
Capuchin cress, 257.
Carallia integerrima, 41.
Caraway oil, 37, 40, 203, 224, 226.
Carbethoxypropionyl chloride, loi.
Carbide, magnesium, from hydrogen cyanide,

56.
Carbides, metallic, and nitrogen for cyanides,
264.
„ „ for acetylene, 22.

„ ,, for anthracene, 237.

„ „ for benzene, 29.

„ „ for ethylene, 53.

„ ,, for methane, 2 ic

„ „ for naphthalene, 166.

Carbohydrates, mannose-yielding, 249, 292.
Carbon and hydrogen, union, 22.
„ disulphide, 25L

„ ,, and ammonia for thiocy-

anates and cyanides, 265,
269.
„ „ for benzene, 30.

,, „ for ethyl alcohol, 54.

„ ,, for methane, 25.

,, monoxide and hydrogen for methyl

alcohol, 43.
,, oxides of, for formic aldehyde, 169.
, , tetrabromide for ethylene, 54.
„ „ generators of, 55.

„ tetrachloride and zinc ethyl for propy-
lene, 98.
„ f, for acetylene, 54.

Carbon tetrachloride for carbon disulphide, 251,
252.
„ ,, for methane, 24.

,, ,, from camphor, 277.

,, ,, from carbon disulphide,

25.
,, ,, from formic acid, 25.

„ ,, from n-propyl chloride,

24.
Carbonyl chloride, 218, 292.
Cardamom oil, Ceylon, 36, 39, 90.
„ ,, Malabar, 37.

)j ,, Siam, 271, 272.

Carob seeds, 249.
Carqueia oil, 92.
Carum carui, 37, 226.
Carvacrol, 135, 286.

,, for o-cresol, 127.
,, for dimethylthymoquinol, 159.
„ for isopropyl alcohol, 67.
,, for phenol, 123.
, , for n-propyl alcohol, 64.
,, for quinol, 149.
,, for thymoquinol, 158.
„ for thymoquinone, 235.
Carve ne = d-limonene, 37.
Carvenone, 277.
Carveol methyl ether, 226.
Carvone, 226, 290.

„ for carvacrol, 136.
,, for o-cresol, 127, 285-
„ for cymene, 33.
,, for dipentene, 38.
,, for terpinene, 39.
Carya tomentosa, 138.
Cascara sagrada, 85.
Cascarilla oil, 28, 36, 38, 124.
Cassava, sweet and bitter, 262.
Cassia flowers oil, 108, 223, 278, 288.

„ oil, 223.
Castanopsis javanica, 41.
Castoreura, salicin in, 117, 250.
Castor-oil soap, 189.
Catechin, 287.
Catechins, 139, 160, i6r.
Catechol, 137, 286.

,, and chloroform, &c., for vanillin, 220.
,, and hydrogen cyanide for toluene

and benzyl alcohol, 116.
„ and phthalic anhydride for alizarin,

238, 291.
„ ,, „ for hysta-

zarin, 240.
„ &c., for piperonal, 222.
,, for antiarol, 163.
„ for hydrogen cyanide, 267.
„ glycerol, and methyl alcohol for
methyleugenol, 158.
Catechol-o-carboxylic acid, 141.
Catecholdisul phonic acid, 140.
Catecholsulphonic acid, 140.
Catechu, 138, 139.
Catha edulis, 104.
Catocarptis alpicolus, 43, 45.
Cecropia schiedeana, 41.
Cedar-leaf oil, 38.
Cedrus a&antica and libani, 192.
Celery, 104.

„ oil, 37.
Cellulose, fermentation, 21, 174.
Cephalorachid liquid, dextrose in, 292.
Ceratonia siliqua, 249.
Ceratophyllin, see atraric acid.

INDEX

305

Cerebrospinal fluid, 286.

,, ,, catechol in, 140.

,, ,, dextrose in, 246, 292.

Cetraria compHcata = C. laureri = Platysma com-
pUcatum, 286.

,, fahluensis, 286.

,, islandica and vars., 286.

,, juniperina, 43.

,, pinastri, 43.

„ sp. yielding atranorin, 42,

„ ,, „ vulpic acid, 43.
Cetraric acid, 286.
Cetyl alcohol, 86.

,, ,, for n-hexane, 79, 81.

,, ,, for suberic acid, 8r.

Chamcerops humilis = Trachycarpus excdsa, 249.
Chamomile, Roman oil of, 72, 79, 83, 280, 281.
Chay root, 236, 238, 240.
Cheiranthus cheiri, 138.
Chelidonic acid for acetone, 200.
Cherries, sorbitol from, 106.
Cherry laurel, 104, 107.
CJiilocarpus densiflorus, 41.
,, denudatus, 41.
Chilognatha, 263.
Chimaphila maculata, 146.
Chinese berries, 138.

„ galangal, 91, 161.

,, green, 160.

„ yeast, 49, 245, 246.
Chione glabra, oil from wood, 228.
Chlamydomucor oryzce, 49, 245.
Chloracetal, in, 133, 187, 225.
Chloracetaldehyde, 58, 108, iii, 187, 199.
Chloracetic acid, 171, 230, 231, 267.

,, ester, 73, 112, 186, 187, 196, 260,

283.
7-Chloracetoacetio ester, 77, 155.
Chloracetone, 94, 193.
Chloracetylacetone, 94.
Chloral, 24, 44, 75, in, 129, 187, 251.
a-Chlorallyi alcohol, 65, 67, 93.

„ chloride, 65, 67, 93.

m-Chlorbenzoic acid, 121, 122.
I : 3-Chlorbrompropane, 102.
a-Chlor-;8-brompropenylbenzene, 212.
a-Chlorbutyric acid, 188.
7-Chlorbutyronitrile, 102.
Chlorbutyryl chlorides, 113.
Chlorcarbamide, 125, 218.
/3-Chlorcitramalic acid, 198.
Chlorcrotonic acids, no, 112, 196.
I '-Chlorcymene = cymyl chloride, 213.
a-Chlorethyl acetate, 181,
Chlorethyl alcohol = glycolchlorhydrin, 175,
Chlorethyl ether, 181.
Chlorethylmalonic ester, 187.
Chlorheptane, 83, 200.
Chlorhexane, 83.

a-Chlor-;8-hydroxybutyric acid, no, 172, 188.
Chlorisobutyl alcohol, 72.
a-Chlorisobutyric acid, 178, i8x.
a-Chlorisopropylene, no.
a-Chlorisovaleric acid, 182.
Chlorlactic acids, 58, 64, 108-111, 114, 116,

151, 170, 173, 176, 177, 178, 187, 199.
Chlormalonic ester, i66.
Chlormethyl acetate, 170.

,, ether, 287.

m-Chlor-p-nitrobonzaldehyde, 222.
o-Chlornitrobenzene, 142.
p-Chlornitrobenzene, 152.
m-Chlor-p-nitrobenzyl chloride, 222.

r'- Chlor - 2 - nitrostyrene = o-nitrophenyl - (o-

chlorethylene, 134.
m-Chlor-p-nitrotoluene, 222.
Chlorocarbonic = chloro formic ester, 221.
2-Chloroctane, 82.
Chloroform and generators and ammonia for

hydrogen cyanide, 266.
Chloroform for acetylene, 29, 54.
„ for benzene, 29.

„ for carbon disulphide, 251, 252.

„ for formic aldehyde, 170.

,, for methane, 23.

„ for methylene chloride, 117, 170.

„ for orthoformic ester, 145.

,, from acetic acid, 25.

,, from acetone, 24, 171.

,, from benzene, 26.

,, from carbon disulphide, 30.

,, from carbon tetrachloride, 30.

„ from ethyl alcohol, 22.

,, from gallic acid, 26, 57.

„ from lactic acid, 25.

,, from methyl alcohol, 30.

,, from phenol, 25.

„ from salicylic acid, 26, 57.

Chloroformic ester = chlorocarbonic ester, 2a i.
Chlorpentanes, 76-79.
o-Chlorphenol, 140, 286.
p-Chlorphenol, 144, 159, 241.
p-Chlorphenolsulphonic acids, 159.
2-(o)-Chlorphenol-4-(p)-sulphonic acid, 140, 286.
/3-Chlorpropionacetal, 177.
a-Chlorpropionic acid, 60, 62, in, 114, 145.
i3-Chlorpropionic acid, 58, 61, 114.

,, diethylacetal, 243.

a and )3-Chlorpropylenes, 65, 93, 94, 109.
Chlorquinizarin, 291.
m-Chlortoluene, 122, 124.
p-Chlortoluene-3-sulphonic acid, 153.
2:4: 6-Chlortrinitrobenzene = picryl chloride,

162.
i^-ChloiTinylphenol, 134.
Choline, fez-mentation of, 21.
„ for acetaldehyde, 180.
,, for formic aldehyde, 173.
„ for furfural, 225.
„ for glycol, 95.
,, for isopropyl alcohol, 69.
,, for mannitol, 106,
Chrysin, 160, 233.

,, &c., for tectochrysin, 234.

Chrysocetraric = pinastric acid, 43.
Chrysomela populi, 213.
Chyle, dextrose in, 246.
Cicuta virosa, 28, 212.
Cineole, 91, 283.

,, for cymene, 33.
,, for dipentene, 38.
„ for methylheptenone, 203.
,, for terpinene, 39.
Cineolic acid and anhydride, 203.
Cinnamein, 219.
Cinnamene = styrene, 33.
Cinnamic and formic acids for cinnamic alde-
hyde, 223.
,, „ ,, aldehydes for benzalde-

hyde, 290.
,, „ malonic esters for hydrojuglone,

168.
„ acid and carbon disulphide for phenyl-

ethyl isothiocyanate, 261.
,, acid for benzaldehyde, 209, 290.
„ ,, for hydrogen cyanide, 268.

306

INDEX

Cinnamic acid for o-hydroxyacetophenone, 228.

,, ,, form-hydroxybenzaldehyde, 215.

,, ,, for p-hydroxybenzaldehyde, 216.

,, ,, for phenol, 121.

,, ,, for phenylethyl alcohol, 118.

,, ,, for phlorol, 134.

„ „ for piceol, 230.

„ ,, for quinol, 147.

,, ;, for salicylic aldehyde, 213.

,, ,, for sallgenin, 117.

„ „ for styrene, 35.

„ aldehyde, 223.

„ ,, and hippuric acid for naph-

thalene, 168.
„ „ for hydrocinnamic aldehyde,

212.

,, benzyl ester, occurrence, 107.
„ ester for phenylpropyl alcohol, 284.
,, methyl ester, occurrence, 42.
„ phenylpropyl ester, occurrence, 119.
Cimiamomum (Laurus) camphora, 36, 271.
,, cassia, 223.

,, culilawan, 158.

„ loureirii, 223.

,, pedatinervium, 282, 287.

,, seylanicum, 205, 223.

Cinnamon leaf oil, 89, 223.

„ oil, 28, 89, 189, 200, 203, an, 213,

223, 224.
„ root oil, 271.

Cinnamylidenehippuric acid, 168.
Oissampelos pareira, 124.
Citrabrompyrotartaric acid, 108, 109, iii, 113,

114.
Citraconic acid for acetone, 196, 197, 198.
,, ,, for isopropyl alcohol, 68, 69.

„ ,, for methvlpropylacetaldehyde,

186, 187".
„ „ for n-propyl alcohol, 62, 63.

I, ,, for quinol, 151.

„ „ for toluene, 113.

„ „ generators, 63, 113.

Citracoumalic acid, r8o.
Citradibrompyrotartaric acid, 185, 186, 187.
Citral, 191, 288.

„ for acetaldehyde, 180.
„ for cymene, 33.
,, for geraniol, 87.
,, for methylheptenone, 203.
Citramalic acid, see hydroxypyrotartaric acid.
Citrene = d-limonene, 37.
Citric acid and methyl alcohol for n-secondary
amyl alcohol, 78.
,, ,, bacterial fermentation, 51.
,, „ for acetaldehyde, 180.
,, „ for acetone, 198.
,, ,, for allylene, 194.
„ ,, for diacetyl, 204.
„ ,, for dihydroxyacetone, 242.
„ ,, for formic aldehyde, 174.
„ „ for glycerol, 99.
,, ,, for isopropyl alcohol, 69.
„ ,, for methane, 26, 277.
„ ,, for orcinol, 154.
, , „ for n-propyl alcohol, 63.
„ „ for quinol, 151.
„ „ for toluene, 113.
,, ester for phloroglucinol, 162.
Citron oil, 212.
Citronella oil, 36, 37, 87, 88, 89, 93, 158, 191,

192, 202, 273.
Citronellal, 192, 289.

,, for acetone, 199.

Citronellal for citronellol, 89.
,, for cymene, 33.

,, for isopulegol, 93, 283.

,, for pnlegone, 226.

Citronellic acid, 192.
Citronellol, 89, 282.

,, for acetone, 199.

„ for citronellal, 289.

1-Citronellol = rhodinol, 89, 90, 282, 288.

,, ,, „ for menthone, 227.

Citrus aurantium, 89, 160.
,, bergamia, 88.
,, bigaradia, 37, 41, 87.
,, decumana, 160.
,, limetia, 36, 37, 88, 160, 202.
,, limonum, 87, 88, 160, 191.
„ madurensis, 37, 42, 88, 90, 191.
,, medica, 37, i6o, 191.
,, nobilis, 191.
„ triptera, 37, 42, 89.
Cladina uncialis, 43.
Cladonia amauracrcBa, 156.
,, cocci/era, 156.
,, fimbriata van, 286.
„ floerkeana = baccilaris, 43, 156.
,, pyxidata, 43.
,, rangiferina and vars., 286.
,, rangi/ormis, 43.
,, silvatica, 286.
Cladonic(= j8-usnic) acid, 156.
Cladothrix, saccharose inverter, 244.
Clostridium, anthrax, mercaptan producer, 25a.
,, butyricum — Bacillus amylobaJder, 70.

„ gelatinosum, alcohol producer, 53.

,, ,, saccharose inverter, 244.

,, pastorianum, 279, 280.

Clove bark oil, 158.

„ oil, 40, 42, 200, aoi, 224.
,, stems, oil, 39.
Cluytia oblongifolia, 41.
Cocaine, 4a.
Coccellic acid, 156.
Coccellinic acid, 156.
Cochlearia armoracia, 256.

„ officinalis, 37, 254, 256.
Coco, 249.

Cocoa-nut palm, mannitol from, 104.
Cocos nucifera, 104.
Coffea arabica, 249.
Coffee berries, 104, 249.
Colchicine, 42.
Colchicum autumncde, 42.
Oolpoon compressum, 138.
Coniferse, mannitol in sap, 104.

,, woody tissue, 250.
Coniferin, 139, 220.
Coniferyl alcohol, 139, 220.
Conjunctival secretion, thiocyanate in, 269.
Cordia asperrima, 41.
Coriander oil, 89.
Coriandrum sativum, 89.
Coriaria myrtifolia, 139.
Cork, vanillin in, 219.
Corydaline, 140.
Corydalis {Aristolochid) cava, 140.
Coto bark, 161, 231.
Cotoin, 161.
Cotoneaster vulgaris, 205.
Coumalic acid = formylglutaconic anhydride,

31, 71, 72, 116, 124.
o-Coumaric acid for o-hydroxyacetophenone,
228.
,, „ for phenol, 124.

INDEX

307

o-Coumarilic acid, 134, 214, 228, 229.
Coumarin for hydrogen cyanide, 268.

,, for o-hydroxyacetophenone, 228.

„ for phlorol, 134.

,, for picric acid and phloroglucinol,

162.
,, for salicylic aldehyde, 214.

Coumarone for hydrogen cyanide, 266, 268.
„ for phlorol, 134.

„ for salicylic aldehyde, 213, 214.

Cranberry, 286.
Cratcegus oxyacantha, 138, 205.
Creatinine, bacterial fermentation, 52.
Crepis fxtida, 213.
Cresol for ethyl alcohol, 56,

,, for methane, 25.
m-Cresol, 128, 285.

,, and isopropyl iodide for me nth one,

227.
,, for o-cresol, "127.
,, for p-cresol, 132.
,, for m-hydroxybenzaldehyde, 215.
,, for phenol, 122.
„ for vanillin, 221.
o-Cresol, 124, 285.

,, for m-cresol, 130.
p-Cresol, 130, 285.

,, for m-cresol, 130.
,, for p-hydroxybenzaldehyde, 218.
p-Cresol-2-sulphonic acid, 143.
Cresols for toluene and benzyl alcohol, 115.
,, ,, and quinol, 148.

„ for toluquinol, 151.
Cresorcinol, 155.

a-Cresotic (= 4-hydroxy-m-toluic) acid, 131.
/3-Cresotic (= o-homosalicylic) acid, 126.
m-(7)-Cresotic( = m-homosalicylic=3-hydroxy-

p-toluic) acid, 129, 227, 228.
o-Cresylsulphuric acid, synthesis, 128.
p-Cresylsulphuric acid, synthesis, 133.
Crocin, 244.
Crocus sativa, 244.
Croion elideria, 28, 36, 124.

Crotonic acid and aldehyde for methylpropyl-
acetaldehyde, 186, 188.
,, „ for acetaldehyde, 178.

„ „ for acetone, 196, 197, 198, 199.

„ ,, for allylene and toluene, 109, no.

,, ,, for isopropyl alcohol, 67, 68, 69.

,, ,, for /3-methylglyceric acid, 171,

178.
„ ,, for n-propyl alcohol, 280.

„ aldehyde, 190, 288.
„ ,, and acid for formic aldehyde,

170, 171, 172, 173, 174.
,, „ and hydrogen cyanide for

erythritol, 103.
,, ,, and thiocyanic acid for cro-

tonyl isothiocyanate, 257.
,, ,, for acetaldehyde, 179, 180.

„ ,, for acetone, 199.

,, ,, for n-butyl alcohol, 71.

,, ,, for butyric aldehyde, 183.

„ „ for isopropyl alcohol, 67.

,, ,, for n-propyl alcohol, 60.

„ ,, for quinol, 151.

„ „ for toluene, in, 113.

Crotonyl alcohol, 257.

,, bromide == a-brom-/3-butylene brom-
ide, 257.
,, isothiocyanate, 256.
Crotonylamine, 257.
Crotonyldithiocarbamic acid, 257.

X

Crotonylene for benzene, 30.

„ for methylethyl ketone, 95.

„ from butylene bromides, 30.

,, from tiglic acid, 31.

Cryptogams, mannose-yielding compounds in,

249.
Cryptomeria, wood of, 249.
Cubebs oil, 36.

Cumene =• isopropylbenzene, 32, 207, 211, ai2,

261.
,, ,, for benzaldehyde,

211.
Cumic acid, 32.

,, ,, for benzaldehyde, 211.

,, alcohol from cumic aldehyde, 33.

,, ,, for cymene, 33.

„ aldehyde, 212.

„ „ and acid for salicylic aldehyde,

215-

„ ,, and carbon disulphide for ben-

zyl isothiocyanate, 259,
,, ,, for benzaldehyde, an.

,, ,, for o-cresol, 127.

„ „ for cymene, 33.

,, „ for o-hydroxyacetophenone,

229.
„ ' ,, for thymol, 136.
„ ,, from cymene, 34.

Cumin oil, Roman, 28, 212.
Cuminum cyminum, 28, a 12.
Cunila mariana, 136.
Curcuma sedoaria, 92.

Cyanacetic acid and ester, 61, 63, 1 13, 283.
7- Cyanacetoacetic ester, 77, 155.
i^-Cyanacetophenone, 206, 209, an.
Cyanamide, 269.
Cyanamides, metallic, 263, 264.
Cyancampholic acid, 272.
Cyanides for thiocyanates, 269.

„ organic, in plant oils, 268.
,, synthesis of, 263, 264, 265.
Cyanobutyric acid and ester, 61, 62, 63, no.
Cyanogen bromide, 252, 258.

,, &c., for thiocyanates, 269.
Cyanomaclurin, 155, 160.
7-Cyanopentane-a7€-tricarboxylic ester, 283.
a-Cyanopropionic acid, 176.
o-Cyanotoluene, see o-toluic nitrile, 128.
m-Cyanotoluene, see m-toluic nitrile, 129.
Cyanotoluenesulphonic acid and amide, 228.
Cycads, woody tissue of, 250.
Cyclamen europceum, 104.
Cyclamin, occurrence, 104.
Cyclostemon sp., 41.
Cydonia japonica, 205.
,, vulgaris, 205.
Cymene, 28, 277.

,, and carbon disulphide for benzyl iso-
thiocyanate, 259.
,, ,, „ for phenylethyl

isothiocyanate, a6i.
,, for acetophenone, 118.
„ for benzaldehyde, 211.
,, for carvacrol, 136.
,, for o-cresol, 127.
,, for cumic aldelxyde, 34, 213.
,, for o-hydroxyacetophenone, 229.
,, for isopropylbenzene, 34.
„ for phenol, 123.
„ for phenylethyl alcohol, 118.
,, for salicylic aldehyde, 215.
,, for styrene, 34.
„ for thymol, 137.

308

INDEX

Cjmene tor toluene and benzyl alcohol, 115-

Qfrnoae-a-salphonie acid, 136.

G>ymBiie-3-salphonie acid, 137.

C^mene, aiyntiieses, 3a.

(^xnidiiM, see aminoeymene, 107, 136.

Qntel[taK I fc ry TBC 1 jiJtaf 11 w 43.

HatbiskinOK gnciUbttti, 43.
Hmwmimfiaekmtaris, Brj.

y, foacC^bltd, 88.
Def^ol, aoi.
Deeoie acid, aoi.
n-Deooie and formic acids for deooic aldehyde,

190.
Deeoie aldehyde, 188, a88.

„ ethyl eater, occurrence, 45.
Dehydracetie acid, 155.
Defaydroeamphoric acid, 070.
■PijpJWiiwn* ooNsoIula, x6i.
„ aoiO; 138, 139.
Smirognifka ImnpheBO, a86.
p-De^y]^enol, 037.
Dextrin, bacterial fennentation, 51, 5a.

„ ferments, 48-53.
Dezfaoae, 244^ 393.

„ acetone firom, by fermentation, 193.
„ aldehyde firom, a88.
„ and acetic acid for n-sec amyl al-
cohol, 79.
„ bacterial fermentation, 51, 53, 53,

69,70.

„ fermentability by moulds, 49, 50L

„ fermentation of, 46.
„ „ by Oidium oBneoHS, 174.

„ for ac^l, 94.

„ for acetone, 199.

„ for acrolein, 190.

„ for aldehyde, 180.

„ for d-arabinoae, 343.

„ for catechol, 141.

„ for diacetyl, 304.

„ for errthritol, 103.

„ for erjrthrose, 343.

„ for ethyl alcohol, 56.

„ for formic aldehyde, 173.

„ for furfural, 324.

„ for hydrogen cyanide, 066.

„ for isopropyl alcohol, 63.

„ for la^Tulose, 248.

„ for Tuannitol, 106.

„ for mannoae, 250.

„ for methane, a6.

„ for sorbitol, 107.

„ from glyoogm, 346.

„ glycerol from, by Oidnan, 97.

,, industrial production from starch,

a45-
„ velocity of fermentation of, 379.
Dhurrin, 315.

Diabetic urine and blood, 246, 248.
Diacetonamine, 171, 179, 180, 280.
Diaeetone alcohol = dimethylacetonyl carbi-

nol, 180, 280.
Diaoeturia, 246.
Diacetyl, 203. 289.

„ and methyl alcohol for tort, butyl

alcohol. 76.
„ for metl ylacetyl carbinol, 95.
„ for quinol, 149, 150, 151.
DiacetyTdicarboxylic ( = ketipic) acid, 150.
Diacetyldihydrozyacetic (= diacetylglyo^lic)
acid, 30.

0/9-Diaeetyl-a-methyIpropiouic ester, loa.
Diaeetylmonoxime = isonitrosomethylethyl

ketone = butadioneozime, 149, 304.
i3/3>DiacetyIpropionic ester. loa.
Diaoet^-leuedicarboxylic acid, 183.
Diallyl for butane. 70.

„ for hexane and pentane, 76, 81, 83, 83.
Diaminoacetone, 99, 243.
3 : s-Diaminoanisole, 164.
a-Diaminoauthraquinone, 339.
Diaminohydroxyanisole. 164.
z :3-Diamino-m-hydroxyauthraquinone, 291.
1 : 4-Diamino-8-naphthol. 167.
Diazoacetoaeetic ester, 267.
Diaiomethane, 307.
Dibenzaminodioxytotrol, 99.
Dibenz^ ketone, 309.
Dibenzvlaniline, 206.
Dibromacetoacetic ester, 64, 148.
X* : i'-Dibromaeetoi»henone, aio.
Dibromanth raeene bromide. 238.
Dibromanthraquinone, 338, 241.
t : 3-Dibrombutane, 71, 72.
Dibrombutanes for methylethyl ketone, 95.
4:3: 3-Dibrombuianolic acid, 186.
I>i-(sec.)-butyldithiocarbamate, 254.
o^-Dibrombutyric acid, 171, 17a.
cuS-Dibrombutyronitrile, 173.
Dibrom-m-cresotic acid, 227.

