86 REPORT OF SCHIMMEL Co. oe 1914/ APRIL 1915. 
It was further tried to synthetize oadincie: «“- and §-phellandrene yielded ses- 
quiterpenes of undoubtedly bicyclic nature when heated with isoprene in a sealed tube. 
The sesquiterpene obtained by CoM Cet is 8-phellandrene with isoprene is presumably 
identical with §-santalene. 
The condensation of limonene with isoprene can be started by means of othe 
sulphuric acid. For this purpose limonene and isoprene in the proportion of 2:1 are 
slowly mixed under stirring with three times. their quantity of ethylsulphuric acid, - 
which has been cooled down to — 18°. The reaction begins suddenly with a con- 
siderable rise of temperature; after about 3 to 5 minutes, the product of the reaction 
is poured into water and furnishes after neutralization and distillation a sesquiterpene 
fraction boiling at from 120 to 127° (10 mm.). e 
Re Wallach’s colour reaction of cadinene see page 25. 
Caryophyllene. By heating an alcoholic solution of §-caryophyllene nitrosite, a 
hydrocarbon is formed which E. Deussen’) calls y-caryophyllene, whereas he formerly 
named it isocaryophyllene’). y-Caryophyllene boils at 124 to 125° (14 mm.); «—22,22°, 
Following Paal’s process, it can be reduced to y-dihydrocaryophyllene (b. p. 124 to 
124,5° at 12°/s mm.; doio 0,8872; ep — 29,419; npao 1,4880). . 
Deussen farther describes some halogen derivatives of @-caryophyllene nitrosite, 
i.e. the already known 6-hydrochlorocaryophyliene nitrosite*) (from blue 6-caryophyllene 
nitrosite and hydrochloric acid), @-bromocaryophyllene nitrosite, melting at 104 to 105° 
(from @-nitrosite and bromine in chloroform) and -iodocaryophyllene nitrosite, from 
iodine and (-nitrosite in chloroform; m.p. 125°. 
In the same treatise, Deussen mentions the action of sodium alcoholates on 
«-caryophyllene nitrosochloride. When «-caryophyllene nitrosochloride is treated with 
sodium methylate, «-methoxynitrosocaryophyllene results, which melts at 116°. Sodium 
ethylate and propylate cause hydrochloric acid to be split off from the nitrosochloride, 
when @-nitrosocaryophyllene is formed. 
Besides, Deussen writes about the action of sulphuric acid on caryophyllene from 
clove oil and on alkoxy compounds of -caryophyllene nitrosite and their optical rotation. 
He prepares said bodies by treating $-caryophyllene nitrosite with alcohols, in which 
caustic potash is dissolved. Ethoxynitrosocaryophyllene (m.p.163°)*) has been described 
by him already some time ago. 
Deussen also mentions a crystalline body which he obtained from the mother 
lye resulting from the preparation of 6-caryophyllene nitrosochloride, and which formed — 
yellow crystals melting at 168 to 169°. Its composition may probably be expressed 
by the formula CisH23NO. 
He finally reports on the melting point of mixtures of e-caryophyllene nitrosobromide 
and «-bromocaryophyllene nitrosochloride, as well as on the nomenclature of optically 
active caryophyllene compounds. 
As to the properties of gurjunenes and their derivatives see page 25. 
The tricyclic sesquiterpene copaene has been described on page 14 of this Report. 
1) Journ. f. prakt. Chem. Il. 90 (1914), 324. — *) K. Meyer, Inaug.-Dissert., Leipzig 1912. — Deussen, 
Copaivabalsame und thre Verfdlschung