1 : 2-Dibromethyl ether, 225.

I* : i*-Dibromethjlbenzene = styrene brom-
ide, 34, 307, aa», 237.

1 : 2-Dibromheptane, 201.

a3-I>ibromhydrocinnamic = phenyl-«^-di-
brompropionic ester, 209, 228.

I* : I'-Dibrom-p-hydroeoumaric methyl ether
= p-methoiydibromdihYdrocinnaiuie acid,
229.
/3-DibromliBvulic acid, 149.

Dibrom-melilotic acid and ether, 214, 228.

Dibrom-menthone, 136.

1 : 3-Dibrom-3-metliylbutane = i8-dimethyltri-
methylene bromide = amylene bromide,
202. 203.

2 : 3-Dibrom-3-methylbutan6 = trimethyl-
ethylene or amylene bromide, 194, 195, 202,
203.

a :3-Dibrompentane, 188.

3 : 5-Dlbromphenol, 162. 163.

2 : 2-Dibrompropane, 98.

ao- and a^-Dibrompropionic acids, 61, no,
114, 145. 151, 176. 187.

Dibrompropionic aldehyde, 106.

a^Dibrompropyl alcohol, no.

Dibrompropylamine, 98.

I : a-Dibrompropylene, 195.

Dibromsebacic acid, 81.

Dibromsuccinic acid, 26, 57, 63, 64, 116, 177,
179. 183, 184, 268.

3 : 5-Dibromtoluene. 154,

3 : 5-Dibrom-2-toluidine, 154.

3 : 5-Dibrom-4-toluidine, 154.

78-Dibromvaleric acid, 102.

Dicarboxyglutaconic ester, 31, 62. 124.

Dichloracetal. 98.

Dichloracetaldehyde, in, 187.

Dichloracetic acid, 74.

I : i-Dichlr»racetone, 60.

I : 3-Dicbloracetone = i : 3-dichlorpropanone,

98.
Dichloranthraquinone, 238.
aj3-Dichlorbutyric acid, no, 188.
a)3-Dichlorcrotonic acid, in.

INDEX

309

I : I'-Dichlorethyl ether = ethylidene oxy-

chloride, 254.
I : 2-Dichlorethyl ether, iii, 187, 225, 236, 255,

1 :i-DichIorheptane <= oenaiith>lidene chloride,
27, 201.

DichJorhydrin = dichlorisopropyl alcohol, 67,

94-
^-I>ichlorIsopentane, 196.
Dichlorisopropyl alcohol = dichlorhydrin, 67,

94-
Dichlorlactic acid, iii, 187,
Dicblormalelnimide, loi.
I* : i'-Dichlor-3-nitrotolaene, 122.

2 : 2-Dichlorpropane, 65. 94, 98.

a a-Dichlorpropionlc acid, iii, 114, 151, 187,

»99-
a ^-Dichlorpropionic acid, 178.
a ^-Dicblorpropyl alcohol, 178.
Dichlorpropylenes, 93, 94, 11 1.
Dicrotonic acid, 1 10.

„ ,, for p3rrotartaric acid, 60.

I>ieffenbachia seguine, 262.
Diethoxalic (= hydroxydiethacetic) acid, 78,
P-Diethoxypropionic acid, 177.
Diethyl carbinol = 3-i>entanol, 78, 188.
Diethylamine for erythritol, 103.
a-Diethyl-^-hydroxybutyric acid, 178.
Diethyl' ketone, 78, 188, 281.
Diffusin, 153.
Digiialis leaves, 234.
Digitoflavone = luteolin, 234.
Dihydrocarveol, 38, 127, 285.

,, for terpinene, 39.

Dihydrocarvyl amine for dipentene, 38,
„ for terpinene, 39.

Dihvdrolutidine-dicarboxylic ester, 129.
Dihydromethylpyrrole= methylpyrroline, 100.
Dihydro-m-xylene, 127.
Dihydroxyacetone, 242, 292.

„ fermentability of, 46.

,, for glycerol, 99.

1 : 4-Dihydroxyanthraquinone = qninizarin,

241.
2 : 4-Dihydroxybenzoic ( = P-TeaatcjMii) acid,

i43» 144. 232, 233.
2 : 5-Dihydroxybenzoic [ = gentisic) acid, 146,

147, 148, 232, 233.

2 : 6-Dihydroxybenzoic acid, 143.

3 : s-Dihydroxjbenzoic ( = o-resorcylic) add,

144, 239, 241.
Dihydroiybatane for erythritol, 100.
a^Dihydroxy butyric ( = ^- methylglyceric) acid,

170-173, 177, 178-
Dihydroiyc-amphoric acid, 272.
Dihydroxymaleic acid, 106, 172, 225, 267.
I :3-Dihydroxynaphtlialene, 115.
I : 5-Dihydroxynaphthalene, 167.
I : 8-Dihydroxynaphthalene, 167.

1 : 6-Dihydroxynaphthalene-3-8ulphomc acid,

130.

2 : 3-Dihydroxypentane = sym. methylethyl-
ethylene glycol, 188.

8-DiJbydroxyphenylacetic( = 3 : 5-phenediolethy-

lic) acid, 154.
Dihydroxyphenyltricarboxylic ester, 154.
aa-Dihydroxysebacie acid, 81.
3: 4-Dihydroxj-styrene = Tinylcatechol, 14a.
Dihydroxyterephthalic (= quinoldicarboxylie)

acid and ester, 64, 148, 149.
Diiodoacetone, 98, 190.

2 : 5-Diiodohexane, 81.

3 :5-Diiodosalicylic acid, 159.
Diisonitrosoacetone, 99.

Diisopropyl, 83.

„ carbinol, 196.

„ glycol, 2cx>.

„ ketone, 68, 69, 196, aoo,

Diketoiq>oeamphoric ester, 272.
IHkeiohexamethylene-dihydroresoreinoI, 144.
Dill, oil of, 37, 226.

2 :6-Dimethoxybenzoic nitrile, 143-

3 : 4-Dimeihoxybenzoylbenzoic acid, 240.

3 : 5-Dimethoxyqainone and qninol, 163, 164.
Dimethyl sulphate, 221, 268, 284, 285.
Dimethylacetoaeetie ester, 267.
Dimethylaoetonedicarboxylie ester, 77.
Dimethylaeetopropyl carbinol and iodide, 203.
^-Dimethylacrylie acid and ester, 73, 75, 182,

183, 197, 273. a8o-
Dimethylallyl carbinol, 73, 183.
Dimethylallylacetoacetic ester, 203.
Dimethylallylene = 3-methyl-i : 2-bu*adiene,

195, 202, 203.
Dimethylaniline, 150, 207.

„ for naphthalene, 166.

1 : 3-Dimethyl-4-benzoic ( = xyUc) acid, 126, 129.
Dimethylbatanone = pinacolin, 75.
Dimethylethyl carbinol, see mider amyl alco>

hoi, tertiary.
^^Dimethylglntarie acid, 272.

2 :6-Dimethyl-2 : 5-heptadienone, see phorone.
a : 6-Dimethyl-2-heptenol-6, 86, 28a.

„ „ for acet<me, 199.

,1 t, for diaeetyl, 204.

„ tt f<^ dimethyUiep-

tenone, 203.

„ „ for erythritol, 103.

„ >, for Ixrolic acid,

103.

„ „ for qninol, 151.

Dimethylhydroresorcinol, 272.
Dimethylhydroresorcylic ester, 372.
Dimeihylisopropyl carbinol, 74, 75, 76, 193,

196-199.
Dimethylphloroglacinol, 161.
Dimethylpiperidine, 103.
Dimethylpropanetricarboxylic ester, a^a.
Dimethylpyrrolidine, 100, 103.
Dimethylpyrrolidine-methiodide, loi.
Dimethylthymoqoinol, 158.
3 : s-Dinitroanisole, 164.
o-Dinitroanthraqoinone, 239;
m-Dinitrobenzene, T43.

3 : 5-Dinitro-p-cresol ether, 154,

1 :3-Dinitro-m-hydroxyanthniqainone, 291.
Dinitromesitylene, 157.
Dinitro-o-naphtholsnlphonic acid, 123.

2 : 4-Dinitrophenylacetie acid, 193, larj, 134,

148,286.
3:4-Dinitrophen7laeetoaeeticester, 134.
Dinitroprojtanes, 62, 64, 186, z88, 197.
4 : 1'-Dinitrostyrene, 216.

2 :4-Dinitiotolnene, 127, 131, 148, 156, a86.
3 : 5-Dinii3t>tolaene, 154^

3 : 5-Dinitro-4-toIaidine, 154.
Dinitrooraminobenzoic acid, 147, 233.
3 : 5-Dinitro-p-xylene, 156.
Diosmaalba, 160.
Dio^ifiras IsakL, 249.
Dioxytartarie acid, zi6, 267.
Dipentene, 36, 27&

„ for canrone, 226.

„ for cymene, 32.

,, for terpinene, 39.

„ for terpineol, 91.

Diphenylketipic aJihydride, 43.

310

INDEX

Diphenylthiourea, 253.
Dipropyl ketone = butyrone, 85.
Disaccharides, synthetical, fermentability of,

46.
Dispora caucasica, 51.

2 : 4-Disulphobenzoic acid, 143.

3 : 5-Disulphobenzoic acid, 144, 239.
Divaricatic acid, 153.

Divinyl = erytlirene, &c., 100, lor.
Dodecyl alcohol, n-primary, 85.
Dorema ammoniacuni, 133, 139.
Dragon's blood, 161.
Dryobalanops camphor a = aromatica, 272.
Dulcitol, bacterial fermentation, 51, 52,
Dyers* broom, 139, 230, 234.
Dypnone, 135, 261.

Echinocadus lewinii, 159.

Elaieriospermum tokbrai, 41.

Mceocarpus resinoaus, 41.

Elais guineensis, 249.

Elaphomyces granulatus, 105.

Elastin, anaerobic putrefaction, 252.

,, methane fermentation of, ai.
Elemi resin, 36, 39.
Elettaria aromaticum, 91.

,, cardamomum, 36, 37, 39, 90, 91, 271,

273-
Ennoic = nonoic aldehyde, 189.
Enterococcus from milk, 279.
Enzymes of yeast, 244.
Epacris leaves, 161.
Ephedra distachya, 104, 250.
Epichlorhydrin and nitrile, no, 178.
Epigcea repens, 146.

Epinephrine = adrenalin = suprarenin, 286.
Ergot of rye, 249.
Ergotised rye, mannitol in, 105.
Erigeron canadensis, 37, 90.
Eriobotyra japonica, 262.
Erythea edxdis, 249.

Erythrene = pyrrolylene = di vinyl, 100, loi.
Erythrin ( = erythricacid) and ^-erytlirin, 100,

153, 156.
Erythritol, 100.

,, and carbon disulphide for sec. butyl

isothiocyanate, 255.
,, and formic acid for acetone, 199.

,, ,, for acetaldehyde,

179.
„ ,, for n-butyl alcohol,

71.
„ ,, for formic aldehyde,

172.
,, bacterial fermentation, 51, 242.

, , for d-erythrulose, 242.

,, for isopropyl alcohol, 67.

,, for n-propyl alcohol, 60.

Erythrose, 243.

d-Erythrose for erythritol, 103.
Erythroxylon coca, 41, 42, 192.
d-Erythrulose, 103, 242.
Estragol, 137.

Ethane for acetaldehyde, 175, 176, 181, 288.
,, for acetone, 199.
„ for ethyl alcohol, 54, 279.
,, from acetic acid, 56.
,, from acetylene, 53.
,, from isopropyl alcohol, 279,
,, from isovaleric acid, 57.
„ from methyl alcohol, 54.
,, from propionic acid, 56.
„ generators of, 54, 55.

Ethanedinitro-tetracarboxylic ester, 166.
s-Ethanetettacarboxylic ester = acetylenetetra-

carboxylic ester, 166.
Ethanoylcyclopropane = acetyltrimethylene, 77.
o-Ethoxyacetophenone, 214.
Ethoxychloracetoacetic ester, 98.
i3-Ethoxycinnamic acid, 210.
3-Ethoxy-3^ : 4^-dimethoxyflavanone, 275.
3-Ethoxy-3^ : 4^-dimethoxyflavonol, 275.
Ethoxyfumaric acid, 63, 64, 116.
Ethoxymethylene-acetoacetic ester, 285.
Ethoxymethylene-malonic ester, 145.
Ethyl acetate, occurrence, 45.

,, alcohol, 44, 278.

,, ,, anaerobic production by intra-

cellular respiration, 44, 278.

,, ,, and acetaldehyde for acetal, i8r.

,, ,, and acetic acid for erythritol,

lOI.

,, ,, and acetic or isovaleric acid for

mesitylenic acid, 126.

,, ,, and butyric acid for nonyl alco-

hol, 85.

,, ,, and carbon disulphide for sec.

butyl isothiocyanate, 255.

,, ,, and hydrogen cyanide for quinol,

151-

,, ,, and oenanthol for nonyl alcohol,

85.

„ „ by glycolysis, 279.

,, ,, &c., for methylpropylacetalde-

hyde, 187.

,, ,, &c., for n-secondaryamyl alcohol,

77-

,, ,, &c., for thiocyanates, 269.

,, ,, for acetal, 181.

,, ,, for acetaldehyde, 175, 288.

,, ,, for allylene, 114.

,, ,, benzene, 29.

,, ,, for n-butyl alcohol, 70, 280.

,, ,, for carbon disulphide, 251.

), ,, for erythrose, 243.

,, ,, for ethyl sulphide, 253.

,, ,, • for formic aldehyde, 170.

,, ,, for furfural, 225.

,, ,, for glycerol, 98.

„ „ for glycol, 95.

,, ,, for hydrogen cyanide, 266.

,, ,, for isopropyl alcohol, 66.

,, ,, for mannitol, 106.

,, ,, for methane, 23, 277.

,, ,, for methyl alcohol, 44.

,, ,, for naphthalene, 287.

,, ,, for n-propyl alcohol, 58.

,, ,, glycerol from, by Mycoderma, 97.

,, and methyl alcohols for tert. butyl alco-
hol, 75.

,, butyrate, occurrence, 45.

,, chloride for methane, 23.

,, chlorocarbonate, 125.

,, cinnamate, occurrence, 45.

,, cyanide = propionitrile, 61, 66, in, 114,
151, 187, 196, 199.

,, decoate, occurrence, 45,

,, esters in fusel oil, 46.

,, ,, in rancid butter, 53.

,, ether, 23, in, 170, 176, 187, 225.

,, ,, for methane, 23.

,, hexoate, occurrence, 45.

,, iodide and acetic anhydride for methyl-
ethyl ketone, 95.

,, ,, from propionic acid, 56.

,, isobutyl-acetoacetate, 281.

INDEX

311

Ethyl laureate, occurrence, 45.

,, p-methoxycinnamate, occurrence, 45.
,, octoate, occurrence, 45.
,, oleate, occuri-ence, 45.
,, palmitate, occurrence, 45.
,, sulphate, salt of, in urine, 53.
,, sulphide, 253.
,, valerate, occurrence, 45.
Ethylacetoacetic ester, 64, 186, 188.
Ethylacetylacetone, 77.
a-Ethylallyl alcohol, 184.

,, chloride, 184.

Ethylallylamine, 102.
Ethylamine for acetaldehyde, 1 80.
,, for acetonitrile, 207.

,, for ethyl alcohol, 57.

,, for hydrogen cyanide, 268.

,, for methane, 26.

Ethyl-m-aminobenzene, 135.
Ethyl-p-aminobenzene, 135.
Ethylbenzene, 286,

,, and carbon disulphide for

phenylethyl isothiocyanate,
260, 261.
,, for anthracene, 237.

„ for benzaldehyde, 207, 211.

„ for 3-ethylphenol, 135.

„ for o-hydroxyacetophenone, 229.

,, for methylphenyl carbinol, 118.

,, for w-phenylethylamine, 34.

,, for phlorol, 133, 134, 135.

,, for salicylic aldehyde, 215.

„ for styrene, 34.

,, for a-toluic aldehyde, 34, 260.

,, syntheses, 133.

Ethylbenzene-m-sulphonic acid, 135.
Ethylbenzene-o-sulphonic acid, 133.
Ethyl-2-brombenzene-3- or 5-sulphonic acid,

135-
Ethyl-4-brombenzene-2-sulphonic acid, 133.
Ethyl-7-bromphenyl ether, 119.
Ethylbutylacetaldehyde, 189,
Ethylchlorether = a-ethyl-i-chlorbutyl ether,

255-
a-Ethylcrotonic acid, 77, 78.

,, ester, 188.

Ethyl-aS-dibrompropyl malonate, 102.
Ethyldipropyl carbinol = 4-ethyl-4-heptanol, 85,
Ethylene and hydrogen cyanide for acetone,
199.

,, bromide, 66.

,, chloride, 58, 108.

,, for acetaldehyde, 175, 176, 177.

,, for anthracene, 237.

,, for benzene, 29.

,, for benzyl alcohol, 108.

,, for crotonic aldehyde, 71, 190.

,, for erythritol, 100.

,, for erythrose, 243.

,, for formic aldehyde, 170.

,, for furfural, 225.

„ for glycol, 95.

,, for isopropyl alcohol, 66.

,, for methane, 23.

,, for methylpropylacetaldehyde, 187.

,, for phloroglucinol, 162.

,, for n-propyl alcohol, 58.

„ for styrene, 33.

,, from acetic acid, 56.

,, from acetylene, 53.

,, from azelaic acid, 26, 57.

,, from bromoform, 56.

,, from carbides, 54.

Ethylene from carbon disulphide, 54,

,, from cresol, 56.

,, from ethyl alcohol, 23.

,, from heptane, 54.

,, from n-hexane, 55.

,, from isobutylene, 55.

,, from isovaleric acid, 57.

,, from lactic acid, 57.

,, from malonic acid, 25, 57.

,, from mannitol, 57.

,, from metallic carbides, 54.

,, from methyl chloride, 54.

,, from methylene iodide, 55.

,, from phenol, 56.

,, from propionic acid, 56.

,, from succinic acid, 25, 57.

,, generators, pyrogenic, 23.

„ glycol, 95.

,, ,, &c., for sec. butyl isothio-

cyanate, 255.

,, ,, ethyl ether, 225.

,, ,, for furfural, 225.

,, iodide, 225.

,, oxide, 175, 280, 281, 288.
Ethyleneacetoacetic ester, 77.
Ethylglyoxylic ( = propionylformic) acid, 187.
Ethylhexyl carbinol = 3-nonanol, 85.
a-Ethyl-;3-hydroxybutyric acid, 77.
Ethylidene bromide, 181.
„ chloride, 55.

,, oxy chloride = i : I'-dichlorether,

254-
Ethylidenemalonic ester, 62, no.
7-Ethylidene-7-methylpyrotartaric acid, loi.
Ethylisobutyl ketone, 197.
1 : 3 : 5-Ethylisophthalic acid, 134, 211, 260.
Ethylisopropyl ketone, 197, 199.
Ethylmalonic acid for isopropyl alcohol, 67, 68,
69.
,, >) for methylpropylacetalde-

hyde, 186, 187.
,, ,, for n-propyl alcohol, 61, 62,

64, 68.
Ethyl-m-nitrobenzene, 135.
Ethyl-p-nitrobenzene, 135.
Ethyloxalyl chloride = chlorethanalic ester,

208, 216, 218, 221.
3-Ethylphenol, 136.
Ethylphenyl carbinol, 212,

,, ketone, 212.

Ethylpropyl ketone, 62, 188.
a-Ethyl-iS-propylacrole'in = octenoic aldehyde,

189.
Ethylsulphuric acid, salt of, in fistula bile, 53.

„ „ synthesis, 53.

a-Ethyltartronic acid, 187.
Eucalyptus aggregaia, amyl ester in oil, 79.
,, amygdalina, cineole in oil, 92.
,, angophoroicles, cineole in oil, 92.
,, baileyana, cineole in oil, 92.
,, bicolor = largiflorens, cineole in oil, 92,
,, camphora, cineole in oil, 92.
,, capitellata, cineole in oil, 93.
,, citriodora, citronellal in oil, 192.
,, coi-ymhosa, cineole in oil, 92.
,, crebra, cineole in oil, 92.
,, dealbata, citronellal in oil, 192.
,, dextropinea, cineole in oil, 92.
,, dumosa, cineole in oil, 92.
,, eugenioides, cineole in oil, 92.
,, fletcheri, cineole in oil, 9a.
,, globulus, a8, 45.
,, ,, butyric aldehyde in oil, 181.

812

INDEX

Eucalyptus globulus, eineole In oil, 92.

,, ,, cumic aldehyde in oil, 212.

,, ,, hexoic aldehyde in oil, 185.

,, ,, isoamyl alcohol from oil, 79.

„ ,, valeric aldehyde in oil, 183.

,, goniocalyx, eineole in oil, 92.

,, hwmastoma, 28.

,, „ eineole in oil, 92.

,, „ cumic aldehyde in oil,

212.

„ „ menthone in oil, 227.

,, hemipMoia, eineole in oil, 92.

„ ,, cumic aldehyde in oil, 213.

,, intermedia, eineole in oil, 92.

„ intertexta, eineole in oil, 92.

,, lactea, eineole in oil, 92.

,, IcBvopinea, eineole in oil, 92.

,, loxophleba, eineole in oil, 92.

,, macarthurif geraniol in oil, 87.

,, macrorrhyncha, amyl ester in oil, 79.

ff ,, eineole in oil, 92.

,, ,f quercetin complex in

leaves, 138.

„ macidata, citronellal in oil, 192.

,, maculosa, eineole in oil, 92.

„ melliodora, eineole in oil, 92.

,, microcorys, eineole in oil, 92.

„ morrisii, eineole in oil, 92.

,, obliqua, eineole in oil, 92.

,, odorata, cumic aldehyde in oil, 212,

,, oleosa, eineole in oil, 92.

,, ,, cumic aldehyde in oil, 212,

„ ovalifolia, eineole in oil, 92.

,, patentinervis, amyl ester in oil, 79.

„ ,, citral in oil, 191.

„ ,, geraniol in oil, 87.

„ „ linaloOl in oil, 88.

,, piperita, eineole in oil, 92.

,, planchoniana, citronellal in oil, 192.

„ polybractea, eineole in oil, 92.

„ populifera, cumic aldehyde in oil, 212,

,, populifolia, eineole in oil, 92.

„ pulverulenta, eineole in oil, 92.

,, punctata, eineole in oil, 92.

„ resinifera, eineole in oil, 92.

„ ,, kino from, 138.

„ risdonia, eineole in oil, 92.

„ rosirata, eineole in oil, 92.

,, „ valeric aldehyde in oil, 183.

,, smithii, eineole in oil, 92.

,, species yielding eineole, 92.

„ staigeriana, citral in oil, 191.

„ umbra, eineole in oil, 92.

,, viridis, eineole in oil, 92,

„ „ cumic aldehyde in oil, 213.

„ vitrwa, eineole in oil, 92.

,, „ citral in oil, 191.

,, wilkinsonia = Icevopinea var. minor,
eineole in oil, 92.

,, woollsiana,. eineole in oil, 92.
Euonymus japonica, 244.
Euphorbiaceae, methyl salicylate in, 41.
Euphrasia, mannitol in species of, 104.
Eurotiopsis gayoni, alcoholic ferment, 50.

,, ,, aldehyde producer, 174.

,, ,, glycerol producer, 97.

Eurotium (Aspergillus), oryzae from * Koji ' fer-
ment, 49, 50.
Euxanthic acid, 232, 233.
Euxanthone, 142, 146, 232.
,, for quinol, 148.

,, for resorcinol, 145.

Evernia divaricata, 153.

Evemia prunastri and vars. ihamnodes and vul-
garis, 152, 153.
,, species yielding atranorin, 42.
Evernic acid, 152.
Evemiopsis trulla, 42.
Excoecaria glandulosa, 151.
Excoecarin, 151.

Fat of ovarian cysts, 86.
,, rancid, butyric aldehyde in, 182.
,, ,, hexoic aldehyde in, 185.
,, ,, oenanthol in, 189.
Fats, hydrolysis of, 95.

,, rancid, 84.
Fennel, bitter, 28.

,, ,, French oil, 218.

„ oil, 36, 37, 137, 158.
Fermentation, alcoholic, by Mucor, 48, 278.
,, ,, ,, Mycoderma, 48.

,, ,, ,, O'idium, 279.

,, ,, ,, Torvla, 48.

» >! » yeasts, 45.

,, selective, by yeasts, 47, 278

Ferulaic acid, 140.

,, ,, for vanillin, 221.

Feverfew oil, 271, 273.
Fibrin, cinnamic aldehyde among products of

pancreatic fermentation, 223.
Ficus, methyl salicylate from, 41.
Filixic acid, 161.
Fisetin, 139, 142, 275.
Fish, acetone among products of putrefaction,

193-
Fish, methyl mercaptan among products of

putrefaction, 252.
Fistula bile, salt of ethylsulphuric acid in, 53.
Flavaspidic acid, 161.
Fleabane, oil, 37, 90.
Fodder, phenol among decomposition products,

285.
Foeniculum panmorium, 137.
„ vulgare, 36, 137.
Formamide, 266.
Formanilide, 207.

Formic acid and methyl alcohol for carbon
disulphide, 252.
,, ,, for carbon tetrachloride, 25.

,, ,, for formic aldehyde, 171.

,, ,, for hydrogen cyanide, 266.

,, ,, for methane, 25.

,, ,, for methyl alcohol, 44.

,, aldehyde, 169, 287.
,, ,, and ethyl alcohol for n-pro-

pyl alcohol, 59.
,, ,, and hydrogen cyanide for

mannoheptol, 107.
,, ,, and methyl alcohol for

dihydroxyacetone, 242.
,, ,, and plienol for p-hydroxy-

benzyl alcohol, 118.
,, ,, and phenol for saligenin,

117.
„ ,, and n-propyl alcohol for

n-biityl alcohol, 71.
,, „ for dextrose, 246.

,, „ for furfural, 225.

,, ,, for hydrogen cyanide, 266.

„ „ for mannitol, 105.

,, ,, for mannose, 250.

,, ,, for methyl alcohol, 44, 278.

,, ,, for n-propyl alcohol, 60.

„ and acetic esters for crotonic aldehyde,
71, 190.

INDEX

313

Formic and isobutyric aldehydes for isovaleric
aldehyde, 184.
,, ethyl ester for n-sec. amyl alcohol, 78.
,, methyl ester for ethyl alcohol, 56.
Formimino-ethyl ether, 181.
Formopyroracemic ester, 94.
Formylacetic (= hydroxymothyleneacetic =

/3-hydroxyacrylic) acid, 30, 71, 176.
Formylbornylamine, 274.
Formylglutaconic ester and acid, 31, 71.
Fragaria vesca, 139.
Fragarianin, 139.
Frankincense oil, 37.
Fraxinus excelsior, 104.

,, ornus — Ornus europcca, Sec, 104.
Fraxitannic acid, 139.
i-Fructose, 246.

1-Fructose, non-fermentable, 46.
Fukugi, Japanese, 286, 287.
Fulminate, mercury, and anisole for anisic
aldehyde, 218.
,, ,, and benzene for benz-

aldehyde, 207.
Fumaric acid for acetaldehyde, 179.
,, ,, for benzene, 31.

,, ,, for hydrogen cyanide, 268.

,, ,, for isopropyl alcohol, 69.

,, ,, for methane, 26.

,, ,, for n-propyFalcohol, 64.

„ „ for toluene and benzyl alcohol,

116.
,, ,, for valeric aldehyde, 184.

Furfural, 224.

,, acetone, and phloroglucinol for gen-

tisin, 233.
,, ,, and resorcinol for euxan-

thone, 233.
,, and acetone for quinol, 150.
„ „ for quinone, 235.

,, ,, for resorcinol, 145.

,, and aniline for hydrojuglone, 168.
,, for acetaldehyde, 180.
,, for catechol, 140.
,, for erythritol, 103.
,, for phloroglucinol, 163.
Furfuryl alcohol, 225.
Fusel oil, acetal in, 181.

,, ,, acetaldehyde in, 174.

,, „ borneol in, 273.

,, ,, esters in, 46.

,, ,, from beet molasses spirit, 72.

,, ,, from brandy, 70, 72, 80, 82, 83.

,, ,, from grain spirit, 70, 72.

,, ,, from potato starch spirit, 64, 70, 72,

77-
,, ,, furfural in, 224.
,, ,, hexyl alcohol in, 80.
,, ,, n-propyl alcohol in, 58.
,, ,, tertiary butyl alcohol in (?), 73.
,, oils, isoamyl alcohol in, 79.
Fustin, 139.

Galactose, bacterial fermentation, 52, 70.
,, fermentability by moulds, 49.

d-Galactose, fermentation of, 46, 50.
Galangin. 161.
Galbanum, 142.
Gall-stones, 99.
Gallic acid for alizarin, 239.

,, ,, for carbon disulphide, 252,

,, ,, for ethyl alcohol, 57.

,, ,, for methane, 26.

,, ,, for phenol, 121.

Gallic acid for pyrogallol, 159

,, and benzoic acids for anthragallol, 240.
Gambir catechu, 139, 160.
Garcinia morella, 42, 161.
Garden cress, 257.
Gardenia oil, 89, 90, 108, 118.

,, species of, 41, 42, 89, 90.
Garlic-mustard, 256.

„ oil, 253.
Gasparinia elegans and medians, 45.
Gastric juice, thiocyanate in, 268, 269.
Gaultheria leucocarpa, 40.

,, procumbens, 40, 146.
,, punctata, 40.
Gaultherin, 40.

Gelatine, bacterial fermentation, 51.
Genipa brasiliensis, 104.
Genista tinctoria, 139, 161, 230, 234.

,, tridentata, 92.
Genistein, 161, 230.

„ phenol complex in, 119.

Gentiana lutea, 233.
Gentiauose, 29a.

„ hydrolysis of, 245, 247.

Gentiobiose, hydrolysis of, 245.
Gentisic acid (=2 : 5-dihydroxybenzoic =5-hy-
droxysalicylicacid), 146, 147,
148, 232, 233.
,, ,, generators and phloroglucinol for

gentisin, 233.
,, ,, ,, and resorcinol for eux-

anthone, 232, 233.
Gentisin, 142, 146, 233.

,, and resorcinol for ouxanthone, 233.
,, for quinol, 148.
,, phloroglucinol complex in, 161.
Geranic acid, 191, 192.
Geraniol, 87, 282.

„ for citral, 191.
,, for cymene, 32.
,, for dimethylheptenol, 86.
,, for dipentene, 38.
,, for ethyl alcohol, 55.
,, for linalool, 89.
,, for methylheptenone, 203.
,, for terpinene, 39.
,, for terpineol, 91.
Geranium oils, 36, 87, 89, 227, 282.
Geranyl chloride, 89.

„ phthalate, 89.
Ginger-beer plant, 51.

„ oil, 212, 274.
Gironniera subcequalis, &c., 41.
Glands, caudal, cetyl alcohol in, 86.
Gleditschia triacanthos, 249.
Globularia alypum, 276.
Globulariacitrin, 276.
Globulins of blood, 292.
Glomelliferin, 153.
Glucamine, 26.
Glucogallin, 287.
Gluconasturtiin, 260.
Gluconic acid for d-arabinose, 243.
,, „ for dextrose, 246, 247.

,, ,, for erythritol, 103.

,, ,, for erythrose, 243.

,, ,, for mannitol, 106.

,, lactone for dextrose, 247.

Glucononose, non-fermentable, 46.
Glucose, see also iinder dextrose.

„ bacterial fermentation, 24a.
Glucosides, 244.
Glucosone, 107, 248.

314

INDEX

Glucotropaeolin, 257.
Glutaconic ester, 124, 285.
Glutamic acid for erytliritol, 103.
Glutaric acid for n-hexane, 79, 81.

,, „ for n-hexyl alcohol, 81.

,, „ for n-primary amyl alcohol, 77.

Gluten, phenol from, by putrefaction, 119.
Glutose, non-fermentable, 46,
Glyceric acid, bacterial fermentation, 51.

,, ,, for acetaldehyde, 177, 178.

,, ,, for acetone, 196, 199.

,, ,, for diacetyl, 204.

,, ,, for formic aldehyde, 170, 172,

173-
,, ,, for methylpropylacetaldehyde,

185, 187.
,, ,, for pyrotartaric acid, 58, 108-

III, 114, 116.
,/ „ for quinol, 150, 151.

,, ,, for resorcinol, 144.

,, aldehyde and oxime, 243.
,, ,, fermentability, 46.

Glycerol, 96, 284.

,, and hydrogen cyanide for manno-

heptol, 107.
,, and thiocyanic acid for allyl isothio-

cyanate, 256.
,, bacterial fermentation, 51, 58, 69,

70, 95, 203, 242.
„ &c., for diacetyl, 204.
,, &c., for formic aldehyde, 172.
,, fermentation of, 43, 69.
,, for acetaldehyde, 177, 178.
,, for acetol, 94.
,, for acrolein, 24, 106, 190, 288.
,, for allyl alcohol, 24.
,, for allylene and acetone, 194, 195.
,, for amyl alcohol, n-primary, 76.
,, for benzene, 31.
,, for n-butyl alcohol, 70.
,, for dextrose, 246.
,, for dihydroxyacetone, 242.
,, for erytliritol, 103.
,, for erythrose, 243.
,, for ethyl alcohol, 55.
,, for furfural, 225.
„ for glycerophosphoric acid, 99.
,, for n-hexane, 79.
,, for hexyl alcohol, active, 83.
,, for hydrogen cyanide, 268.
,, for isopropyl alcohol, 67.
,, for isopropyl iodide, 67.
,, for mannitol, 106.
,, for mannose, 250.
,, for methane, 24.
,, for methyl alcohol, 44.
,, for methylpropylacetaldehyde, 185.
,, for phenol, 120.
,, for n-propyl alcohol, 59.
,, for toluene, 109, no.
,, for trimethylene glycol, 95.
,, from sugars during fermentation, 97.

,, monochlorhydrin, 195.
„ n-propyl alcohol from, by fermenta-
tion, 58.
Glycerol-acetobromhydrin, 195.
Glycerophosphoric acid, 89.
Glycerose, 106, 242.

,, fermentation of, 46.

Glyceryl esters, occurrence, 96.
Glycidic acid, see under oxyaerylic acid.
Glycocoll and chloroform for isocyanacetic acid.
26a

Glycocoll for hydrogen cyanide, 267.

,, for isopropyl alcohol, 69.

,, for n-propyl alcohol, 64.
Glycogen, bacterial fermentation, 70.

,, dextrose from, 246.

Glycol (ethylene), 95.

,, chlorhydrin = chlorethyl alcohol, 59, 66,

175, 279-
,, for acetaldehyde, 175, 179.

,, . for crotonic aldehyde, 288.
,, for ethyl alcohol, 279.
,, for formic aldehyde, 170, 173.
,, for isopropyl alcohol, 66, 69.
,, iodhydrin = iodethyl alcohol, 66, 175,

255-
Glycolazide, 171.
Glycollic acid for formic aldehyde, 171.

,, ,, for methane, 25.

,, aldehyde for dextrose, 246.

„ „ ,, by rabbits, 292.

„ „ for erythrose, 243.

,, ,, for formic aldehyde, 170,

172, 173.

,, ,, for furfural, 225,

,, ,, for mannitol, 106.

,, ,, for mannose, 250.

Glycol urethane, 171.
Glycuronic acid for catechol, 141.
„ ,, for furfural, 225.

Glycyphyllin, 160.
Glyoxal, no, in, 116.

,, for cyanogen and hydrogen cyanide,
266, 267, 268.
Glyoxime, 266, 267.
Gnetum gnemon, 41.
Golden-rod oil, 273.
Gossypetin, 139, 161.
Gossypium herhaceutn, 139, 161.
Graminin, 248,
GranMZoftadeyiirt^j/Zicwm, n-propyl alcohol producer,

58.
,, polymjjxa, 69.

„ saccharobutyricum, glycerol ferment,

51, 69.
Grapes, colouring-matter of, 138, 160.
Grass, quinone among products of fermentation,

235-
Great millet, 215.
Guaiacol, 140, 141, 142, 163, 220.

„ &c., for vanillin, 220.
Guaiacolcarboxylic acid, 220.
Guaiacum officinale, 139, 190.

,, resin, 139, 190.
Guanidine for thiocyanic acid, 269.
Gulose, non-fermentable, 46.
Gum from yeast, 250.
Gum-ammoniac, 133, 139, 142, 249.
Gum kino, 139.
Gummigutt resin, 43, 161.
Gyalolechia aurella, 45.
Gymnema latifoUuvi, 205.
Gymnosperms, ligneous tissue of, 249.
Gynocardia odorata, 293.
Gynocardin, 293.
Gyrophora (Umbilicaria) deusta, 153.

,, hirsuta, 153.

,, hyperborea, 153.

„ polyphylla, 153.

,, proboscidea, 153.

,, pustulata, 153.

,, spodochroa, var. depressa, 153.

,, velka, 153.
Gyrophoric acid, 153.

INDEX

315

HcBmatomma coccineum, 45.

,, species yielding atranorin, 42.

,, ventosum, 153.

Haematommic acid, 45.
Haematoxylin, 139, 159.
Hasmatoxylon campeachianum, 139, 159.
Hamamelis virginica, 168.
Hawk's-beard, 213.
Hawthorn flowers, 138.
Heather, 138.
Hedeomapulegioides, 226,
Helicin for salicin, 250.
Hemipic acid, 239.

Hendecatyl alcohol, secondary, 85, 282,
Hentriacontane, 28, 277.
n-Heptane, 27.

,, for anthracene, 237.

„ for benzene, 29.

,, for ethyl alcohol, 54.

,, for n-heptyl alcohol, 83,

,, for methane, 22.

„ for methyl-n-amyl ketone, 200.

„ for toluene and benzyl alcohol, 115.

n-Heptacosane, 27-
4-Heptanone = dipiopyl ketone, 85.
Heptine, 27, 115, 201.
Heptoic and acetic acids for n- heptane, 27.
n-Heptoic ( = cenanthic) acid for hexyl alcohol,

active, 83.
„ „ ,, for n-hexyl alec-

hoi, 81.

,, aldehyde = oenanthol, 189.

,, ,, and nitromethane for octoic

aldehyde, 189.
,, ,, for n-heptane, 27,

,, ,, methyl-n-amyl ketone, 201.

Heptoses, non-fermentable, 46.
Hoptoyl chloride, 82.
u-Heptyl alcohol, 83.

„ ,, and ethyl alcohol for n-nonyl

alcohol, 85.

,, ,, and palmitic acid formethyl-

n-amyl ketone, 201.

„ ,, and n -propyl alcohol for

methyl-n-heptyl ketone,
201.

,, ,, from heptoic aldehyde, 27,

Heptyl alcohol, secondary = 2-heptanol, 200.

,, ,, tertiary, for acetone, 196, 197.

n-Heptylene, 201.
Heradeum gigantemn, 40, 45, 80, 84.

,, sphondylium, 40, 45, 80, 84.
Hesperetinic acid, 140.
Hesperidene = d-limonene, 37.
Hesperidin, phloroglucinol complex in, 160.
Hexachlorethane, 236.
3 :4-Hexadionediacid = ketipic acid, 150.
Hexahydro-m-hydroxy-p-toluic acid, 128.
Hexahydroxybeiizene, 29.
Hexamethylbenzene, 30, 31.
Hexamethylenamine, 259.
Hexane ( = diisopropyl) Irom n-heptoic acid, 83.
n-Hexanefor butane, 71.

,, for butylenes, 255, 256.

,, for ethylene, 55, 57.

,, for formic aldehyde, 173, 174.

,, for glycerol, 99.

,, for n-hexyl alcohol, 80.

,, for isopropyl alcohol, 67.

,, for n-pentane, 76.

,, from.adipic acid, 81.

,, from n-butyric acid, 77. 82.

,, from glutaric acid, 77, 81.

n-Hexane from glycerol, 76, 81.
from mannitol, 79, 81.
from n-propyl alcohol, 80.
from sebacic acid, 81.
from suberic acid, 81.
generators of, 67, 79, 80, 81.
Hexanediinedicarboxylic acid, see diacetylene-

dicarboxylic acid, 183.
n-Hexoic acid for n-hexyl alcohol, 81.

,, ,, for n-primary amyl alcohol, 76.

,, ,, for valeric aldehyde, 184,

Hexoic aldehyde, 185, 288.
n-Hexoic aldehyde for n-hexyl alcohol, 81.
Hexoic ethyl ester, occurrence, 45.
i-Hexoses, resolution by partial fermentation,

46.
Hexoylacetic acid, 201.
Hexyl alcohol, active, 83, 281.
,, normal, 80.
,, ,, for ethyl alcohol, 57.

,, ,, for n-hexane, 256.

chlorides, n- and sec. , 80.
iodide from mannitol, 60.

,, secondary = 2-iodohexane, 70, 71,
81.

„ „ tertiary, 75.

n-Hexylacetamide, 82.
n-Hexylamine, 80.

,, for n-hexyl alcohol, 81, 82.

Hexylenes, 70, 81.
Hibiscita ahelmoschus, 224.
Hippophae rhamnoides, 104, 138.
Hippuric acid and carbon disulphide for benzyl
isothiocyanate, 258.
„ ,, for benzonitrile and benzalde-

hyde, 211.
,, ,, for dihydroxyacetone, 242.

Homoanthranilic ( = 3-amino-p-toluic) acid, 129,

228.
Homocamphoric acid, 272.
Homogentisic acid, 146.

,, ,, for quinol, 148.

m-Homosalicylic ( = m-(7)-cresotic = 3-hydroxy-
p-toluic) acid, 129, 227, 228.
o-Homosalicylic (^ 2-hydroxy-m-toluic) acid,

126.
Homovitexin, 161.
Honey, 244, 247.
Hops, 138.

,, oil of, 89.
Horse-chestnut, 138, 139.
Horse-mint, American oil, 37.
Horse-radish, 256.
Hydnocarpics alpinus, 262.

,, inebrians = (?) wightiana, 262.

Hydracrylic acid, 62.

,, ,, for isopropyl alcohol, 68.

,, ,, for n-propyl alcohol, 59.

,, ,, for toluene and benzyl alco-

hol, 116.
Hydrastine, 140.
Hydrastis canadensis, 140.
Hydratropic nitrile and acid, 229.
Hydrobenzamide, 258-
Hydrocaffeic acid, 140.
Hydrocinnamic aldehyde, 211.

,, and formic acids for hydro-

cinnamic aldehyde, 212.
Hydrocotoin, 231.

,, for methylhydrocoto'in, 232.

,, phloroglucinol complex in, 161,

Hydrocoumarone, 134.
Hydrogen and carbon, imion of, 22.

316

INDEX

Hydrogen cyanide, 262, 293.

,, ,, and acetic acid, &c., for

diacetyl, 204.
,, ,, &c., for thiocyanates, 269.

,, ,, for ethyl alcohol, 56.

a-Hydrojuglone, 165, 287.

,, for catechol, 141.

,, for plienol, 124.

Hydroparacoumaric acid, p-cresol from by
putrefaction, 131.
,, ,, phenol from by

putrefaction, 119.
Hydropyromellitic acid, 120.
o-Hydroxyacetophenone, 228.

,, for ketocoumaran,

230.
,, for salicylic aldehyde,

213, 214.
p-Hydroxyacetophenone, see under piceol.
/3-Hydroxyacrylic ( = formylacetic = hydroxy-

methylene-acetic) acid, 30, 71, 176.
m-Hydroxyanthraquinone, 236, 291.

,, for alizarin, 239.

,, for anthragallol,

291.
„ for purpurin, 291.

,, for quinizarin, 291.

i-Hydroxyanthraquinone for alizarin, 239.

, , -2-sulphonic acid, 239.

m-Hydroxybenzoic acid, 121, 122, 215, 236.

p-Hydroxybenzoic acid and amide for p-hydr-

oxybenzyl alcohol,

118.

„ ,, for p-hydroxybenzoic

aldehyde, 290.
,, ,, for phenol, 121.

m-Hydroxybenzoic aldehyde, 215.

,, ,, for vanillin, 220,

221.
p-Hydroxybenzoic aldehyde, 215, 290.

„ ,, for anisic alde-

hyde, 218.
,, ,, for p-cresol, 132.

„ ,, for p-hydroxy-

benzyl alcohol,
118.
„ ,, for vanillin, 221.

„ ,, triacetate, 218.

p-Hydroxybenzyl alcohol, 117.

,, ,, for anisic aldehyde,

218.
,, isothiocyanate, 261.

p-Hydroxybenzylamine, 262.
a-Hydroxybutyric acid, 186, 187, 188.
/3-Hydroxybutyric acid for acotaldehyde, 1 79.
,, ,, for acetone, 194, 199.

jf ,, for crotonic aldehyde,

71, 190.
„ ,, for formic aldehyde,

172.
., ,, for isopropyl alcohol,

68.
,, ,, for n-propyl alcohol, 62.

,, ,, for toluene, 113.

,, aldehyde = aldol, 71.

o-Hydroxy-cD-chlorstyrene = i^-chlorvinylphe-

nol, 134.
Hydroxydieth acetic acid, 78,
Hydroxydihydrogeranic acid, 191.
2i-Hydroxy-4^-ethoxy-3 : 4-dimethoxychalkone,

275-
Hydroxyglutaric acids, 124, 285.
cis-5-Hydroxyhexahydro-p-toluic acid, 283.

a-Hydroxyhexoic ( = 2-hexanolic) acid, 184.
p-Hydroxyhydratropic acid, 229.
a-Hydroxyisobutyric acid, 1 78-181, 195-198.

,, isoamyl ester, 281.

7-Hydroxyisohexoic anhydride, loi,
Hydroxyisophthalic acid, 120, 123.
a-Hydroxyisovaleric acid, 183.
/3-Hydroxyisovaleric acid, 73, 75, 183, 280.
4-Hydroxymesitylenic acid, 132.
Hydroxymethoxybenzoylbenzoic acid, 239.
p-Hydroxy-m-methoxybenzoylcarbonic acid,

see vanilloylcarbonic acid.
Hydroxymethoxybenzylaniline, 220.
Hydroxymethylene-acetone, 30.
s-Hydroxymethylterephthalic ( = methyl-4-phe-

nol-2 : 5-carboxylic) acid, 132.
5-Hydroxy-a-naphthaquinone = juglone, 167.
a-Hydroxypentenoic acid, 103.
p-Hydroxyphenylacetic acid, p-cresol from by
putrefaction, 131.
,, ,, for p-cresol, 13a.

p-Hydroxyphenylglyoxylic acid, 215.
Hydroxyphthalic acids, 122, 123.
/3-Hydroxypropionacetal, 177.
Hydroxypyrotartaric acid, 68, 113, 186, 196, 197.
Hydroxyquinol, 160.

,, and hydrogen cyanide, &c., for

asaryl aldehyde, 224.
,, for asarone, 165.

5-Hydroxysalicylic (=gentisic) acid, 146, 147,

148, 232, 233.
Hydroxysebacic acid, 81.
Hydroxyterephthalic acid, 121, 123.
2i-Hydroxy-4^ : 6^ : 3 : 4-tetramethoxychalkone,

276.
2-Hydroxy-m-toluic acid, 126, 127.
4-Hydroxy-m-toluic (=p-homosalicylic) acid,

131, 132.
5-Hydroxy-m-toluic acid, 128, 129.
6-Hydroxy-m-toluic acid, 126, 127.
3 Hydroxy-o-toluic acid, 128.
5-Hydroxy-o-toluic acid, 128, 130, 285.
6-Hydroxy o-toluic acid, 122.
2-Hydroxy-p-toluic acid, 125, 127, 128, 285.
3-Hydroxy-p-toluic ( = a-cresotic) acid, 129, 130.
5-Hydroxytrimellitic acid, 123.
Hydroxy trim esic acid, 123.
2'-Hydroxy-4' : 6^ :4-trimethoxychalkone, 276.
m-Hydroxyuvitic (= a-coccinic = 5-methylphe-

nol-2 : 4-dicarboxylic) acid, 129.
Hygric ( = N-methylpyrrolidine-2-carboxylic)

acid, 102.
Hymenwa courharil, 139.
Hypholoma fasciculare, 105.
Hystazarin, 140, 240.

,, for alizarin, 239.

Iberis amara, 256.
,, sempervirens, 256.
,, umbellata, 256.
Illicium religiosum, 92.

„ verum, 137, 152.
Iminobenzoylmethyi cyanide = benzacetodini-

trilo, 206, 209, 211.
Indian yellow, 232.
Indigo for phenol, 123.
,, for picric acid, 162.
,, for quinol, 148.
Indigo/era galego'ides, 40, 45, 205, 262.
Intracellular respiration, 44, 278.
Inulase, 247.

Inulin, bacterial fermentation, 51, 70.
,, resolution of, 247.

INDEX

317

Invert sugar for acetaldeliyde, i8o.

Invertin of yeast, 249.

m-Iodaniline, 143.

lodethyl alcohol = glycol iodhydrin, 66, 175,

255-
2-Iodethyl ether, 225.
lodethylmalonic ester, 187.
2-Iodobutane = secondary butyl iodide, 59, 60,

66, 67, 254, 255.
3-Iodobutane-2-carboxylic acid, 255.
/J-Iodocinnamic acid, 35, 210,
Iodoform, &c., for acetone, 199.
,, for acetylene, 29, 55.

,, for acrylic acid, 58, iii.

„ for formic aldehyde, 169, 170.
„ for methane, 23.
„ for methylpropylacetaldehyde, 187.
,, from acetaldeliyde, 24, 170.

„ from acetone, 24, 171, 277.

„ from acetylene, 169.

,, from n- butyl alcohol, 24.

,, from butyric aldehyde, 25.
,, from carbon tetrachloride, 56.

,, from dextrose, 26.

,, from ethyl alcohol, 23, 29, 145.

,, from lactic acid, 25, 57, 171.
,, from octyl alcohol, 24.

,, from n-propyl alcohol, 24.
lodohexanes, 60, 67, 70, 71, 81.
m-Iodonitrobenzene, 143.
a-Iodopentane, 77, 78, 79.
m-Iodophenol, 143.
o-Iodophenol, 140.
p-Iodophenol, 144, 146.

a-Iodo-;3-phenyl-;3-hydroxypropionic acid, 261.
/3-Iodopropionic acid and ester, 144, 145, 178, 283.
3-Iodosalicylic acid, 141, 232.
5-Iodosalicylic acid, 146.
Iretol, 164.

,, for phloroglucinol, 163.
Iridin, 159, 164.
Irigenin, 164.
Iris Jlorentina, 40, 159, 164,
,, germanica, 40.
,, pallida, 40.
,, pseudacorus, 249.
Isatropylcocaine, 42,

Isoamyl alcohol = isobutyl carbinol, 79, 281.
,, ,, and carbon disulphide for

angelyl isothiocyanate, 257.
,, ,, and carbon disulphide for

secondary butyl isothiocya-
nate, 255.
,, ,, aud formic aldehyde for iso-

hexyl alcohol, 82.
,, „ and isovaleric acid for nonyl

alcohol, 84.
,, ,, and malonic ester for ethane-

tetracarboxylic acid, 166.
„ „ for isobutyl alcohol, 72.

„ „ for isobutyric aldehyde, 183,

,, ,, for isovaleric aldehyde, 184.

„ ,, for methane, 26.

„ ,, for methylethylacetaldehyde,

184.
„ ,, for n-butyl alcohol, 70.

,, ,, in fusel oils, 79.

,, and ethyl alcohols for isoheptyl al-
cohol, 83.
,, a-hydroxyisobutyrate, 281.
,, iodide, 70, 180, 184, 195.
„ magnesium bromide and ethylene
oxide for isoheptyl alcohol, 281.

Isoborneol, 274.
Isobutenyl chloride, 182.
Isobutyl alcohol, 72, 280.

,, and acetoacetic ester for iso-

hexyl alcohol, 281.
,, and carbon disulphide for sec.

butyl isothiocyanate, 254.
,, and carbon disulphide for cro-

tonyl isothiocyanate, 256.
,, &c., for isoheptyl alcohol, 84.
,, for acetone, 194.
,, for ally lene, 114.
„ for butyl alcohol, tert., 74.
,, for butylenes, 254.
„ for isobutylene glycol, 96.
,, for isobutyric aldehyde, 182.
„ for isopropyl alcohol, 66.
„ for methane, 24.
bromide, 66.
chloride, 66, 74.

,, or bromide for methane, 24.
cyanate, 74.
esters, occurrence, 7a.
hypochlorite, 182.
iodide, 74, 84, 194.
Isobutylacetic ( = 4-methylpentanoic) acid for

isohexyl alcohol, 82,
Isobutylacetic and formic acids for isocaproic
aldehyde, 185.
„ aldehydeforisohexyl alcohol, 82.

Isobutylacetoacetic ester, 84, 281.
Isobutylamine, 74, 75.
Isobutylbenzene for naphthalene, 165.
Isobutylene and acetyl chloride for mesityl
oxide, 94.
,, and generators, &c., for crotonyl

isothiocyanate, 257.
,, bromide, 96, 182, 256.

,, for acetaldehyde, 181.

,, for acetone, 194.

,, for ethylene, 55.

,, for isobutyric aldehyde, 182.

,, for propylene and glycerol, 99.

,, for toluene, 116.

,, from acetic acid, 74.

,, from acetone, 73.

,, from acetone-chloroform, 73.

,, from butyl alcohol, tertiary, 66,

72, 96, 183, 281.
,, from ^-dimethylacrylic acid, 73.

„ from glycerol, &c., 73.

,, from isoamyl alcohol, 72, 75, 183,

194.
,, from isobutyl alcohol, 66, 74, 75,

96, 281.
,, from isovaleric acid, 72, 75, 183.

„ generators of, 55, 96, 257.

,, glycol, 96.

,, ,, for acetaldehyde, 181.

,, ,, forisobutyric aldehyde, 183.

,, oxide, 182, 288.

Isobutylformic acid and nitrile, 194.
Isobutylsulphuric acid, 75.
Isobutyric acid and acetaldehyde for formic
aldehyde, 173.
,, ,, &c., for isobutyric aldehyde,

182. *

,, for acetone, 196, 289.
,, for butyl alcohol, tertiary, 75.
,, for isopropyl alcohol, 68.
,, for n-propyl alcohol, 6a.
aldehyde, 181.

,, &c., for acetone, 200.

318

INDEX

laobutyric aldehyde for hydrogen cyanide, 266.

„ ,, for isobutyl alcohol, 280.

,, ,, for isopropyl alcohol, 69.

,, and acetic aldehydes for formic

aldehyde, 173.

,, phloryl ester, occurrence, 135.

Isobutyrylacetoacetic ester, 197.
Ifiocaproic aldehyde, 185.
Isocyanacetic acid, 268.
Isodiazoacetic ester, 267.
Isodibromsuccinic acid, 26, 179, 180.
Isoeugenol, 140, 157, 286.

,, for isoeugenol methyl ether, 157.

,, for vanillin, 222.

Isoeugenyl acetate and benzoate, 222.
Isoeugenylsulphuric acid, 222.
Isoglucosamine, 248.
Isoheptane for isoheptyl alcohol, 83, 84.
Isoheptyl alcohol, 83, 281.

,, chloride, 84.
Isohexoic acid for diacetyl, 204.

,, ,, for erythritol, loi.

,, n for quinol, 150.

Isohexyl alcohol, 82, 281.
Isonitrosoacetone, 112, 186, 196.
Isonitrosoacetophenone, 293.
Isonitroso - 3 - ethoxy - 3M 4' - dimethoxyflava -

none, 275.
)3-Isonitrosol8evulic acid, 149.
Isonitrosomethylethyl ketone = butadione-

oxime = diacetylmonoxime, 149, 204.
Isonitroso- 1 : 3 : 3^ : 4' - tetramethoxyflavanone,

276.
Isonitroso-i : 3 : 4'-trimethoxyflavanone, 376.
7-Isonitrosovaleric = oximinolsevulic acid, loi.
Isophorone, 203.
Isophthalic acid, 120.

„ ,, for phenol, 123.

Isoprene for dipentene, 38.
Isopropenyl carbinol, 182.
Isopropyl alcohol, 64, 280.

,, ,, for acetone, 193, 289.

„ ,, for erythritol, 103.

,, ,, for ethyl alcohol, 279.

„ ,, for hexyl alcohol, active, 83.

,, ,, for methane, 277.

„ ,, for n-propyl alcohol, 59.

,, iodide, 65, 67, 165, 227.

,, ,, from camphor, 280.

Isopropylacetylene, 195, 196, 197, 203.
Isopropylamine, 68.

,, for isopropyl alcohol, 65.

Isopropylbenzene = cumene, 32, 207, 211, 261.
,, for acetophenone, 34, 207,

211, 212.
„ for benzaldehyde, 207.

„ for salicylic aldehyde, 215.

Isopropylbutyramide, 68.
Isopropylethylene = amylene, 183, 184, 194,

195-
„ for acetone, 195.

„ glycol, 184.

Isopropyihexyl ketone, 197.
Isopropylidene-acetoacetic ester, 73.
Isopropylisophthalic acid, 32.
Isopulegol, 93, 283.

,, for pulegone, 226, 227.

Isorhamnetin, 139, 160.

Isosuccinic ( = methylmalonic) acid, 176, 177.
Isovaleric acid and carbon disulphide for sec.
butyl isothiocyanate, 255.
„ ,, and ethyl alcohol for acetone,

197.

Isovaleric acid and isoamyl alcohol for nonvT
alcohol, 84.

,, ,, for allylene and acetone, 194.

,, „ for benzene, 31.

,, ,, for butyl alcohol, tertiary, 75.

,, ,, for citraconic acid, 113.

,, ,, for ethyl alcohol, 57.

„ „ for glycerol, 98.

,, ,, for isoamyl alcohol, 80.

,, ,, for isobutyl alcohol, 72.

,, ,, for isobutyi-ic aldehyde, 183.

„ ,, for isopropyl alcohol, 68.

,, ,, for isovaleric aldehyde, 184.

,, „ for methane, 26.

,, ,, for methylpropylacetaldehyde,

186.

„ ,, for propylene, 98.

,, ,, for toluene, 114.

„ aldehyde, 184.

,, ,, and acetone for methyl-

heptenone, 203.

,, ,, for acetone, 196.

,, ,, for isoamyl alcohol, 80,

281.
Isovaleryl chloride, 184.
Itaconio acid, 63, 69, 113, 115, 200.

,, ,, for methylpropylacetaldehyde,

186, 188.
Itachlorpyrotartaric acid, 186.
Itamalic ( = 4-butanol-3-carboxylic) acid, 186.
lulus terrestris, 235.
Ivory-nut, 247. 249.

Jacaranda ovalifolia, 151.
Jack-fruit, 142.
Jasmine oil, 43, 88, 108.
Jasminum grandiflorum, 42, 88, 108.
Juglans regia, 165.

Juglone = 5-hydroxy-a-naphthaquinone, 167.
Juniperus sabina, 204, 224, 278.
,, virginiana, 38.

Kaempferia galanga, 27, 45.

,, rotunda, 91.

Kampheride, 161.
Kampherol, 276, 287.

,, in robinin, 119, 138, 160, 161.

Kawa-root, 42.
Kei hir ferment, 51, 247.
Kesso oil, 36, 90, 183, 273, 274.
Ketipic ( = diacetyldicarboxylic) acid, 150, 204.
Ketocoumaran = coumaranone, 230.

,, for salicylic aldehyde, 213, 314.

Ketocoumarancarboxylic ester, 231.
Ketocyclo-octane, 82.
j8. Ketoglutaric (= 3 -pentanonedicarboxylic)

acid, see under acetonedicarboxylic acid.
S-Ketohexahydrobenzoic acid, 283.
3-Keto-i-methylhexahydrobenzene = methyl-

cyclohexanone, 124, 228.
Kino, 159, 161.
Kinoin, 159.
Kino-red, 139.
Knotweed, spotted, 139.
Koji ferment, 49, 244, 245.
Kd-sam seeds, 277.
Koumiss, 51.
Kuromoji oil, 36, 37, 90, 226.

Lacfarius, sp. yielding mannitol, 104, 105.
Lactic acid and methyl alcohol for acetone, 198.
,, „ „ „ „ for butyl al-

cohol, tertiary, 76.

INDEX

319

Lactic acid bacterial fermentation, 51, 52, 58.
,, ,, for acetaldehyde, 177.
,, ,, for allylene and acetone, 194.
,, ,, for chloroform, 25.
,, „ for citraconic acid, 113.
,, ,, for crotonic aldehyde, 71, 190.
,, „ for diacetyl, 204.
,, ,, for ethyl alcohol, 57.
,, ,, for formic aldehyde, 171.
,, ,, for hydrogen cyanide, 267.
,, ,, for iodoform, 25.
,, „ for isopropyl alcohol, 68.
„ ,, for methane, 25.
,, ,, for methylpropylacetaldehyde, 186.
,, ,, for n-propyl alcohol, 62.
,, „ for propylene and glycerol, 98.
,, ,, for quinol, 151.
,, ,, for toluene, 114.
„ ,, n-propyl alcohol from, by fermenta-
tion, 58.
Lactic azide, 177.
Lactomyces, fermentation by, 48.
Lactose, bacterial fermentation of, 51, 52, 70.
,, fermentability by Oidium, 50.
„ hydrolysis of, 345.
Leevo-isoterpene, 39.
Laevomannan, 247.
Laevulic acid for acetylacetone, 102.

,, ,, for allylacetoacetic ester, 102.

,, ,, for amyl alcohol, n-sec. , 79.

„ ,, for crotonic aldehyde and hy-

drogen cyanide, 103.
,, ,, for diacetyl, 204.

,, ,, ,, ,, and quinol, 148, 150.

„ „ for dimethylheptenol, 103.

„ „ for erythritol, loi.

,, „ for ethyl alcohol and acetic acid,

lOI.

,, „ for isohexoic acid, loi.

„ „ for laevulose, 103.

,, „ for malonic acid and glycerol, 102.

„ ,, for mannose, 103.

,, „ for naethylheptenone, 103.

„ ,, for succinic acid, loi.

„ „ generators of, 79.
Laevulose, 247, 292.

„ and acetic acid for n-sec. amyl al-
cohol, 79.

., fermentability by moulds, 49.

„ fermentation of, 46.

„ ,, „ by Oidium albicans,

174-
„ for dextrose, 246.
,, for diacetyl, 204,
,, for erythritol, 103.
,, for hydrogen cyanide, 266.
,, for mannitol, 106.
,, for mannoso, 250.
„ for quinol, 150.
,, for sorbitol, 107.
,, glycerol from, by Oidium, 97.
„ mannitol from, by fermentation, 105.
Laminaria saccharina, 104.
Larch, mannitol from, 104.
Larix decidua, 273.
,, europcea, 104.
Laurel, Californian, 283, 287.
Laurie acid for dodecyl alcohol, 85.
,, ethyl ester, occurrence, 45.
Lauras henzom, 41.

,, camphora, see under Cinnatnomum cam-

phora, 90, 91, 174, 271.
„ nobilis, 91.

Laurus persea, 104, 107.

Lavender oil, 87, 88, 90, 91, 273, 281, 282, 283,

288.
Lavandula pedunculata, 91.

,, species yielding geraniol, 87.

,, spica, 88, 90, 91, 271, 272, 274.
Lecanora badia, 153.
,, parella, 153.

,, species yielding atranorin, 42,
,, ,, „ parellic acid, 43.

,, tartar ea, 153.
Lecanoric «= parmelic acid, 100, 153.
Leeidea cinereo-atra, 43.

„ griseUa, 153.
Lecidic acid, 43.
Lecithin, 99.
Ledum palustre, 146, 161.
Leiocarpus sp., methyl salicylate from, 41.
Lemon oil, 37, 87, 88, 90, 158, 189-192, 202,

289.
Lemon-grass oil, 28, 36, 87, 88, 90, 191, 192,

202, 289.
Lemon-scented verbena, 191.
Lspidium sativum, 257.
Lepra cholerina, 153.
Lepraria flava, 43.
Leucine for butyric aldehyde, 183.

„ for isovaleric aldehyde, 184.
Leuconostoc mesenterioides, mannitol producer, 105.

,, „ saccharose ferment, 247.

Levisticum officinale, 90.
Licareol = linaloOl, 88, 282.
Licarhodol, 88, 90.
Ligustrum vulgare, 104, 159.
Lilac, mannitol from, 104.
Lilium, mannose-yielding compounds from,

249.
Lima bean, 263.
Lime bark, vanillin from, 220.

,, leaves, oil, 36, 201.
Limes, oil of, 282.
Limetto oil, 37, 42.
Limonene, 37, 278.

„ for terpinene, 39.

„ for terpineol, 91.

„ tetrabromide, 226.

Linaloe = lignaloe, oil of, 86, 87, 88, 90, 202.
LinaloOl, 88, 282.

,, for citral, 191.

,, for cymene, 32.

,, for dipentene, 38.

,, for geraniol, 88.

,, for terpinene, 39.

,, for terpineol, 90.
Lindera sericea, 36, 90, 226.
Linum usitatissimum, 263.
Lippia (Aloysia) citriodora, 191.

Liquidambar orientalis, sSt 45; ^°1j ^^9? 219.

„ styraciflua, 33, 119, 219.

Lodoicea seychellarum, 249.
Logwood, 139.
Lokain, 160.
Lotoflavin, 142.

,, phloroglucinol complex in, 142.

Lotus arabicus, 142, 160, 263.

,, australis, 263.
Lotusin, 142, 160, 263.
Lovage, oil of, 90.
Lucern, 249.
Lupinus cdbus, 219.
Luteolin, X39, 140, 160, 234.
Lymph, dextrose in, 246.
Lysine for hydrogen cyanide, 268.

320

INDEX

Lysine for n-propyl alcohol, 64.

,, for toluene and benzyl alcohol, 116.

Mace oil, 36.

Madura aurantiaca, see Morus tinctoria, 139, 142.

Maclurin, 139, 160.

Madder, 238, 239, 240.

Magnesium benzyl bromide, 284.

„ p-bromphenyl bromide, 285.

„ carbides from hydrogen cyanide,

56.
„ ethiodide, 137, 157, 212, 283.

„ ethobromide, 281.

„ isoamyl bromide, 281.

,, methiodide, 22, 74, 76, 87, 119, 281,

282, 283, 289.
„ methobromide, 199.

„ methyl, 74.

,, nitride, 207.

,, phenyl bromide, see phenyl mag-

nesium bromide.
„ propyl bromide, 70.

,, o-toluyl bromide, 285.

,, p-toluyl bromide, 285.

Magnolia fuscata, 45.
Mahwa flowers, sugar from, 244, 247.
Maleic acid for acetaldehyde, 179.
,, „ for benzene, 31.
,, ,, for isopropyl alcohol, 69.
,, ,, for methane, 26.
,, ,, for n-propyl alcohol, 64.
,, „ for toluene and benzyl alcohol, 116.
Malic acid, bacterial fermentation, 51.
,, „ for acetaldehyde, 179.
,, ,, for benzene, 31.
,, ,, for n-butyl alcohol, 72.
,, ,, for crotonic aldehyde, 72, 190.
,, ,, for ethyl alcohol, 57.
,, ,, for formic aldehyde, 173.
,, ,, for isopropyl alcohol, 69.
,, ,, for methane, 26, 277.
,, ,, for n-propyl alcohol, 64.
,, ,, for toluene and benzyl alcohol, 116.
Malonic acid and acetaldehyde for acetone, 194,
198.
,, ,, and ethyl alcohol for phenol, 124.

,, ,, and glycerol for erythritol, 102.

,, ,, &c., for acetaldehyde, 176.

,, ,, &c., for formic aldehyde, 172.

,, ,, &c., for isopropyl alcohol, 69.

,, ,, &c., for methylpropylacetalde-

hyde, 187.
,, ,, &c., for toluene, no.

,, ,, foJ" ethyl alcohol, 57.

„ „ for ethylene, 25,

,, ,, for methane, 25, 277

,, J, for methyl alcohol, 44.

„ ,, for orcinol, 155.

,, and citric acids, &c., for resorcinol,

145-

,, and oxalic acids, acetone, &c., for cam-
phor, 272.

,, and propionic acids for allylene and
acetone, 194, 198.

J J ,, „ for citraconic acid,

113-
,, ester and glycerol for quinol, 150.
„ ,, &c., for ethanetetracarboxylic

ester, 166.
,, ,, for hydrogen cyanide, 268.

,, „ for phloroglucinol, 162.

„ ,, for n-propyl alcohol, 62.

„ semi-aldehyde, 177.

Maltose, alcoholic fermentation of, 47, 278,
,, bacterial fermentation, 52, 70.
,, fermentability and hydrolysis of, 47,

244.
,, fermentability by moulds, 49, 50.
,, glycerol from, by Oidium, 97.
Malus communis, 205.
Mandarin orange oil, 37, 42, 189-192.
Mandelic acid and nitrile, 258, 259, 261.

,, ,, for benzaldehyde, 208, 210.

Mandelonitrile for styrene, 35.
Mangi/era, species yielding methyl salicylate,

41.
Mang-koudu, 241,
Manihot root, 263.

,, utilissima, 263.
Manna and manna ash, 104, 243, 247.

,, from Pinus larix, 245.
Mannans or mannosides, 248, 249, 250.
Manneotetrose = stachyose, 292.

,, fermentation of, 46.

,, hydrolysis of, 247, 248.

Manninotriose, 248.
Mannitol, 104, 284.

,, and aniline for hydrojuglone, 168.
,, and carbon disulphide for sec. butyl

isothiocyanate, 256.
,, bacterial fermentation of, 51,52,69,70.
,, ferment, 52, 97.
,, ,, glycerol producer, 97.

,, for acetone, 200.
,, for acrolein, 99, 190.
,, for amyl alcohol, n-primaiy, 76.
,, for n-butyl alcohol, 71.
,, for diisopropyl, 83.
,, for ethyl alcohol, 57.
,, for formic aldehyde, 172.
„ for glycerol, 99.
,, for n-hexane, 79, 81.
,, for hexyl alcohol, active, 83.
,, for isopropyl alcohol, 67.
,, for Isevulose, 248.
,, for mannose, 250.
,, for methylpropylacetaldehyde, 188.
,, for n-propyl alcohol, 60.
,, for toluene and benzyl alcohol, 116.
,, Isevulose fi-om, by bacteria, 247.
i-Mannitol, mannose, and mannonic acid, 246.
Mannogalactans, 249.
Mannoheptol = perse'itol, 107.

,, for toluene and benzyl alcohol,

114.
d-Mannoheptonic acid, 107.
Mannonic acids, 105, 106.
d-Mannonic acid for dextrose, 246.

,, ,, for d-mannose, 250.

Mannononose, fermentation of, 46.
Mannose and acetic acid for amyl alcohol, n-
secondary, 79.
,, for catechol, 141.
,, for diacetyl, 204.
,, for erythritol, 103.
,, for furfural, 224.
,, for leevulic acid, 103.
,, for quinol, 150.
d-Mannose, 248, 292.

,, and hydrogen cyanide for manno-

heptol, 107.
,, fermentability by moulds, 49.

,, fermentation of, 46.

,, for dextrose, 247.

,, for leevulose, 248.

i-Mannose, 105,

INDEX

321

d-Mannose for mannitol, io6.

,, for sorbitol, 107.

1-Mannose, non-fermentable, 46.
Maple, sugar, 250.
Marjolaine, 290.
Massoia bark, oil, 36, 37.
Matico oil, 158, 164.

Matricaria {Pyrethrum) partheniuni, ^71, 273.
Meadowsweet, 40.
Medicago sativa, 249.
Medlars, sorbitol from, 106.
Melaleuca acuminata, 91.

,, leucadendron, go, 181, 205.

„ ,, var. lancifoKa, 9I.

,, viridifolia, 90, 205. •
Melezitose, 49.

,, hydrolysis of, 245.

Melibiose, fernientability, 50.

,, resolution and fermentation of, 245.

Melilotus leucantha, 2^2.
Melissa officinalis, 87, 88, 193.
Mellitic acid, 29, 30, 31, ido.
Melodmus kevigatus, 41.

,, orientalis, 41.
Memecylon, species yielding methyl salicylate,

41-

Mentha aquatica var. crispa, 226.

,, arvensis vars. piperascens and glabrata,

93-
,, canadensis, 135, I36, 226.
,, piperita, 92, 136, 227, 283, 388, 290.
„ pulegium, 37, 92, 93, 226, 227.
„ viridis, 38, 88, 226.
Menthadiene = terpinene, 39.
Menthene, 274.

,, for cymene, ^78.

Menthocitronellal, 89.
Menthol, 92, 283.

,, compounds, genesis In plahts, 93.
,, for cymene, 33.
,, for menthene, 275.
,, for menthone, 227, 290.
Menthone, 227, 290.

,, for acetone, 200.

„ for citronellol, 89.

,, for m-cresol, 130.

,, for isopropyl alcohol, 68.

,, for menthol, 93, 283.

,, for n-propyl alcohol, 61.

,, for thymol, 136.

,, for toluene and benzyl alcohol, 1I5.

Menthonic acid, 200.
Menthyl chloride, 275,
Mercury fulminate for thiocyanates, 269.

,, ,, and benzene for benzaldo-

hyde, 207.
Mesaconic acid, 63, 11 a, 113.

,, ,, for acetone, I96, 198.

,, ,, for methylpropylacetaldehyde,

186, 187.
,, „ for quinol, 151.

Mcsadibrompyrotartaric acid, 186.
Mesidine, 157.

Mesitenecarbonic lactone, 180.
Mesitol=i :3 :5-trimethyl-2-phenol, 132.
Mesityl oxide, 94, 179, 180, 181, 272, 280.
Mesitylene for benzene, 30.
,, for m-cresol, 129.

,, for o-cresol, 126.

,, for p-cresol, 13a.

,, for mesorcinol, 157.

,, for phenol, 123,

,, for toluene, 108-114.

Mesitylenic acid for benzene, 31.
,, ,, for o-cresol, 126.

)f ,, for p-cresol, 132.

,) ,, for phenol, 123.

,, ,, for toluene, 114.

,, ,, from isovaleric acid, 114.

MesitylenesUlphonic acid, 132.
Mesorcinol, 156.
Mespihis japonica, 205,
Mtsquit tree, 247.

Meta- ; see also under m- with respective suf-
fixes.
Metacetone, 188.
Metacresol for menthone, 227.
Metahydroxyanthraquinone, 236.
Metahydroxybenzoic aldehyde, 215.
Methane, 21, 277.

„ and methyl chloride for methyl sul-
phide, 353.
,, and nitrogen for hydrogen cyanide,

268.
,, for acetaldehyde, 175.
,, for benzene, 29.
,, for cal'bon disulphide, 251.
,, for ethyl alcohol, 54.
,, for formic aldehyde, 169.
,, for methyl alcohol, 43.
Methazonic acid, 267, 268.
Methenylbisacetoacetic ester, 285.
Methovinyl = j8-alIylbenzene, 32.
o-Methoxyacetophenone, 2I4.
p-Methoxyacetophenone, 229, 230.
t : 3 Methoxy-4-aminobenzene, 165.
p-Methoxybenzoic acid, see anisic acid.
m-Methoxybenzoic aldehyde, 221.
o- M M 223.

2-Methoxybenzoylacetic ester, 214, 228.
p-Methoxybenzyl( = anisyl) alcohol, 218, 219.
m-Methoxycinnamic acid, 221.
p-Methoxycinnamic acid, 229.

,, ethyl ester, occurrence,

45-
p-Methoxydibromdihydrocinnamic( = i' : I'-di-

brom-p-hydrocoUmaric) methyl ether, 229.
p-Methoxyhydratropic aldehyde and acid, 229.
p-Methoxy-p-nitrobenzaldehyde, 221, 222.
m-Methoxyp-nitrocinnamic ester and acid,

221.
p-Methoxyphenyl magnesium bromide, 290.
p-Methoxyphenylglyoxylic acid, 218.
p-Methoxyphenylpropiolic acid, 230.
3-Methoxyphthalic acid, 122.
Methoxyquinone and quinol, 165.
6-Methoxy-o-toluic acid, 122,
Methyl acetate for formic aldehyde, 170.
,, alcohol, 40, 278.

,, ,, and butyric acid for amyl alco-

hol, n-secondary, 77.
,, ,, and formic acid for glycerol,

98.
,, ), and methyl chloride for carbon

disulphide, 251.
„ ,, and phosgene for tertiary butyl

alcohol, 281.
,, ,, &c., for hydrogen cyanide, a68.

,, ,, for acetaldehyde, 180.

,, ,, for benzene, 30.

,, ,, for chloroform, 30.

„ „ for ethyl alcohol, 54.

,, „ for formic aldehyde, 169, 287.

„ ,, for methane, 22.

,, „ for methyl mercaptan, 25a.

„ „ for methyl sulphide, 253.

322

INDEX

Methyl alcohol for nitromethane, 98, 99.

„ ,, glycerol, and carbon disulphide

for sec. butyl isothiocyanate, 254.
,, and ethyl alcohols, acetic and propionic
acids, and acetone
for methylhepte-
none, 202.
„ „ „ „ and hydrogen cyan-

'. ide for acetone, 199.

,, „ „ „ for isopropyl alco-

hol, 66.
„ ,, ,, „ formic acid, and car-

bon disulphide for
sec. butyl isothio-
cyanate, 255.
,, I, ,, ,, glycerol, potassium

cyanide, and acetic
acid for terpinool,
283.
,, anthranilate, occurrence, 41, 278.
,, benzoate, occurrence, 41, 4a, 278.
„ chloride, 26, 43, 44, 54, 57, 170.
„ „ for ethylene, 54.

,, ,, for methane, 26.

,, ,, from trimethylamine, 26, 173.

,, cinnamate, occuri-ence, 42.
,, cyanide = acetonitrile, 54, 71, 199, 211.
,, ether, 169.
,, iodide for methane, 22.
,, ,, from camphoi", 277, 278.

,, mercaptan, 252, 292.
,, salicylate, occurrence, 40, 41, 278.
,, sulphide, 253.
,, ,, and hydrogen cyanide for

methyl mercaptan, 252.
,, thiocyanate and thiocyanurate, 252.
Methylacetoacetic ester, 112, 149, 186, 196,
Methylacetosuccinic ester, a and ^, 63, 112, 186,

196.
Methylacetyl carbinol = dimethylketol, 94, 283.
Methylal, 169, 170, 171, 173, 287.
Methylamine and benzoyl chloride for benzoni-
trile, 258.
,, for formic aldehyde, 174.

,, for hydrogen cyanide, 267.

,, for methane, 26.

,, for methyl alcohol, 44.

Methyl-n-amyl ketone, 200.
Methylanthranilic methyl ester, occurrence, 42.
Methylarbutin, 146, 152, 251.
Methylbenzamide, 258.
Methylbenzyl ketone, 212.
3-Methyl-i : 2-butadi6ne = dimethyl ;ilylene,

195, 202.
Methyl-a-chlorethyl ketone, 95.
a-Methyl-j3-cyanosuccinic ester, 113, 187, 196.
i-Methylcyclohexanol-2-carboxylic-4-acid, 285.
Methylcyclohexanone = 3-keto-i-methylhexa-

hydrobenzene, 115, 124, 130, 228.
Methyl- i-cyclohexenone-3, 145.
Methylcyclopropane, 71, 72.
Methyl-n-decyl ketone, 202.
Methylene bromide, 287.

,, chloride, 117, 170, 171, 173, 236.

„ iodide, 55, 56, 57, 129, 145, 170, 171,

223, 287.
Methylethenyltricarboxylic ( = propanetricar-

boxylic) acid, 62, no, 113.
Methylethylketol, 188.
Methylethyl ketone, 95, 204, 283.

,, ,, for sec. butyl alcohol, 255.

„ ,, from pseudobutylene, 95,

254, 255.

Methylethylacetaldehyde, 184.
Methylethylacetylene = 3-pentine, 78.
Methylethylacrolein, 185, 186.
s-Methylethylethylene = 3-pentene, 78, 188,

194-
,, glycol = 2 :3-dihydroxy-

pentane, 188.
i-Methyl-4-ethylonecyclohexanol-a, 285.
Methylethylpropyl carbinol = active hexyl alco-
hol, 83.
Methyl eugenol, 140, 157, 286.
a-Methylglucoside, alcoholic fermentation of,
278.
„ fermentability by moulds,

49.
^-Methylglyceric ( =a3-dihydroxybiityric) acid,

170-173, 177-179-
6-Methylglycidic acid, 172, 188.
Methylglycollic acid, 171.
Methylglyoxal, 188.
Methylheptenol, 203.
Methyl heptenone, 202, 282.

„ and methyl alcohol for di-

methylheptenol, 86.
,, for acetone, 199, 289.

,, for o-cresol, 127.

,, for diacetyl, 204.

,, for erythritol, 103.

,, for laevulic acid, 103.

,, for quinol, 151.

Methyl-n-heptyl ketone, 201.
2-Methyl-6-hexanone, 84.
Methylhexyl carbinol = 2-octanol, 82, 84.
Methyl-n-hexyl ketone and oxime, 8x, 8a.
Methylhydrocoto'in, 232.

,, phloroglucinol complex in,

161.
a-Methylhydroxyglutaric anhydride, loi.
Methylhydroxytrimesic ester, 285.
Methylisoeugenol, 140, 157.

,, for acetaldehyde, 181.

Methylisophthalic acid, see under uvitic acid.
Methylisopropyl ketone, 194, 195, 196, 197, aoo.
Methylisopropylketohexamethylene, 227.
Methyl-)3-ketohexamethylenecarboxylic ester,

227.
3-Methyl-A2-keto-R-hexene( = i -methyl cyclo-3-

hexenone), 129.
Mcthylketohexenyleneearboxylic esters, 145.
/3-Methylmalic acid, 68, 114, 187, 198.
MethylmaIonic(=isosuccinic) ester and acid,

no, 176, 177, 187.
8-Methyl-9-nonanol, 201.

Methyl-n-nonyl carbinol = hendecatyl alcohol,
85.
,, „ ketone, 201.

,, ,, „ for the carbinol, 85.

Methyloxalacetic ester, 114, 187, 198.
Methylparapropiocoumaric acid, 137.
4-Methylpentanoic acid for isohexyl alcohol,

82.
4-Methylphenol-2 : 5-dicarboxylic (= s-hy-

droxymethylterephthalic) acid, 132.
5-Methylphenol-2 : 4-dicarboxylic (= m-hy-

droxyuvitic) acid, 129.
Methylphenyl carbinol = styrolyl alcohol, 118,
284.
„ „ for styrene, 34, 35.

a-Methyl-/3-phenylhydroxypropionic acid, 212.
/3-Methylpimelic acid, 227.
Methylpropyl carbinol, 77, 281.

„ ketone, iSo, 62, 64, 77, 78, 188,

aSi.

INDEX

323

Methylpropylacetaldehyde, 185, 288.
Methyl propyl-acetoacetic ester, 178.
a-Methylpropyl-/3-hydroxybutyric acid, 178.
Methylpurpuroxanthin, 142, 241.
a-Methylpyridine = a-picoline, 82.
N-Methylpyrrole, 100, loi.
3-(/3)-MethyIpyrrolidine, 38.
N-Methylpyrrolidine, 100, 102.
N - Methylpyrrolidine-2 - carboxylic ( = hygric)

acid, loa.
Methylsuccinamic acid, loi.
Methylsuccinimide, loi.

Methylterephthalic ( = a-xylic) acid, 30, 123.
/3- Methyltetramethylenediamine, 38.
a-Methyltetronic (= tetrinic) acid, 149.
Methyl-m-toluyl ketone, 131.
/3- Methyl -N- trimethylpyrrolidyl - ammonium

iodide, 38.
Methylumbelliferone, 142,

,, for paeon ol, 231.

Methylundecyl ketone, 202.
Methysticin, 42.
Metroxylon sagu, 249.
Meum athamanticum, 104.
Mezcalin, 159.
Micrococcus acidi paralactici, saccharose ferment,

69.
Milk, alcohol in curdled, 279.

„ anaerobic putrefaction, 53, 1 19, 252.
,, fermentation by Bacillus butyricus, 70.
,, fusel oil in, 80.
Milk-sugar, acetone from, by fermentation, 193.
„ „ fermentability, 47, 50, 51.
,, ,, hydrolysis of, 245.
„ ,, methane fermentation of, 21,
Mint oil, see under Mentha and Monarda.
Mitchella repens, 262.
Monarda didyma, 136.

„ fistulosa, 28, 37, 135, 136, 158, 235.
,, punctata, 28, 37, 135, 136.
Monilia Candida, alcoholic ferment, 47, 50.

,, „ resolution of saccharose by,

244.
„ ,, trehalose ferment, 245.

,, javanica, from Javan ' raggi,' 49.
, , , , resolution of saccha rose by, 244.

,, sitophila, alcoholic ferment, 50.
„ (?) sitophila, saccharification of starch

by, 246.
,, used for Japanese ' awamori,' 49.
,, variabilis, alcoholic ferment, 47.
Monkshood, 104.
Monotropa hypopitys, 41.
Morin, 142, 160.
Morinda umbellata, 241.

Morus tinctoria = Madura aurantiaca, 139, 142.
Mosla japunica, 136.

Mould-fungi as alcoholic ferments, 49.
Mountain-ash berries, sorbitol in, 106.
„ ,, flowers, 263.

„ savory, 135.
Mucobromic acid, 142, 145, 163, 235.
( Mucor alternans, alcoholic ferment, 49, 278.

,, /3- and y-amylomyces, starch saccharifica-
tion by, 245, 246.
,, Cambodia from Chinese yeast, 49.
,, „ starch saccharification by, 246.

„ circinelMdes, alcoholic ferment, 49.
„ „ aldehyde producer, 174.

,, duUus from Javan ' raggi,' 49.
„ erectus, alcoholic ferment, 49.
,, ,, starch hydrolyser, 245.
„ industrial production of dextrose by, 245.

Mucor javanicus from Javan 'raggi,' 49.

,, mucedo, alcoholic ferment, 49.

„ racemosus, alcoholic ferment, 49.

„ „ aldehyde producer, 174.

,; „ glycerol producer, 97.

,, ,, resolution of saccharose by, 244.

,, {Amylomyces) rouxii from Chinese yeast, 49.

M u >> starch hydrolyser, 245.

„ species as alcoholic ferments, 49.

,, spinosus, alcoholic ferment, 49.

,, siolonifer, alcoholic ferment, 49.

,, „ from ' koji ' ferment, 49.

Muscle, dextrose in, 246.
Mustard oil, carbon disulphide in, 251.

,, oils, see under respective isothio-
cyanates.
MycoUastus sanguinarius, 42, 43.
Mycoderma aceti, 93.

„ fermentation by, 48.
,, vini, glycerol producer, 97.

Mydaus marchei, Philippine badger, 253.
Myoporum platycarpum, 104.
Myrcia {Eugenia) acris, 158.
Myrica cerifera, &c., 96.

„ gale, 159.

„ nagi = sapida, &c., 159.
Myricetin, 159, 160.
Myristic acid for heptacosane, 28.

„ „ for n-hexane, 79, 81.

,, ,, for suberic acid, 81.

,, ,, for tetradecyl alcohol, 86,

,, aldehyde for tetradecyl alcohol, 86.
Myristica fragrans, 36.
Myronate, potassium = sinigrin, 256.
Myrosin, 256.
Myroxylon {Toluifera) pereirce, 107.

,, tolui/erum, 107.
Myrticolorin = osyritrin, 138,
Myrtle oil, 36, 92.
Myrtus cheken, 9a.

„ communis, 36, 92.

Naphthalene, 39.

„ for anthracene, 236.

,, for benzaldehyde, 211,

„ for benzonitrile, 211, 259.

,, for m-eresol, 130.

„ form-hydroxybenzaldehyde,2i5.

„ for phenol, 122.

„ for phthalic acid, 115, 284.

,, for toluene, 114, 115.

,, from ethyl alcohol, 287.

„ syntheses of, 165, 166.

I : 5-Naphthalenedisulphonic acid, 167.
Naphthalenedisulphonic and nitrodisulphonic

acids, 115.
Naphthalene-a-sulphonic acid and amide, 122.
Naphthalene-j3-sulphonic acid and amide, 123.
Naphthalenetrisulphonic acids, heteronucleal,

130.
a-Naphthaquinone, 167, 168.
a-Naphthol and acetate, 122.
I : 5-Naphtholsulphonic acid, 167.
a-Naphthylamine, 168.
Naphthylaminesulphonic and disulphonic

acids, 115, 122.
1 : 5-Naphthylaminesulphonic acid, 167.
I : 8-Naphthylaminesulphonic acid and sultone,

167.
I : 4-Naphthylenediamine, 168.
Narcotine, 140, 159.

Naringin = aurantiin, phloroglucinol complex
in, 160.

Y 3

324

INDEX

Nasal secretion, thiocyanate in, 269.

Nasturtium officinale, 260.

Nauclea, species of, 41.

Nedandra rodioei, 124.

Neroli oil, 37, 41, 42, 87-90, 118, 274, 278, 282,

284, 288.
Ngai camphor, Chinese, 273.
Niauli oil, 90, 91, 205.
Nigritella suaveolens, 219.
m-Nitraniline, 143.
o-Nitraniline, 14a, 214.
p-Nitraniline, 150, 230.
o-Nitroacetophenone, 213, 214, 228, 229.
p-NitroJicetophenone, 230.
a-Nitroacetophenone-oxime = /3-styrene nitro-

site, 293.
I : 4-Nitroacetnaphthalide, 168.
a-(4)-Nitroalizarin, 241.
/3-Nitroalizarin, 240.
5-Nitro-2-aminobenzoic acid, 147, 233,
3-Nitro-4-aminoethylbenzene, 135.
2-Nitro-4-aminophenylacetic acid, 134, 148.
6-Nitro-3-amino-p-toluic acid, 125, 127.
5-Nitro-3-ainino-p-xylene, 156.
o-Nitroanisole, 140, 141, 142, 220.
a-Nitroanthraquinone, 238, 239.
a-Nitroanthraquinonesulphonic acid, 239.
p-Nitrobenzaldehyde diacetate, 217.
o-Nitrobenzaldoxime, 134, 148.
p-Nitrobenzaldoxime, 216, 217, 218.
Nitrobenzene, 120, 142, 143, 130, 163, 214, 217,

219.
Nitrobenzenesulphonic acids, 143, 220.
m-Nitrobenzoic acid, 121, 122, 147, 236.
o-Nitrobenzoic acid, 121, 124, 147, 148, 214,

215, 233.
p-Nitrobenzoic acid, 230.
m-Nitrobenzoic aldehyde, 121, 122, 130, 215,

220, 223.

o-Nitrobenzoic aldehyde, 117, 134, 147, 148,
214.
,, ,, for saligenin, 117.

p-Nitrobenzoic aldehyde, 216, 217, 218, 230,

290.
o-Nitrobenzonitrile, 215.
p-Nitrobenzonitrile, 230.
o-Nitrobenzoyl chloride, 214.
p-Nitrobenzoyl chloride, 217, 230, 262.
o-Nitrobenzoylacetoacetic ester, 214.
p-Nitrobenzoylacetoacetic ester, 230.
o-Nitrobenzyl alcohol. 117.
p-Nitrobenzyl alcohol, 217.
o-Nitrobenzyl chloride, 117.
p-Nitrobenzylacetamide, 262.
p-Nitrobenzylamine, 262.
p-Nitrobenzylaniline and sulpho-acid, 217.
/3-(^-Nitrobenzylliydroxylamine, 217.
m-Nitrobenzylidene chloride, 122.
p-Nitrobenzylideneaniline and sulpho-acid, 217.
o-Nitrocinnamic acid, 117, 121, 134, 147, 213,

214, 228.
p-Nitrocinnamic acid, 216, 230.
Nitrocoumarone, 213.

, , for hydrogen cyanide, a66, 268.

5-Nitro-3(ni)-cresol, 154.
4-Nitro-3(m>cresol ether, 132, 221.
6-Nitro-3(m)-cresol ether, 127.
4-Nitro-2(o)-cresol, 155.
5 Nitro-2(o)-cresol, 151.
2-Nitro-4(p)-cresol, 155.
3-Nitro-4(p)-fresol, 130.
3-Nitrocumic aldehyde, 127.
m-Nitro-p-cyanotoluene, 129, 228.

2-Nitrocymene, 136.
Nitrocyinylidene chloride, 127, 136.
a-Nitro-/3-dimethylacrylic ester, 182.
Nitroethane from acetaldehyde, 55.
o-Nitroethylbenzene, 133.
Nitroheptanes, 83, 200.
Nitrohexane, 80, 82.
p-Nitrohydratropic acid, 229.
m-Nitro-p-hydroxybenzoic aldehyde, 221.
Nitroisobutylene, 182, 183.
Nitroisobutylglycerol, 99, 242.
Nitroisophthalic acids, 123.
Nitrolactic acid, 267.
Nitromalonic aldehyde, 142, 145, 163, 235.

,, ester, 166, 268.

Nitromesidine, 157.
Nitromesitol, 157.
Nitromesitylene, 157.
4-Nitromesitylenic acid, 132.
Nitromethane for fulminates, 207.
„ for glycerol, 98, 99.

,, for hydrogen cyanide, 266, 268.

,, from acetic acid, 98, 216.

p-Nitro-m-methoxybenzoic aldehyde, 221, 22a.
6-Nitro-2-methoxybenzonitrile, 143.
Nitromethoxyphenylpyroracemic acid, 221.
a-Nitronaphthalene, 122, 167, 168.
1 : 5-Nitronaphthalenesulphonic acid, 167.
1 : 8-Nitronaphthalenesulphonic acid, 167.
I : 4-Nitronaphthol, 168.
I :4-Nitronaphthylamine, 168.
Nitro-octanal, 189.
Nitro-octylene, 189.
p-Nitrophenetole, 15a.
m-Nitrophenol, 143.
o-Nitrophenol, 140, 142, 164, 220.
p-Nitrophenol, 144-147, 150, 152, 232, 233,

235-
o-Nitrophenylacetylene, 214, 228.
a-o-nitrophenyl-;3-bromnitroethylene, 117.
a-p-nitropheny l-;3-bromnitroethylene, 216.
o-Nitrophenyl-w-chlorethylene = i ^-chlor-a-

nitrostyrene, 134.
p-Nitrophenyldibrompropionic acid and ester,

230.
o-Nitrophenylpropiolic acid, 214, 228.
p-Nitrophenylpropiolic acid and ester, 230.
p Nitrophenylpyroracemic acid, 218.
3-Nitrophthalic acid, 122.
4-Nitrophthalic acid and estei', 122.
Nitrophthalimidine, 130.

Nitropropane from a-brombutyric acid, 60, 67,
69.
,, from propaldoxime, 61.

Nitropseudocumene, 149.
3-Nitrosalicylic acid, 141, 142,
5-Nitrosalicylic acid, 146, 147, 232, 233.
I ^-Nitrosoacetophenone, 210.
Nitrosoanthrol, 291.
Nitrosobenzene, 1^2, 150, 266,
Nitroso-o-cresol = toluquinoneoxime, 152.
Nitrosodimethylaniline, 150.
Nitrosoguanidine, 269.
I : 4-Nitrosonaphthol, 168.
p-Nitrosophenol = quinoneoxime, 146, 150.
Nitrosotriacetonamine, 126.
I ^-Nitrostyrene = phenylnitroethylene, 216.
Nitrotartaric acid, 267.
Nitroterephthalic acid, 123.
Nitrotoluenes, 117, 125, 128-131, 143, 148, 151,

154, 214, 217, 218, 222, 230.
4-Nitrotoluene-2-sulphonic acid, 143.
a-Nitro-m-toluic acid, 126.

INDEX

325

4-Nifcro-m-toruic acid, 131.
6-Nitro-m-toluic acid, 126.
5-Nitro-o-toluic acid, 128.
6-Nitro-o-toluic acid, 12a.
a-Nitro-p-toluic acid, 125.
3-Nitro-p-toluic acid, 129, 228.
4-Nitro-m-toluidine, 132.
5-Nitro-m-toluidine, 154.
6-Nitro-m-toluidine, 125, 127.
4-Nitro-o-toluidine, 155.
5-Nitro-o-toluidine, 130, 151.
a-Nitro-p-toluidine, 148, 155.
3-Nitro-p-toluidine, 128, 129, 130, 222, 228.
3-Nitro - p - tolunitrile = 3 (m) - nitro -4- cyano-

toluene, 129, 228.
o-Nitrovanillin methyl ether, 239.
o-Nitroveratric acid, 239.
4-Nitro-m-xylene, 131.
6-Nitro-m-xylene, ia6, 127.
5-Nitro-o-xylene, 128.
Nitro-p-xylene, 129.
5-Nitro-p-xylenoI-3, 156.
Nonoic (= ennoic) aldehyde = nonanal, 84,

189.
Nonoic and formic acids for nonoic aldehyde,

189.
Nonyl alcohol, secondary, 85, 28a.
Nutmeg oil, 36, 212.

Oats, vanillin glucoside in, a 19.

Ochrolechia pallescens-y-parella, see LecatiorapareUa,

153-
Ocimum basilicum, 371.
Ocotea caudata, 88.
Octadecyl alcohol, 86.
Octane for anthracene, 237.
n-Octane for n-octyl alcohol, 84.
,, from n-butyl alcohol, 82.
„ from sebacic acid, 84.
Octanediol, 81.
Octanes, generators of, 82, 84.
2-Octanol, 82.
Octenoic aldehyde = a-ethyl-;9-propylacrolcin,

189.
n-Octoic acid for n-octyl alcohol, 28a.
Octoic aldehyde, 189.

„ and formic acids for octoic aldehyde, 189.
„ ethyl ester, occurrence, 45.
Octoses, non-fermentable, 46.
Octyl alcohol, n-primary, 84, 28a.
n-Octyl alcohol and acetoacetic ester for methyl-
n-nonyl ketone, 202.
,, ,, for iodoform, 24.

„ „ for methane, 24,

,, „ for methyl alcohol, 56.

,, „ for octoic aldehyde, 189.

Octyl chloride, secondary = 3 chluroctane, 82.

,, esters, occurrence, 84.
n-Octyl iodide, 202.
n-Octylacetoacetic ester, 202.
Ocyvmm basilicum, 88, 91.
Qidema, malignant, bacillus of, 52, 53.
(Enanthe crocata, 104.

,, phellandrium , 249.
(Eaanthic (= n-heptoic) acid for active hexyl

alcohol, 83.
„ „ ,, for n-hcxyl al-

cohol, 81.
(Enanthol (heptoic aldehyde) and ethyl alcohol
for nonyl alcohol, 85.
,, for heptane, 27.

„ for n-heptyl alcohol, 83.

„ for methyl-n-amyl ketone, aoi.

CEnanthylidene, see under heptine.

„ chloride = i : i-dichlorhep-

tane, 27, aor.
(Enocarpus bacaba, 349.
Otdium (Monilia) albicans, 50, 97.

„ ,, „ aldehyde producer,! 74.

„ lactis, 50.

,, ,, alcohol producer, 279.

Oldenlandia umbeUata, 236, 238, 240.
Oleaceee, mannitol in, 104.
Oleic ethyl ester, occurrence, 45.
Oleum citri, 19a.
Olive oil, catechol in, 138.

,, ,, rancid, oenanthol in, 189.
Olives, mannitol in, 104,
Ononin, 286.
Ononis spinosa, 286.
Opoponax chironium, aig.
Orange blossoms, steam distilled oil. 384.

,, sweet, oil of, 84, 189.
Orchis morio, 348.
Orcinol, 152, a86.

,, for phloroglucinol, 163.
/3-Orcinol, 156, a86.
Origanum floribundum = cinereum, 136.
,, hirtum, a8, 135.
,, majorana, 39, 90, 226.
,, smyrnamw, a8, 88, 135.
Ornus europcea, roiundi/olia, &c., 104, 244.
Orobancheacese, mannitol in, 104.
Oroxylin, 205.
Oroxylon indicum, 205.
Orris-root, 40, 159, 164.
Orsellic acid, 153.

Ortho, see under o- with respective suffixes.
Orthocoumaric acid for o-hydroxyacetophe-
none, 228.
„ „ for salicylic aldehyde,

314.
,, aldehyde methyl ether, 223.

Orthoformic ester, 145, 385.
Orthohydroxyacetophenone, 228.
Osmorrhisa longistylis, 137.
Oswego tea, oil, 136.
Osyritrin = myrticolorin, 138, 160.
Ovarian cysts, fat of, 86.
Oxalacetic acid and ester, 63, 64, 116.
Oxalic acid and methyl alcohol for acet-

aldehyde, 180.
„ ,, „ „ ,, for acetone,

198.
,, ,, for hydrogen cyanide, 267.
,, and acetic acids, &c., for diacetyl, 304.
„ „ „ „ for glycerol, 97.

,, and acetic esters for n-propyl alcohol, 63.
„ „ „ „ for quinol, 150.

,, and propionic esters for citraconic acid,

114.
„ ester and acetic acid for toluene and

benzyl alcohol, 116.
,, ,, and isopropyl alcohol for isobutyric

aldehyde, 183.
,, „ and magnesium methiodide for

diacetyl, 289.
,, „ for n-sec. amyl alcohol, 78.
Oximinosuccinic estor, 63.
Oxyacrylic (= glycidic) acid, 170, 173, 177.
a-Oxy-/a-benzainino-/3-oxypyrroIine, 98.
Oxyliishydrocarvoxime, 226.
/3-Oxyglutaric acid, 62, 63, 174, i8o, 186.
Oxymesitonedicarboiiic acid, 179.
Oxymethanesulphonic acid, 170.
Oxymethylene, 60.

326

INDEX

Oxymethyleneacetic (= formylacetic) acid, 71.
a-Oxyphenylpropionic lactone, 261.
Oxypulvic methyl ester = chrysocetraric acid,
43-

Pachnolepia decussata, 42, 153.
Pceonia moutan, 231.
Paoonol, 142, 231.
Palm nuts, 249.
Palmarosa oil, 36, 87, 89.
Palmitic acid for cetyl alcohol, 86.
,, ,, for hentriacontane, 28.

,, ,, for pentadecane, 27.

,, aldehyde for cetyl alcohol, 86.
,, ethyl ester, occurrence, 45.
Pancreatic cyst, acetone in fluid of, 289.
Pangium edule, 262.
Papaverine, 140.

Para-, see also under p- with respective suf-
fixes.
Paraconic acid, 186.
Paracoto bark, 157, 252.
Paracresol, 130.

„ for p-hydroxybenzaldehyde, 218.

,, for orcinol, 154.

Parahydroxybenzoic aldehyde, 215.
Parahydroxybenzyl isothiocyanate, 261.
Parellic (= psoromic acid), 43.
Parmelia aleurifes, 153.
borreri, 153.
caperata, 43.

fuliginosa, \&y. ferruginaacens, 153.
glabra = oUvacea and glabra, 153.
glomellifera, 153.
locarnensis, 153.
olivetorum, 153.
omphahdes, 153.
perforata, 153.
perlata, 45, 153.
saxatilis, vars.
&c., 153, 286.
sordida, 153.
sorediata, 153.

species yielding atranorin, 42.
tiliacea, var. scortca, 153.
tinciorum = corallo'ides, 153.
verruculifera, 153.
Parmelin = atranorin, 42.
Parmeliopsis hyperopia, 42.
Parsley, 104, 160, 234.
Pastinaca sativa, 40, 45, 84.
Patellaric acid, 153.

Pavefta, species yielding methyl salicylate, 41.
Peach flowers, 263.
Pears, sorbitol from, 106.
Pelargonic and formic acids for nonyl alcohol,

84.
Pelargonium odoratissimum, 89.

,, species yielding geraniol, 87.

PeniciUium duclauxi, saccharose resolved by, 244.
„ glaucum, alcoholic ferment, 49.
,, ,, arbutin decomposed by, 146,

,, ,, mannitol producer, 105.

„ ,, methylpropylcarbinol re-

solved by, 79.
,, ,, raffinose inverted by, 247.

,, ,, trehalose hydrolyser, 245.

Penny-cress, 256.
Pennyroyal oil, 37, 92, 93, 226.
Pentabromdehydrothymol, 136.
Pentacetylgluconitrile, 243.
Pentachlorcthane, 236.
Pentadecane, 27.

panni/ormis, pJueotropa,

Pentaglycol, 184.

Pentallylcarbindimethylamine, 82.

2 : 4 : 6 : 3I : 4I -Pentamethoxybenzoylacetophc-

none, 235.
n-Pentane for amyl alcohol, n-primary, 76.

,, ,, ,, ,, n-secondary, 79.

,, for formic aldehyde, 173, 174,

,, from acetic acid, 76.

,, from n-butyric acid, 77.

„ from glycerol, 76.

„ from mannitol, 76.

,, from pyridine and piperidine, 76.
Pentane, secondary, for acetaldehyde, 180.
Pentane-a7€-tricarboxylic acid, 283.
3-Pentanol = diethyl carbinol, 78.
3-Pentene, 77, 78.

Pentine (= valerylene) for cymene, 33.
3-Pentine = methylethylacetylene, 78.
Pentosans, fermentable, 48.
Pentoses, fermentable and non-fermentable, 48.
Peppermint oils, 38, 91, 92, 174, 183, 227, 253,

275, 283, 288, 390.
Pepperwort, 28, 135, 212.
Perchlorethylene, 236.
Perchlormethyl formate, 253.
Perchlorpyrrole chloride, loi.
Persea {Laurus) Ungue, 139, 161.
Perseitol = mannoheptol, 107.
Persian berries, 138, 139.
Persica vulgaris, 305.
Perlusaria amara, 286.

„ lactea, 153.
Peru balsam, 107, 219.

Petit-grain oil, 37, 87, 88, 90, 224, 278, 282.
Petunga roxburghii, 41.
Peucedanum grareolens, 37, 226.
Phaseolunatin, 192.
Phaseolus lunatus, 192, 263.
p-Phenetidine, 152.
Phenetole, 152.
Phenol, 119, 285.

,, and acetic acid for ketocoumaran, 231.
,) ,, ,, ,, &c,, for piceol, 229.
,, and anisole for iretol, 164.
,, and benzoic aldehyde for anthracene,

237-

,, and benzyl chloride, &c., for anthra-
cene, 236.

„ and chloroform, &c., for p-hydroxy-
benzoic aldehyde, 315.

„ and chloroform, &c., for salicylic alde-
hyde, 213.

„ and chloroform for p-hydroxybenzyl
alcohol, 118.

„ and ethyl alcohol for quinol ethyl
ether, 152.

,, and hydrogen cyanide for anisic alde-
hyde, 218.

,, and hydrogen cyanide for p-hydroxy-
benzoic aldehyde, 390.

,, and phthalic anhydride for m-hydroxy-
anthraquinone, 236.

,, and phthalic anhydride for purpurin,
241.

,, and resorcinol, &c., for euxanthoue,
233.

„ &c., for benzoic aldehyde, 211.

,, &c., for saligenin, 117.

,, &c,, for vanillin, 220.

,, for carbon disulphide, 252.

,, for catechol, 140.

„ for chloroform, 56.

,, for ethyl alcohol, 56.

INDEX

327

Phenol for ethylene, 56.

„ for hydrogen cyanide, 266.
,, for methane, 25.
,, for phloroglucinol, i6a.
„ fur phlorol, 133.
„ for pyrogallol, 159.
,, for quinol, 146.
,, for quinone, 235.
,, for resorcinol, 144.
„ potassium cyanide, and carbon disul-
phide for benzyl isothiocyanate, 259.
,, propionic acid, hydrogen cyanide, &c.,

for asarone, 164.
,, propionic acid, and methyl alcohol for
anethole, 137.
a-Phenoldisulphonic acid, 140.
Phenol-o-sulphonic acid, 140.
Phenol-p-sulphonic acid, 235, 286.
Phenoltrisulphonic acid, 140.
Phenopropyltrimethylammonium hydroxide,

212.
Phenoxyacetic acid, 231.
5-Plienoxybutylamine, 102.
7-Phenoxybutyronitrile, 102.
Phenoxylacetal, 133.
Phenyl isocyanide, 207.

,, magnesium bromide, 284, 285, 289.
,, mustard oil, 253.
,, thiocarbimide, 207.
Phenylacetamide, 259.

Phenylacetic acid and carbon disulphide for
benzyl isothiocyanate, 258.
,, „ &c., for styrene, 35.

,, ,, for benzaldehyde, 209, 289.

,, ,, for o-cresol, 127.

,, ,, for p-cresol, 286.

„ ,, for phenol, 123.

,, „ for phlorol, 134.

„ ,, for quinol, 148.

„ ,, for toluene and benzyl al-

cohol, 115.
,, aldehyde, see also a-toluic alde-

hyde, 118, 293.
„ „ for styrene, 34.

„ and formic acids and caibon

disulphide for phenylethyl iso-
thiocyanate, 261.
,, and formic acids for phenylethyl

alcohol, 118.
„ and oxalic esters for piceol, 229.

, , ester for phenylethyl alcohol , 284.

Phenylacetylene for acetophenone, 208, 210.

„ for o-hydroxyacetophenone,

228, 229.
,, for salicylic aldehyde, 214.

„ for styrene, 34.

,f from acetophenone, 34.

„ from cinnamic acid, 35, 209.

,f from ethylbenzene, 34.

„ from yS-iodocinnamic acid, 35.

,, from phenylpropiolic acid, 35.

Phenylalanine and carbon disulphide for
phenylethyl isothiocyanate,
261.
„ for styrene, 35.

Phenylaminoacetic acid and nitrile, 258.
Phenylbromacetic acid, 258.
Phenyl-a-bromlactic acid, 261.
Phfenyl-/3-bromlactic acid, 35, 261.
Phenyl-/3-brompropionic (= i ^ - bromhydro-

cinnamic) acid, 209.
Plienylbutylene for naphthalene, 165.
Phenylchloracetic acid, 208, 259.

Phenyl-a-chloi'laclic acid, 35, 209, 261.
Phenyl-/3-chlorlactic acid, 35, 261.
Phenyl-a/3-dibrompropionic (= aj3-dihydro-
cinnamic) acid and ester, 209, 228, 261, 290.
Phenyl-a;3-dibrompropionic acid for styrene, 35.
m-Phenylenediamine, 143.
o-Phenylenediamine, 142.
p-Phenylenediamine, 150, 217, 235.
Phenylethyl alcohol, 118, 284.

,, isothiocyanate, 260, 293.

w-Phenylethylamine, 260, 261.

,, for styrene, 34.

„ from benzoic aldehyde,

&c., 34.
,, from ethylbenzene, 34.

„ from mandelonitrile, 34.

,, from phenylalanine, 35.

,1 from phenylpropionic

acid, 35.
,, from toluene, 34.

Phenylglyceric acid, 35, 261.

„ „ for benzaldehyde, 210.

Phenylglycidic (= )3-phenyloxyacrylic) acid,
260, 261.
,, ,, for benzaldehyde, 209.

,, ,, for CO - phenylethyl-

amine, 34.
„ „ for styrene, 34.

Phenylglycuronic acid, a salt of, in urine, 119.
Phenylglyoxal, see also benzoylformaldehyde,

210.
Phenylglyoxylic acid for benzaldehyde, 208,

210,
Phenylhydrazine, 208.
Phenylhydroxylamine, 142, 150, 216, 266.
Phenyliodhydracrylic (= a-iodo-/3-phenyl-;3-

hydroxypropionic) acid, 261.
Phenyliodopropionic acid for styrene, 35,
Phenylisocrotonic (= /3-benzalpropionio) acid,

168, 216.
Phenylisoxazole and carboxylic acid, 211.
Phenyl-a-lactic acid, 260, 261.
Phenyl-)3-lactic acid, 207-211.

„ „ for styrene, 35.

Phenylmalonic ester, 229.
Phenylmethylmalonic acid and ester, 229.
Phenylnitroethylene = I'-nitrostyrene, 208,

210, 216.
Phenylnitromethane = I'-nitrotoluene, 259.
Phenyloxalacetic ester, 229.
/8-Phenyloxyacrylic (= phenylglycidic) acid,

260, 261.
Phenylpropiolic acid for benzaldehyde, 208-
210.
,, ,, for o-hydroxyacctophc-

none, 228.
,, ,, for salicylic aldehyde,

214.
,, n for styrene, 35.

y3-Phenylpropionic acid and carbon disulphide

for phenylethyl isothiocyanate, 261.
3-Phenylpropionic acid for styrene, 35.
Phenylpropyl alcohol, 119, 284.
Phenyisulphuric acid, salt of, in urine, irg.

,, ,, synthesis of, 120.

Phenyl-o-toluyl ketone, 237.
Ta i-Phenyltrimethylene -2:2:3- tricarboxylic

ester and acid, 168.
Phloracetophenone dimethyl ether, 276.

,, trimethyl ether, 233, 234.

Phloretin, phloroglucinol complex in, 160.
Phloridzin, phloroglucinol complex in, 160.
Phloroglucinol, 160, 287.

328

INDEX

Phloroglucinol acetic and veratric acids, &c.,
for luteolin, 234.
,, and quinol, &c., for gentisin,

233-
,, anisic and acetic acids, &c., for

apigenin, 334.
,, anisic aldehyde, acetic acid, &c.,

for kampherol, 376.
,, benzoic and acetic acids, &c.,

for chrysin, 333.
„ benzoic acid, &c., for hydro-

cotofn, 231.
„ „ „ „ for methyl-

hydrocotoin, 331.
,, for acetone, 300.

„ for antiarol, 164.

,, vanillin, acetic acid, &c., for

quercetin, 276.
Phloroglucinolcarboxylic acids, 163.
Phlorol, 133, 286.

Phloryl isobutyrate, occurrence, 135.
Phwnix canariensis, 249.

„ dactylifera, 249.
PhoUofa rachcosa, 105.
Phorone, 30, 123, 126, 129, 133, 203.
Phosgene, 125.
Phospham, 265.

Phthalic acid and phthalimide for benzonitrile,
211, 359.
„ „ for anthraquinone, 337.
„ „ for benzonitrile and benzalde-

hyde, 211.
„ „ for benzyl alcohol, 384.
„ ,, for m-cresol, 130.
„ „ for phenol, 122.
„ „ for toluene, 114.
„ ,, from the naphthols, &c., 284.
„ anhydride and benzene for anthra-
quinone, 237.
Phthalide, 115, 122, 336.
Plithalidedicarboxylic acid, 30, iia, 114.
Phthalidetricarboxylic acid, 30.
Phthalimide, 115, 211.
Phthalimidine, 115, 130.
Phthaloyl chloride, 115, 237.
Phyllanthus zeylanicus, 41.
Physcia ccesia, 45.

,, (Anaptychia) ciliaris, 153.
,, medians, 45.
,, parietina, 104.
,, species yielding atranorin, 42.
Physcianin = atraric acid = ceratopiiylIin, 43,

156.
Phytelephas tiiacrocarpa, 347, 249.
Picea alba, 273.
,, excelsa, 273.
„ nigra. 273.
,, vulgaris, -a-]^.
Picein, 229.

Piceol = p-hydroxyacetophcnone, 229.
a-Picoline for n-hexyl alcohol, 82.
Picric acid ( = 2 14: 6-trinitrophenol), 162-164.
,, ,, for p-liydroxybenzaldehyde, 216.
„ ,, for phloroglucinol, 162.
Picrocrocin, 244.
Picryl chloride = 2:4: 6-chIortrinitrobenzenc,

163.
Picryl-p-hydroxyphenylglyoxylic ester and

acid, 216.
Picrylphenol, 216.
Pierardia dukis, &c. , 41.
Pimenta acris, 36, 191.
Piinenta-leaf oil, 191.

PimpineUa aiiisum, 137, 174, 218.
Pinacolin = dimethylbutanone, 75, 76.
Pinacone ( = tetramethylethylene glycol), 75,
76, 8a, 197.
,, for active hexyl alcohol, 83.
,, generators of, 82, 83.
Pinastric (=chrysocetraric) acid, 43.
Pine-apple, mannitol from, 104.
Pine-needle oil, 36.
Pine-wood oil, 28.
Pinus and Abies, 39, 104.
„ jeff'reyi, 27.
,, larix, 245.
,, montana, 273.
,, picea, 37, 229.
,, pumilio, 273.
,, sabiniana, 27.
,, sylvestris, 119, 273.
a-Pipecoline, 82.
Piper angustifolium, 158, 164.
,, belle, 158.
,, cubeba, 36.
,, methysticum, 42.
,, nigrum, 36.
,, peltaium, 137.
Piperic acid, 140.

,, ,, for piperonal, 223.
Piperidine for amyl alcohol, n-primary, 76.

,, for erythritol, 103.

Piperonal, 222.

,, for vanillin, 221.

Piperonylic acid, 140.

„ „ for catechol, 141.

Pistacia lentiscus, 159.

,, terebinthus, 159.
Pivalic (=trimetliylacetic) acid, 75, 76.
Placodium aaxicolum, &c. , 42.

„ species yielding parellic acid, 43.
Platysma compUcatum, 286.
,, diffusum, 153.
,, glaucum, 42.
Phopsidium chlorophanum, 45.
Pleural fluid, laevulose in, 348,
Plums, sorbitol in, 106.
Pneumococc^^s, alcohol producer, 52.
,, glycerol ferment, 51.

Podocarpic acid, 131.
Podocarpus chinensis, 41.

,, cupressina var. imbricaia, 131.

„ nagcia, 41.

Podophyllotoxin, 153.
Podophyllum emodi, 138, 153.

,, peltatum, 138, 153.

Polygala, species containing methyl salicylate,

41-
Polygonum fagopyrum, 138.
„ persicaria, 139.
Polypodium vulgare, 104.
Pomegranate root, 104.
Populin, 250.

,, decomposed hy Aspergillus, 117.
Populus balsamifera, 333.

,, nigra, 333.

,, pyramiduUs, 233.

,, sp. yielding chrysin, 160.

„ „ „ populin, 250.

,, ,, „ salicin, 116, 250.

Porphyra laciniata, 249.
Portugal laurel, 263.

,, orange oil, 37, 41.
Potato, solanin in, 288.
Potato-peel, vanillin complex in, 219.
PotentiUatormentilla, 161, 139.

INDEX

329

Privet, niannitol in, 104.
Prepaid oxime, 61,
Propane for acetol, 94.
,, for glycerol, 97.
,, for isopropyl alcohol, 67.
,, for n-propyl alcohol, 58,
,, from acetone, 60.
,, from butyl alcohol, tertiary, 66.
„ from butyl iodide, tertiary, 59.
,, from n-butyric acid, 61, 66, 68,
„ from glycerol, 59, 67.
,, from a-iodobutane, 59.
„ from isobufyric acid, 62, 68.
,, from isopropyl alcohol, 59.
,, from methyl and ethyl alcohols, 66.
Propanetricarboxylic acid and ester, 62,69, 187,

198.
Propenylbenzene, 21a.
Propinal for acetylene, 32, 58.
Propiolic (=propargylic = propinic) acid, 31,

183.
Propionamide, 6r, 114, 187, 196.

,, and magnesium ethobromide for

diethyl ketone, a8i.
Propionic acid and methyl alcohol for tertiary
butyl alcohol, 75.
,, ,, &c., for methylpropylacetalde-

hyde, 187.
,, ,, for acetaldehyde, 176,

,, ,, for acetone, 196.

,, ,, for amyl alcohol, n-sec, 78.

,, „ for n-butyl alcohol, 71.

,, ,, for diacetyl, 204.

,, ,, for ethyl alcohol, 56.

,, ,, for formic aldehyde, 17a.

,, ,, for hydrogen cyanide, 267.

„ ,, for isopropyl alcohol, 68.

,, ,, for n-propyl alcohol, 61.

„ „ for quinol, 151.

,, ,, for toluene, 114.

,, aldehyde = propanal, a88.
,, ,, for methane, 34.

,, „ for methylpropylacetalcle-

hyde, 185.
,, „ forn-propyl alcohol, 61, a8o.

,, and acetic aldehydes for crotonic
aldehyde, 190.
Propionitrile = ethyl cyanide, 61, 66, iii, 114,

151, 187, 196, 199.
Propionyl chloride, 114, 187.

„ cyanide, 187.

p-Propionylanisole, 137.

Propionylformic ( = ethylglyoxylic) acid, 187.
n-Propyl alcohol, 58, 279.

,, ,, and acetic acid for amyl alco-

hol, n-sec, 79.
,, ,, and carbon disulphide for sec.

butyl isothiocyanate, 255.
,, ,, for allylene, 114.

,, ,, for n-butyl alcohol, 70.

,, „ for ethyl alcohol, 55,

,, ,, for n-hexyl alcohol, 80.

,, ,, for isopropyl alcohol, 65, 280.

„ ,, for propanal and methyli^ro-

pylacetaldehyde, 185,
Propyl alcohols for acetol, 93.
,, ,, for acetone, 193.

,, ,, for acrolein, 109, 190.

,, ,, for benzene, 30.

,, ,, for diacetyl, 204.

,, ,, for formic aldehyde, 173.

„ „ for glycerol, 97.

,, „ for methane, 24.

Propyl alcohols for quinol, 151.

,, „ for toluene, 109.

,, chloride for methane, 24.

,, cyanide =butyronitrile, 70, 72.

„ ether, 173.
Propyl;! mine for propyl alcohols, 58, 66, 67.
Propylbenzene for hydrocinnamic aldehyde,

211, 213.

,, foro-hydroxyacetophenone, 229.

Propylene bromide, 65, 97, 109, 185, 193.

,, chlorhydrin, 185.

,, chloride, 65, 66, 93, 97, 109, 185, 193.

,, cyanide, see pyrotartaric nitrile.

,, for acetol, 93.

,, for acetone, 193, 195.

,, for acrolein, 190.

,, for diacetyl, 204.

,, for formic aldehyde, 173.

,, for glycerol, 97.

„ for isopropyl alcohol, 65.

,, for methylpropylacetaldehyde, 185.

„ for n-propyl alcohol, 59.

,, for quinol, 151.

,, for toluene, 109.

,, from acetic acid, 68, 97.

,, from acetone, 98.

„ from amyl alcohols, 66, 97.

,, from azela'ic acid, 69, 98.

,, from butyl alcohols, 66, 99.

„ from butyric acids, 68, 98.

,, from ethyl alcohol, 66, 98.

,, from glycerol, 67, 195.

,, from n-hexane, 67.

,, from isovaleric acid, 68, 98.

,, from lactic acid, 68, 98.

, , from oxalic and acetic acids, 68, 97.

,, from propyl alcohols, 65, 97, 109,

193, 280.

,, from thymol, 67, 98.

,, glycol («= I : 2-dihydroxypropane),

65, 193-
„ ,, bacterial fermentation of, 93.

,, „ for acetol, 93.

„ ,, for acetone, 193, 195.

,, ,, for methylpropylacetalde-

hyde, 185, 188, 189.
Propylene oxide, 65, 185, 288, 289.
n-Propylene ( = trimethylene) glycol, 85.
n-Propylethylene = amylene, 79.
Propylisobutyl ketone, 197.
Prosopis dulcis, 247.
Protea melli/era, quinol in, 146.
Proteids, p cresol from, by putrefaction, 131.
,, phenol from, by putrefaction, 119.

Proteus vulgaris, phenol producer, 119.

,, ,, saccharose inverter, 244.

Protocatechuic acid, 140.

,, ,, for catechol, 141.

,, ,, for hydrogen cyajiide, 267.

„ ,, for toluene and benzyl

alcohol, 116.
,, aldehyde-carboxylic ester, 221.

,, aldehyde, &c., for vanillin, 220,

221.
,, „ methyl benzyl ether,

22a.
Protocetraric acid, 286.
Protococcus vulgaris, 100.
Prunus laurocerasus, 104, 107, 262.
,, padus, 263.

,, species yielding amygdalin, 205.
,, spinosa, 276, 287.
Pi'ussic acid, see under hydrogen cyanide.

330

INDEX

Pseudaconitine, 140.

Pseudobutylene and carbon disulphide for sec.
butyl isothiocyanate, 254.

J, for methylacetylcarbinol, 95.

„ for methylethyl ketone, 95,

255-
,, from angelic and tiglic acids,

255-
„ from isoamyl alcohol, 255.

,, from isobutyl alcohol, 254.

,y from isovaleric acid, 255.

„ from tert. butyl alcohol, 74,

75-
,, generators of, 95.

Pseudocumene, 30, 123, 126, 129, 132, 149.
,, for o-cresol, 126.

,, from camphor, 285.

Pseudocumenesulphonic acid and amide,

132.
Pseudocumidine = 5 amino- 1 : 2 : 4-trimethyl-

benzene, 149.
Pseudosarcine, 277.
Psora ostreata, 153.
Psychotria celastroides, 41.
Pterocarpus {Dcmnonorops) draco, 161.
,, erinaceus, 138.
,, marsupium, 138, 139, 159.

Ptychotis ajowan, 136, 212.
Pulegone, 226, 290.

„ and isopropyl alcohol for menthone,

228.
,, for acetone, 199.

,, for m-cresol, 130.

,, for isopropyl alcohol, 68.
,, for menthol, 93.

,, for phenol, 124.

,, for n-propyl alcohol, 60.
,, for toluene and benzyl alcohol, 115.

Pulveraria {Lepraria) latebrarum, 42.
Pulvic acid and anhydride, 210.

,, methyl ester, 43.
Punica granatum, 104.
Purpurin, 240, 291.

,, for purpuroxanthin, 239.
Purpurinamide, 240.
Purpurincarboxylic acid, 240.
Purpurogallin, 168.
Purpuroxanthin, 142, 239.

,, for purpurin, 241,

Purree, 232.
Putrescine ( = tetramethylenediamine) for n-

butyl alcohol, 72.
Pycnanthemumlanceolatum= Thymus virginicus, 135,

226.
Pygium, sp. yielding amygdalin, 205.
Pyrazolin-3 : 5-dicarboxylic ester, 124.
Pyridine for amyl alcohol, n-primary, 76.

,, for n-hexyl alcohol, 82.
Pyrogallol, 159, 287.

,, and plithalic anhydride for anthra-

gallol, 240.
,, for antiarol, 163.

,, for naphthalene, 168.

,, trimethyl ether, 287.

Pyroglutamic acid, 103.
Pyrola, sp. yielding arbutin, 146.
Pyromellitic acid, 120.
Pyromucic acid, 103, 142, 145, 163, 168, 180,

235-
Pyroracemic ( = pyruvic) acid and magnesium

methiodide for
isoamyl alco-
hol, 281.

Pyroracemic (= pyruvic) acid, &c., for ethyl-
benzene and
phenylethyl
isothiocyanate,
260
,, ,, for acetaldehyde, 176,

177.
„ ,, for acetone, 193, 196,

198, 199.
,f ,, for amyl alcohol, n-

sec, 79.
,, ,, for benzaldehyde, 211.

,, ,, for benzene, 31.

), ,, for a-crotonic acid and

formic aldehyde, 171-

173-
,, ,, for diacetyl, 204.

,, ,, for ethyl alcohol, 57.

,f ,, for methylpropylacro-

lein and methylpro-
pylacetaldehyde, 186,
187.
„ ,, for phlorol, 134.

,, ,, for n-propyl alcohol,

61-63.
„ ,, forquinol, 150, 151.

,f „ for uvitic acid and to-

luene, no. III, 113,
114.
,, ,, generators of, 79.

,, nitrile = acetyl cyanide, 61, 63,

no 112, ii6, 151, 171, 176, 186,
187.
Pyrotartaric acid for acetone, 193, 196, 198, 199.
,, ,, for ally lene and toluene, 108-

III, 113, 114, 116.
,, ,, for isopropyl alcohol, 65-69.

,, ,, for methyl propylacetalde-

hyde, 185-187.
,, ,, for n-propyl alcohol, 58, 62,

63.

,, nitrile =^ propylene cyanide, 38,

109, 185.
Pyrrole for erythritol, 100, 103.
Pyrrolidine, 103.
Pyrrolylene = divinyl, &c., 100.
Pyrus mains, 205.

Quebracho Colorado, 139, 275.
Quercetin, 276.

,, catechol complex in, 138.

,, phloroglucinol complex in, 160.

Quercitrin, 138, 160.
Quercus, sp. yielding methyl salicylate, 41.

,, tinctoria, 138.
Quinizarin = i : 4-dihydroxyanthraquiuone for
purpurin, 241, 291.
,, from iinthriiquinone, 291.

Quinol = hydroquinonc, 146, 286.

,, and phloroglucinol, &c., for gentisin, 233,
,, and phthalic anhydride for purpurin,

241.
,, and resorcinol, &c., for euxanlhone, 232,

=33-
,, &c., for asarone, 165.
,, ethyl ether, 152.
,, for hydroxyquinol, 160.
,, for quinone, 235.
,, for I'esorcinol, 146.
,, methyl ether, 152.

,, ,, ,, and dextrose for methyl-

arbutin, 251.
Quinoline for hydrociunamic aldehyde. 212.

INDEX

331

Quinone, 235.

,, &c., for asarone, 165.
,, for hydrogen cyanide, 267.
,, for hydroxyquinol, 160.
,, for quinol, 146.

Racemic acid and propionic aldehyde for phlo-

rol, 134.
„ ,, and n-propyl alcohol for benzalde-

hyde, 211.
„ ,, and n-propyl alcohol for phenyl-

ethyl alcohol, 118.
,, ,, for quinol, 151.
,, ,, for toluene, 114.
Radish, 356.

Kaffinose ( = melitriose), bacterial fermentation,
52.
,, fermentability by moulds, 49.
,, fermentable by yeasts, 50.
,, hydrolysis of, 245, 247.
Raggi, Javan, 49, 244, 245.
Ramalic acid, 153.
Ramalina ceruchis, 286.

,, poUinaria, 152, 153.
Rangiformic acid, 43.
Rape-seed oil-cake, 256, 357.
Raphanus sativus, 256.
Raphiosphora flamvirescens, 45.
Rassamala resin, 205, 223.
Red bearberry, 146, 251.
Red whortleberry, 146.
Resacetophenone, 231, 275.
Reseda liiteola, 138, 139, 234.

,, roots, 260.
Resins, pine and larch, vanillin from, 219,
Resorcinol, 142, 286.

,, and acetic or citric acid, &c., for

pseonol, 231.
,, and carbon disulphide for cresor-

cinol, 186.
,, and quinol or salicylic acid, phenol,

&c., for euxanthone, 232, 233.
,, &c., for asarone, 165.

,, for catechol, 141.

,, for phloroglucinol, 162.

,, vanillin, acetic acid, &c., forfisetin,

275-
Resorcinoldicarboxylic ( = i8-dihydroxybenzoic)

ester and acid, 145.
Resorcinoldithiocarbonic acid, 156.
Resorcinoltricarboxylic ( = dihydroxytrimesic)

ester, 145.
i3-Resorcylic ( = 2 : 4-dihydroxy benzoic) acid,

143) 144, 232, 233.
Rhamnazin, 139, 160.
Rhamnetin, 139, 160.
Rhamnose, non-fermentable, 46.
Rhamnus chlorophonts, 160.

,, utilis, 160.
Rhinanthus, mannitol from sp. of, 104.
Rhizocarpic acid, 45.
Rhizocarpon geographicum, vars., 43, 156.

,, sp. yielding rhizocarpic acid, 45.

Rhizonic and rhizoninic acids, 156.
Rhizopus nigricans, alcoholic ferment, 49.

,, orysce, starch saccharification by, 245.
Rhodinal, 89, 191, 193, 288.
Rhodinol (1 citronellol), 89, 90, 282, 388.

., for methone, 227.
Rhubarb, Chinese, 287.
Rhus coriaria, 159.
„ cotinus, 139, 159, 275.
,, mctopium, 139, 159.

Rhus rhodanthema, 138, 275.

,, succedanea, 96.

,, thymifoUa, 139.
Ribes aureum, 262.

,, nigrum, 262.

,, rubrum, 262.
Ricinine, 42.
Ricinus communis, 43.
Robinia pseudacacia, 159, 161, 234.
Robinin = kampherol glucoside, 119, 138, 160,

161.
Roccella fuciformis, 100, 152, 153, 156.
„ intricata, 43, 100, 152, 153.
„ montagnei, 100, 152, 153.
,, peruensis, 153.
,, iinctoria, 43, 100, 152, 153.
Rohdea japonica, 249.
Rosa alba, 87.

,, damascena, 87.
Rose leaves, 138.

,, oil of, 87-89, 118, 191.
Rosemary oil, 91, 271, 272, 274.
Rosmarinus officinalis, 91, 271, 272.
Rottlera dispar, 41.
Ruberythric acid, 238.
Rubia iinctoria, 238.
Rubus sundaicus, 41.

Rue, oil of, 38, 41, 43, 45, 85, 201, 202, 205.
Rutigallic acid =1:2:3:5:6: 7-hexahydroxy-

anthra quinone, I3i, 339.
Rumex obtusifolius, 138.
Ruscus acvdeatus, 349.
Russula integra ~ Agaricus integer, 104.
Riita graveolens, 43, 138, 201.
Rutin, 138, 160.
Rye, stalks of, mannans from, 249.

Sabal serrulata, 45.
Saccharic acid, 103.

Saccharobacillus pastorianus, alcohol pi'oducer, 52.
Saccharomyces anornalus, amyl acetate producer,
80.
„ as alcoholic ferments, 45,

,, ellipsoideus, isobutylene glycol

producer, 96.
,, of ginger-beer plant, 51.

,, of kephir, 51.

,, selective fermentation by, 47.

, , vordermanni, from Javan ' raggi, '49.

Saccharose (cane sugar), bacterial fermenta-
tion, 51-53.
„ n-butyl alcohol from by Bacillus

orthobutylicus, 70.
,, fermentability of, 47, 49, 50.

„ fermentation by Leuconostoc meser^er-

oides, 247.
,, for hydrogen cyanide, 366.

,, isobutylene glycol from, 96.

,, resolution by yeasts, moulds, &c.,

244, 247.
Saclisia suavcolens, alcoholic ferment, 47.
Safflower, 138.
Saffron, meadow, 43.
,, oil of, 92.
,, plant, 244.
Sagapenum, 142.
Sage, oil of, 91, 212, 271, 273.
Sake, 49, 244, 245.
Salop mucilage, 248, 292.
Salicin, 250, 284.

,, and benzoic acid for populin, 250.
,, for salicylic aldehyde, 213.
,, occurrence in plants, 116.

S82

INDEX

Salicylic acid and acetic ester for salicylic alde-
hyde, 214.
„ ,, and amide for saligenin, 117.
,, ' ,, and phloroglucinol for gentisin,

233-
„ ,, and resorcinol for euxanthone,

232.
„ ,, &c., for o-liydroxyacetoplienone,

aaS.
„ ,, for anisic aldehyde, 219
,, ,, for carbon disulphide, 25a.
,, ,, for catechol, 141.
,, „ for ethyl alcohol, 57.
,, „ for methane, 26.
„ ,, for phenol, 120, 124.
„ ,, for quinol, 146.
,, and acetic aldehydes, &c., for o-cou-
maric aldehyde methyl ether, 223.
Salicylic aldehyde, 213.

„ ,, and acetic acid for hydrogen

cyanide, 268.
,) ,, and acetic acid for keto-

coumaran, 230.
ff „ and acetic acid for phlorol,

134-
„ ,, and acid for picric acid and

phloroglucinol, 162.
,, ,, and dextrose for salicin, 250.

f, ,, for saligenin, 117.

,, benzyl ester, occurrence, 108.
,, ester for quinol ethyl ether, 152,
,, methyl ester, occurrence, 40.
Salicyloxyacetic acid, 230.
Saligenin, 116, 284.

,, for picric acid and phloroglucinol, 162.
,, for salicylic aldehyde, 213.
Salinigrin, 215.

Saliva, thiocyanate in, 268, 269.
Salix diaco'or, 215.
,, purpurea, 284.
„ sp. yielding salicin, 116, 250.
Salvia officinalis, 91, 271, 273.

,, sdarea, 88.
Sandal-wood oil, 204, 224, 278.
Sapan wood, 142.
Saponaria officinalis, 146.
Saponarin, 146.

Sarcina, saccharose inverter, 244.
Sassafras bark, oil of, 271.

,, leaf, oil of, 87, 88, 191.
Sassafras officinalis, 191.
Satureia hortensis. 28, 135, 212.
,, montana, 135.
,, ihymbra, 28, 37, 273.
Savin oil, 204, 224, 278.
Schinus molle, 135.

Schizophyllum lobatum, carbon disulphide genera-
tor, 251.
Schizo-Saccharomyces octosporus, 278.
Scoparin, 139, 161, 234.
Scorzonera hispanica, 104, 139.
Scrophulariaceee, mannitol from, 104.
Scurvy -grass or spoon wort, 254, 256.
Scutellaria altissima, 161.
Scutellarin and scutellarein, 161.
Sea-buckthorn, 104, 138.
Sebacic acid for amyl alcohol, n-primary, 76.
,, ,, for cetyl alcohol, 86.
,, ,, for heptoic aldehyde, 189.
,, ,, for n-hexane via suberic acid, 81.
,, ,, for valeric aldehyde, 184.
Semecarpiis sp., 41.
Serum, laevulose in, 248.

Siegburgite, 36.
Sinalbin, 117, 159, 262.
Sinapic acid, 159.
Sinapis alba, 261.
,, juncea, 256.
,, nigra, 256.
Sinigrin = potassium myronate, 256.
Sisymbrium alliaria, 256.
Slaitia sidcroxylon, 41.
Sinilax glycypkylla, 160,
Sodamide, 264.
Sodium ethyl, 75.
Soil bacteria, 53.
Solanum dulcamari, 288.
,, lycopersicnm, 288.
,, nigrum, 288.

,, verbascifolium, 288.

Solidago canadensis, 36.

,, sp., borneol from, 273.
Sophora japonica, 138.
Sorbitol, 106.

,, for dextrose, 246.
Sorbose, bacterial fermentation, 52.
,, bacterium = B. xylimcni, 93, 107.
„ ,, leevulose from mannitol by,

247.
,, non -fermentable by yeast, 46.
Sorbus aria, 205.

,, aucxiparia, 205.
Sorghum, cyanogenetic glucoside of, 263, 293.
Sorghum vulgare, 263.
Spartium scoparium, 161, 234.
Spearmint oil, 38, 88, 92, 226.
Sperm oil, 85.
Spermaceti, 85, 86.
Sphenodesma pentandra, 4 : .
Sphyridium placophyllum, 42.
SpiceAvood oil, 41.
Spike oil, 88, 90, 91, 271, 27a, 274.
Spircea aruncus, 213, 263.
,, digitafa, 213.
,, filipeyuhda, 40, 213.
,, japonica, 263.
,, kamsckatica, 213.
,, lobaia, 213.
,, palmata, 40.
,, piperonal in oil, 222.
,, salicin from flowers, 116.
,, sorbi/olia, 263.
,, ulmaria, 40, 213, 250.
,, vanillin from oil, 219.
Spirasin, 213.
Spleen, juices of, 99.
Spoonwort or scurvy-grass, 254, 256,

„ oil of, 37.

St. Ignatius bean, 249.
Stachyose = manneotetrosc, 292.
Stachys tuber if era, 292.

Staphylococcus pyogenes aureus, lactose ferment,

52.
,, ,, ,, phenol producer,

119.
Star-anise oil, 92, 137. 152, 218.
Starch, alcohol hom, 49, 50.

,, bacterial fermentation, 51-53, 69, 70.
,, fermentation by Bacillus suaveolens, 174.
,, saccharification of, 49, 245, 246.
Stearic acid for n-hexane, 79.

,, ,, for octadecyl alcohol, 86.
,, ,, for suberic acid, 81.
,, ,, for valeric aldehyde, 184.
Stereocaulon dpinum, 153.
,, coralMdcs, 153.

INDEX

833

Stereocaulon pileatum, 153.
,, ramulosum, 45.

,, sp. yielding atranorin, 42.

,, sp. yielding parellic acid, 43.

Sticta palmonaria, 286
Stilbene for benzaldehyde, 289.
Storax, American, 33, 119, 219,
„ bark oil, 39.
„ liquid, 33, 36, 45, 219.
Streblus mauriiianus, 41.
Streptococcus hornensis, saccharose inverter, 244.

,, of kephir, 51.

Streptothrix chromogena, quinone producer, 235.
Strophanthin and strophanthidin, 245, 249.
Strophanthus komhe, 245.
Strophantobiose methyl ethei", 245, 249.
Strychnos ignatii, 249.

,, mix vomica, 249.
Styrax benzoin, 160.
Styrene = cinnamon e, 33, 278.

,, and carbon disulphide for benzyl iso-

thiocyanate, 259.

„ „ „ for phenylethyl

isothiocyanate, 260.

„ bromide =» i^ : i*-dibromethylbenzeno,

34, 207, 208, 237.
„ ,, and glycol for a-toluic alde-

hyde, 260.
„ for anthracene, 237.
,, for benzaldehyde, 208, 289.
„ for benzonitrile and benzyl isothio-
cyanate, 293.
„ for o-hydroxyacetophenone, 229.
,, for p-hydroxybenzaldehyde, ai6.
,, for metastyrene, 36.
„ for methyl phenyl carbinol, 118.
„ for phenylethyl alcohol, 118,
„ forphlorol, 133.
„ for piceol, 230.
„ for salicylic aldehyde, 215.
„ glycol, 207, 208.
,, pseudonitrosite, 293.
/3-Styreno nitrosite = a-acetophenoneoxime,

293-
Styrolyl alcohol = methylphenyl carbinol, 118.
Suberic acid for n-hexane, 81.

„ ,, for n-hexyl alcohol, 81.

,, ,, generators of, 77, 81.

Sublingual, thiocyanate in, 269.
Submaxillary, thiocyanate in, 269.
Succinic acid and methyl alcohol for ei ythritol,
100.

,, ,, for acetaldehyde, 177.

,, „ for acetylene, 26.

„ ,, for benzene, 31.

,, ,, for benzyl alcohol, 116, 284.

,, „ for n- butyl alcohol, 7a.

„ „ for ethyl alcohol, 57.

„ ,, for ethylene, 25, 57.

„ ,, for hydrogen cyanide, 268.

,, ,, for laevulic acid, loi.

,, ,, for methane, 25.

,, ,, for quinol, 148.

,, ,, for toluene and benzyl alcohol,
116.

,, ,, for valeric aldehyde, 183.

,, ester for isopropyl alcohol, 69.

,, ,, for n -propyl alcohol, 63.
Succinimide, 100.

Succinylsuccinic ester, 63, 64, 148, 149, 186.
Sugar-beet, glycerol formed iu, by anaerobic

respiration, 284.
Sugar bush, 146.

Sugar, mannitol from, during fermentation,
105.

,, n- propyl alcohol from, by fermentation,
58.
Sugars, conditions determining fermentability,

46.
o- and p-Sulphamidemesitylenic acids, 123.
4-Sulphamidemethylbenzene-2 : 5-dicarboxylic

acid, 132.
2- and 6-Sulphamide-m-toluic acids, ia6.
5-Sulphamide-o-toluic acid, 128.
Sulphamidetrimesic acid, 123.
4 Sulphamide-a-xylic acid, 123.
Sulphaminotoluic acid and imide = methyl-
saccharin, 228.
Sulphanilic acid, 163, 235.
m-Sulphanilic acid, 143.
m-Sulphobenzoic acid, 121.
Sulphocinnamic acid, 121,
Sulphoisophthalic acid, 120, 123.
a-Sulphomesitylenic acid, 132.
3-Sulphophthalic acid, 123.
4-Sulphophthalic acid, 122, 123.
4-Sulpho-m-toluic acid, 131.
5-Sulpho-m-toluic acid, 128.
6-Sulpho-o-toluic acid, 12a.
2-Sulpho-p-toluic acid, 125, 127.
3-Sulpho-p-toluic acid, 129, 130, 227, 228.
5-Sulphotrimellitic acid, 123.
Sumach, Sicilian and Venetian, 159.
Summer savory, 28, 135.

Suprarenin = adrenalin = epinephrine, 286.
Sweat, combined phenol in, 119.
Sweet basil oil, 88, 91, 271.

,, flag oil, 164.

,, marjoram oil, 39, 90, 2a6.

„ orange oil, 37, 41, 89, 90, 191, 192,
274.
Symbiotic associations, fermentation by, 51.
Symplocos sp., 41.
Syringa vulgaris, 104, 159.
Syringin, 159.

Tagatose, non-fermentable, 46.
d-Talose, non-fermentable, 46.
Tamaris africana, 138.

,, gallica, 138.
Tanacetum vulgare, 138, 271.
Tannins, phloroglucinol complex in, 161.
Tansy, 138, 271.
Tartaric acid and propanal for phlorol, 134,

,, ,, and n-propyl alcohol for phenyl-

ethyl alcohol, 118.

,, ,, bactei-ial fermentation, 51.

,, ,, decomposition by £aciWMs<arfric«»,

94.

,, ,, for acetone, 194, 198.

,, ,, for allylene, 194.

,, ,, for benzene, 31.

„ ,, for dextrose, 246.

„ „ for erythrose, 243.

„ ,, for ethyl alcohol, 57.

,, ,, for furfural, 225.

^ ,, ,, for hydrogen cyanide, 267.

,, ,, for isopropyl alcohol, 69.

,, ,, for mannitol, 106.

,, „ for mannose, 249.

,, ,, for methane, 277.

„ ., for methylpropylacetaldehyde,

187.

„ „ for n-propyl alcohol, 63.

„ „ for quinol, 151.

,, „ for toluene, 114.

334

INDEX

Tartaric acid, n-propj'l alcohol, and carbon
disulphide for phenyltthyl isothio-
cyanate, 260.
,, and butyric acids for amyl alcohol,

n-sec, 79.
,, or racemic acid and n-propyl alcohol

for benzaldehyde, 211,
,, or racemic acid for acetaldehyde, 177.
,, ,, ,, for diacetyl, 204.

,, ,, )> for formic aldehyde,

172.
Tea, oil of, 40, 41, 192.

,, plant, 138.
Tectochrysin, 234.
Terephthalic acid for benzene, 31.
„ ,, for phenol, 123.

Terpene alcohols, transformations in plants, 89.
Terpin for cymene, 32.
,, from geraniol, 32.
,, hydrate for dipentene, 38.
„ ,, for terpineol, 91.

M » from geraniol, 32, 38.

„ „ from linaloOl, 32, 38.

,, „ from terpineol, 32.

Terpinene, 39.

„ for cymene, 33, 277.

Terpineol, 80, 282.

,, for carvone, 226.
5, for cineole, 92.
,, for cymene, 32.
„ for dipentene, 38.
,, for Isevo-isoterpene, 39.
,, for terpinene, 39.
Tetra-acetylenedicarboxylic acid, 183.

„ nitrile, 243.

Tetrabrom-m-cresol, 130.
Tetradecyl alcohol, n-primary, 86.
Tetrahydrochlortoluene, 124.
Tetrahydromethylpyrrole, loo.
Tetrahydronaphthalene - dicarboxylic anhy-
dride, 166.
Tetrahydronaphthalene-tetracarboxylic ester,

166.
A'-Tetrahydro-p-toluic acid, 283.
Tetraiodopyrrole, loi.
3:4:6: 4'-Tetramethoxybenzoylacetophenone,

234-
1:3:3*: 4'-Tetramethoxyflavanone, 276.
1:3:3': 4'-Tetramethoxyflavonol, 276.
Tetramethylenediamine (= putrescine) for

n-butyl alcohol, 72.
Tetramethylenediamine (= putrescine) for cro-

tonic aldehyde, 190.
Tetramethylethylene, 75, 197.

,, glycol = pinacone, 75.

Tetranthera citrata, 191.
Tetrarin, 287.

Tetrinic (= a-methyltetronic) acid, 149, 204.
Tetrolic (= 2-butinic) acid, iii, 112, 196.
Tetroses, synthetical, 243,
Thamnolia vermicularis, 43.
Thamnolic acid, 43.
Thea chinensis, 40.

,, cochinchinensis, 41.
Thiocarvacrol, 127.
Thiocyanates for cyanides, 265.
Thiocyanic aci^, 268.

,, ,, and glycerol for allyl isothio-

cyanate, 256.
,, ,, and methyl alcohol for methyl

mercaptan, 252.
Thiothymol, 130, 227.
Thiourea, 269.

Thlaspi anense, 256.

1-Threose, 243.

Thyme oil, 273, 274. Also under various sp.

of Thymus.
Thymol, 136.

for m-cresol, 130.
for o-cresol, 127.
for cymene, 33.
for isopropyl alcohol, 67.
for menthone, 227.
for phenol, 123.
for n-propyl alcohol, 64.
for propylene and glycerol, 98.
for quinol, 149.
for thymoquinol, 158.
for thymoquinone, 235.
Thymoquinol, 158.

,, for dimethylthymoquinol, 158,

,, for isopropyl alcohol, 67.

,, for n-propyl alcohol, 64.

,, for quinol, 149.

Thymoquinone, 64, 67, 149, 235.
Thymus capitatus, 28, 37.

,, serpyllum, 28, 135, 136, 213.

,, virginicus = Pycnanthemum lanceolatum,

135, 226.
„ vulgaris, 28, 88, 135, 136, 212, 273.
Tiglic acid and carbon disulphide for sec. butyl
isothiocyanate, 255.
,, ,, for acetaldehyde, 179.
,, ,, for benzene, 31.
,, aldehyde, 190.

,, ,, for methylethylacetaldehyde, 184.

,, hexyi ester, occurrence, 83.
,, isoamyl ester, occurrence, 79.
Tilia sp., vanillin in bark, 220.
Tissues, animal, dextrose in, 292.
Toads, isocyanacetic acid from, 268.
Tolu balsam, 107.

Toluene and carbon disulphide for benzyl

isothiocyanate,

259-
„ „ „ for p-hydroxy-

benzyl isothio-
cyanate, 262.

and dimethyl sulphate for ethylben-
zene, 286.
,j M „ for p-xylene,

285.

&c., for naphthalene, 165.
,, ,, piceol, 229, 230.

for anthracene, 236.

for benzene, 30.

for benzoic aldehyde, 205, 206, 289.

for o-benzoylbenzoic acid and anthra-
quinone, 337.

for benzyl alcohol, 108-116, 284.

for m-cresol, 128, 129.

for o-cresol, 124, 285.

for p-cresol, 131, 285.

for cresorcinol, 155.

for hydrogen cyanide, 266.

for menthone, 228.

for orcinol, 153.

for 0-orcinol, 156.

for phenylethyl alcohol, 118.

for phenylethylamine, 34.

for phloroglucinol, 163.

for quinol, 148.

for resorcinol, 143.

for /3-resorcylic acid, 233.

for salicylic aldehyde, 314.

for saligenin, 117.

INDEX

835

Toluene for styreno, 33.
,, for toluquinol, 151.
,, for vanillin, 222.
„ from acetic aldehyde, no, in.
,, from acetoacetic ester, in, 112.
,, from acetone, 109.
,, from acetylene and ethylene, 108,
,, from aconitic acid, 115.
,, from acrolein, 109, n6.
,, from alanine, 116.
,, from allyl isothiocyanate, 112.
,, from benzene and dimethyl sulphate,

284.
,, from benzoic aldehyde, 108.
,, from butyl alcohols, 116.
,, from n-butyric acid, 112.
,, from camphor, 284.
„ from catechol and hydrogen cyanide,

116.
,, from citric acid, 113.
,, from cresols, 115.
,, from crotonic aldehyde, in, 113,

116.
,, from cymene, 115.
,, from ethyl alcohol and acetic acid,

III, 112.
,, from glyceric acid, 109-111, 114,

116.
,, from glycerol, log, no.
,, from n-heptane, 115.
,, from hydracrylic acid, 116.
,, from ^-hydroxybutyric acid, 113.
,, from isobutylene, 116.
,, from isovaleric acid, 114.
,, from lactic acid, 114.
,, from lysine, 116.
,, from maleic or fumaric acid, 116,
,, from malic acid, 116.
,, from malonic acid, &c., no.
,, from mannitol, 116.
,, from mannoheptol, 115.
,, from menthone, 116.
,, from mesitylenic acid, 114.
,, from naphthalene, 114.
,, from oxalic ester and acetic acid, 116
„ from phenylacetic acid, 115.
,, from propionic acid, 114.
„ from propyl alcohols, 109.
„ from propylene, 109.
„ from protocatechuic acid, 116.
,, from pulegone, 115.
„ from racemic acid, 114.
,, from succinic acid, 116.
„ from tartaric acid, 114.
„ potassium cyanide, and carbon disul-

phide for phenylethyl isothiocyan-
ate, 260.

2 :4-Toluenedisulphonic acid, 143, 155.

3 : 5-Toluenedisulphonic acid, 154.
Toluene-o-sulphonic acid, 124, 128.
Toluene-p-sulphonic acid, 131.

Toluic acids for toluene and benzyl alcohol,

114, lis.
m-Toluic acid for o-cresol, 126.

,, „ for p-cresol, 131, 132.

,, ,, for phenol, 123.

o-Toluic acid for anthracene, 236.

„ „ for m-cresol, 128-130.

,, ,, from naphthalene, 115, 122, 236.
p-Toluic acid for o-cresol, 125.

,, „ from cymene, 115.

„ and benzoic acids for methylpur-
puroxanthin, 241,

o-Toluic (= phenylacetic) aldehyde, 118, 293.

„ „ „ for w-phenyl-

ethylamine,
260, 261.

» >i J I for styrene,

34, 35-
p-Toluic aldehyde, 125.

,, ester and amide, syntheses, 125.
m-Toluidine, 122, 127, 130.
o-Toluidine, 266.

„ for m-cresol, 128, 130.

,, for o-cresol, 124, 125, 127.

„ for cresorcinol, 155.

,, for orcinol, 154.

„ for toluquinol, 151.

p-Toluidine for m-cresol, 128.

,, for o-cresol, 124.

,, for p-cresol, 131.

„ for cresorcinol, 155.

,, for orcinol, 154.

,, and sulpho-acid, &c., for menthone,

228.
Toluidines, 0- and p-, for vanillin, 222.
o-Toluidine-3 : 5-disulphonic acid, 154.
o-Toluidine-5-sulphonic acid, 154.
p-Toluidine-3-sulphonic acid, 129,
Toluquinol = hydrotoluquinone, 151.
Toluquinone, 151.

Toluquinone-oxime ( = nitroso-o-cresol), 152.
p-Toluyl-o-henzoic acid, 125.
o-Toluyl carbinol, 284.
2 : 4-Toluylenediamine, 156.
2 : 5-Toluylenediamine, 151,
p-Toluylhydroxylamine, 131, 151.
p-Toluylhydroxylamine-m-sulphonic acid, 216.
p-Toluyl magnesium bromide, 285.
Tormentilla red, 139, 161.
Torula, alcoholic fermentation by, 48.
Trachycarpus excelsa = Chamcerops humilis, 249.
Trehalose, fermentability by moulds and yeasts,

49, 50-
,, hydrolysis and fermentation, 245.
Treniepohlia jolithus, 100.
Trewia sp., methyl salicylate from, 41.
Triacetin, 97.
Triacetonamine, 126.
Triacetylbenzene, 30.
1:3= 5-Triaminobenzene, 162, 163.
2 : 4 : 6-Triaminobenzoic acid, 163.
2 : 4 :6-Tribromaniline, 163.
Tribromanthracene, 238.
Tribromanthraquinone, 241.
I = 3 : 5-Tribrombenzene, 162, 163.
I : 2 : 3-Tribrompropane = tribromhydrin, 97,

195.
Trichloracetic acid, 251.
,, ester, 129.

aaiS-Trichlorbutyric acid, no, in.
Trichlorethane, 236.
Trichlor-aa-glyceric acid, 26, 252.
Trichlorlactic acid, in, 187.
Trichlormethylphenyl carbinol for styrene, 35.
Trichlorphenomalic acid, 26, 252, 266.
1:2: 3-Trichlorpropane = trichlorhydrin, 67, 93,

94, 97-

Trifolium repens, 249, 276.

Trigondla foenum-grcecum, 249.

Trihydroxyhexahydrocymene, 285.

1:3: 6-Trihydroxynaphthalene, 130,

Trimellitic acid, 30, 123,

Trimesic acid, 30, 31.

2:4: 5-Trimethoxybenzaldehyde = asaryl alde-
hyde, 165.

336

INDEX

I : 2 : 4-Trimethoxybenzene, 165.

2:4: 6-Triinethoxybenzoylacetophenone, 333.

1:3: 4'-Trimethoxyflavaaone, 276.

1:3: 4'-TrimetIioxyflavonol, 276.

Trimethyl carbinol, see under butyl alcohol,

tertiary.
Trimethylacetic ( = pivalic) acid, 75, 76,
Trimethylamine and methyl chloride for carbon
disulphide, 252.
,y and methyl chlorideformethyl

sulphide, 253.
„ for ethyl alcohol, 57.

,, for formic aldehyde, 173.

,, for hydrogen cyanide, 267.

,, for methane, 26.

,, for methyl chloride, 44, 57.

Trimethylene ( = cyclopropane), 59, 145, 172.
Trimethylene bromide, 59, 95, 102.

„ ,, and benzene for pro-

pylbenzenes, 207.
„ „ glycol, 05.

Trimethylenebromaminoglycol, 99.
Trimethylenebromnitroglycol, 99.
Trimethylenechlorobromide = i : 3-chlorbrom-

propane, 102.
Trimethylethylamine, 173.
Trimethylethylene = amylene, 75, 173, 176, 180,
194.
„ bromide, see under amylene

bromide.
,, chlorhydrin, 194.

,, for acetaldehyde, 176.

,f for acetone, 194, 195.

„ glycol, 180, 194, 195.

„ oxide, 194.

Trimethylethylene-lactic acid, 173, 197, 200.
Trimethylpentanediol, 69.
Trimethylphloroglucinol, 161.
Trimethylpyrolone, 199.
Trimethylpyrrolidine iodide, loi.
Trimethyltriose, 94.
a :4 :6-TrinitroanisoIe, 164.
1:3: 5-Trinitrobenzene, 163, 164.
a :4 : 6-Trinitrobenzoic acid, 163.
2:4: 6-Trinitrotoluene, 163.
Trioxymethylene, 70, 71, 82, 170-173,284,287.
Triphenylglutaric nitrile, 260.
Trithioaldehyde, 254.
Triticum repens, 104.
TropcBolum majus, 257.
Tuberose blossoms, oil of, 278, 284.
Turanose, hydrolysis of, 245.
Turnip seeds, 256.
Turpentine oil, 274.

Tyrosin, p-cresol from, by putrefaction, 131.
,, phenol from, by putrefaction, 119.
Tyrothrixclaviformis, lactose ferment, 5a.

Umbelliferae, mannitol from, 104.
Umbelliferone, 142.

,, andquinol for euxanthone, 233.

,, for resorcinol, 144.

Umbellularia cali/ornica, 36, 90, 283, 287.
Umbilicaria, see under Gyrophora.
Umbilicaric acid, 153.
Uncaria {Naudea) gambier, 138, 139.
Undecanoic acid, 202,
Upas tree, 163.

o-Uraminobenzoic acid, 147, 233.
Urceolaria cretacea, 153.

,, (PateUaria) scruposa, 153.

,, ,, var. arenaria, 153.

„ sp. yielding atranorin, 42.

Urea, &c., for thiocyanates, 269.
,, for hydrogen cyanide, 268.
Uric acid for glycerol, 99.
Urine, acetone in, 192, 289.

,, arabinose, racemic, in, 243.
,, catechol sulphate in, 140.
,, m-cre^ylsulphuric acid, salt, in, 128.
,, o-cresylsulphuric acid, salt, in, 124,
,, p-cresylsulphuric acid, salt, in, 130.
,, dextrose in, 246.
,, diabetic, ethyl alcohol in, 53.
,, dog's, ethyl sulphide in, 253.
,, glycerophosphoric acid in, 99.
,, horse's, ethylsulphuric acid, salt, in, 53.
,, laevulose in, 248.
,, mannitol in, 105.
,, methyl mereaptan in, 252.
,, phenol, combined, in, 119.
,, quinol in, 146.
,, thiocyanate in, 268, 269,
Vsnea barbata, 153.

,, ,, P'hirta, 156,

,, ceratina, 156.
,, dasypoga, 156.
,, longissima, 156.

,, species yielding parellic acid, 43.
,, ,, ,, i3-usnic acid, 156.

Usnetic = stereocaulic = lobaric acid, 153.
/8-Usnic = cladonic acid, 156.
Uvitic acid for benzene, 31.
,, ,, for phenol, 123.
,, ,, for toluene and benzyl alcohol,

108-114.
,, ,, for m-toluic acid and m-cresol, 129.
,t ,t ,, ,, and o-cresol, 126,

„ „ ,, „ and p-cresol, 13a.

,, J, from pyroracemic acid, 112-114.

Vaccinium vitis-idcea, 146.
Valerian, Japanese, 36.
„ oil, 273, 274.
Valeriana officinalis var. angusiifolia, 36, 90, 183,

273, 274.
n-Valeric acid for n-amyl alcohol, 76.

,, and formic acids for n-valeric alde-
hyde, 183.
Valeric aldehyde, 183, 288.
n-Valeric aldehyde for namyl alcohol, 76.
Valeric ethyl ester, occurrence, 45,
Valeryl ethyl ether, 184.
Valerylene, 78.
Vanilla aromatica, 219.
„ ensi/olia, 219.
,, guyanensis, 219.
,, planifolia, and vars., 219.
,, pompona, 219.
,, saliva, 219.
,, sylvestris, 219.
Vanillic acid, 141.

,, and formic acids for vanillin, 221.
Vanillin, 140, 219.

,, and benzene for alizarin, 239.

,, &c., for isoeugenol, 157.

,, for catechol, 141.

,, phloroglucinol, acetic acid, &c., for

quercetin, 276.
,, resorcinol, acetic acid, &c., for fisetin,

275-
Vanilloylcarbonic ( = p-hydroxy-m-methoxy-

benzoylcarbonic) acid, 222.
Vanillylsulphuric acid, salts of, 222.
Veratric acid, 140, 141.

„ ,, &c., for vanillin, 221.

INDEX

837

Veratric acid for catechol, 141.
,, aldehyde, 275. 276.
,, and acetic acids, phloroglucinol, &c.,
for luteolin, 234.
Veratrole, 141, 158, 221.

„ and phthalic anhydride for hysta-
zarin, 240.
Veratroylcarbonic acid, 222.
Veratroylglyoxylic ester, 221.
Verbena oil, 278, 288.
Verbena triphylla, 38, 87, 278, 288.
Vetiver oil, 40, 204, 224.
Vibrios, acetone producers, 193.
,, alcohol producers, 52.
,, aldehyde producers, 174.
Vicia, hydrogen cyanide from, 263.
Vine leaves, 138.
Vinyl chloride, 58, 108, 187, 199.
„ bromide, 33, 175.
,, ethyl ether, 225.
,, sulphide, 253.
Vinylacetic acid, 63, 174, 180, 186, 280.
fl-Vinylacrylic acid, 102.
Vinylcatechol, see dihydroxystyrene, 142.
Vinylglycollic (= i :3-butenolic) nitrile and

acid, 186.
Viola odorata, 276.

,, tricolor, 41, 138.
Violaquercitrin, 138, 160.
Virginian creeper, 138.
Vitex littoralis, 161.

,, trifolia, 92.
Vitexin, 161.

Volvaria speciosa, trehalose, hydrolysei-, 245.
Vulpic acid, 43, 45.

,, ,, for benzoic aldehyde, 210.

Wallflower, 138.

Wartaraoil, 37, 42, 89.

Water-cress, 260.

Water-dropwort, 104.

Water-hemlock, 28, 212.

Waxes, 96.

Weld, 160, 234.

Wendlandia, sp. yielding methyl salicylate, 41.

Whale oil, 85.

White cinnamon oil, 92.

White clover, 276.

White mustard seed, 159, 261.

Winter cabbage, 256.

Winter cress, 260.

Wintergreen oil, 40.

Witch-hazel, 169,

Woody tissues, mannans in, 249, 250.

Wormseed oil, 91.

Xanthorhamnin, 139, 160.
XanthorrhoBa hastilis, resin, 33, 215, 219.
Xanthoxylon acanthopodium, 37, 42, 89.
,, alafum, 37, 42, 89.

,, clava, 140.

,, piperitum, 191.

m-Xylene for m-cresol, 128, 129.
,, for p-cresol, 131.

,, for hydroxytoluic acid and o-cresol,

125, 126.
,, for isophthalic acid and phenol, 123.

o- Xylene for m-cresol, 128.

,, for naphthalene synthesis, 166.
p-Xylene for m-cresol, 129, 285.
,, for )3-orcinol, 156, 286.
,, from camphor, 285, 286.
Xylenes for quinol, 150.

m-Xylene-2-sulphonic acid, 126.

m-Xylene-4-sulphonic acid, 125, 131.

p-Xylenesulphonic acid, 129.

I :3 :4-Xylenol, 131, 132.

1:4: 2-Xylenol, 129.

Xylic acid = i : 3-dimethyl-4-benzoic acid,

126.
a-Xylidic acid = methyl terephthalic acid, 30,

123.
I : 3 : 4-Xylidine, 131.
p-Xylidine, 129.

Xylidines for pseudocumidine, 149.
p-Xyloquinol, 149.
p-Xyloquinone, 149.
Xylose, bacterial fermentation of, 52.
1-Xylose and xylonic acid, 243.
,, non-fermentable, 46.
o-Xylylene dibromide, 166,

Yeast fat, 97.

,, Isevulose from, 247.

,, velocity of fermentation of dextrose by,
279.
Yeasts, acclimatisation of, 50, 279.
,, maltose ferments, 244.
,, melibiose ferments, 245.
,, raffinose (melitriose) hydrolysers, 247.
,, selective fermentation by, 47, 278.
,, species and forms recognised as alco-
holic ferments, 45.
,, trehalose ferments, 245.
Ylang-ylang oil, 41, 42, 87, 88, 108, 131, 157,
284, 287.

Zinc ethyl and acetaldehyde for sec. butyl alco-
hol, 204, 254.

,, ,, and acetaldehyde for methylethyl
ketone, 95, 255.

,, ,, and bromoforuT for propylene, 98.

,, ,, and butyrone, &c., for nonyl alco-
hol, 85.

,, ,, and carbon tetrachloride for pro-
pylene, 98.

,, ,, and chloroform for n-sec. amyl
alcohol, 77.

,, ,, and dichloracetal for propylene, 98.

,, ,, anddichloretherfor2-ethyl-i-chlor-
butyl ether, 255.

,, ,, and iodethyl alcohol for sec. butyl
alcohol, 255.

,, ,, and isobutyryl chloride for ethyl-
isopropyl ketone, 197.

,, ,, and isovaleryl chloride for ethyl-
isobutyl ketone, 197.

,, ,, and nitropropane for diethyl ketone,
78.

,, ,, andoenanthol for nonyl alcohol, 85.

,, ,, and oxalic ester for s-methylethyl-
ethylene, 188.

,, ,, and oxymethylene for n-pi-opyl
alcohol, 60.

,, ,, an,d propionyl chloride for n-sec,
amyl alcohol, 78,

,, „ for n-octane, 82.

,, methyl and acetyl chloride for acetone,

193-
„ ,, and acetyl chloride for tertiary

butyl alcohol, 74.
„ ,, and benzoyl chloride for aceto-

phenone, 209, 214, 228.
,, „ and a-brom-n-butyryl bromide

for tertiary heptyl alcohol,

197.

INDEX

Zinc methyl and a-brompropionyl bromide for
dimethylisopropylcarbinol, 196,
198.

„ ff and butyryl chloride for n-sec.
amyl alcohol, 77.

,, ,, and chloral for dimethylisopropyl
carbinol, 75.

,, ,, and dimethyl oxalate for a-hy-
droxyisobutyric acid, 198.

,, ,, and heptoyl chloride for methyl-
hexyl ketone, 83.

f,. „ and isobutyryl chloride for di-
methylisopropyl carbinol, 197.

Zinc methyl and isobutyryl chloride for me-

thylisopropyl ketone, 196.
,, ,, and propionyl chloride for me-

thylethyl ketone, 95, 255.
,, ,, and propionyl chloride for tertiary

amyl alcohol, 172, 176, 196, 202.
,, ,, for methane, 22.
„ propyl, 71, 79.
,, ,, and butyryl chloride for dipropyl

ketone, 85.
,, ,, and isovaleryl chloride for pro-

pylisobutyl ketone, 197.
Zymase, 48, 279.

or THI '^

UNIVERSITY

Oxford : Horace Hart, Printer to the University

ERRATA ET CORRIGENDA.

Page 23, right column, line 23 from top, for ' Tischtsclienko ' read ' Tistschenko.'
The same error occurs on p. ^^, right column, line 9 from top ; on p. 60,
left column, line 12 from bottom; and on p. 71, left column, line 21
from top.
30, right column, line 4 from top,ybr 'a-xylic' read ' a-xylidic'
^6, right column, line 6 from top,/br 'Jericia* read ' sericea.'
37, left column, line 7 from top,ybr 'XantJioxyhim' read 'Xanthoxylon^ Also

on p. 42, left column, line 22 from bottom.
62, right column, line 30 from top,_/<?r ' nitro-propane ' read ' nitropropane. '
89, for revision of the formula of ^citronellol ' see Appendix, p. 282.
93, for revision of the formula of 'isopulegol' see Appendix, p. 283.
97, left column, line 21 from bottom, /or ' Eurotiopis' read ' Eurotiopsis.'
139, left column, line 24 from bottom, /or ' Querbracho' read ' Quebracko.'
148, right column, line 14 from to-p, for 'B ' read ' C-'
164, for the formula of ^iretol ' as given : —

OCH, OCH,

HO

:0

H.

read

HO

H,

H,

O O

164, right column, line 7 from bottom,_/or ' arfolium* read * arifolmm*
174, left column, line 14 from bottom, /br ' circellino'ides ' read ' circinellotdes,*
190, left column, line i from top, for ' 8-5' read ' ^-y.'
205, right column, line 1 2 from top, for ' Attmgia ' read ' AUingia.'
226, for revision of the formula of 'carvone' see Appendix, p. 290.
„ right column, line 17 from bottom, for ' origanifolium' read 'origani-
folius.'
228, left column, line 15 from top, for ' o-nitro-p-toluidine ' read ^3-nitro-
p-toluidine.'

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PSYCHOLOGY FOR TEACHERS. By C. Lloyd Morgan, LL.D.,

F.R.S. xii-l-251 pages. Crown 8vo., 3s. 6d.

ANIMAL SKETCHES. By C. Lloyd Morgan, LL.D., F.R.S.

viii + 312 pages, with 52 Illustrations (many of them full-page). Crown Svo.,
cloth, 3s. 6d.

LONDON: EDWARD ARNOLD, 41 db' AZ MADDOX STREET, IV.

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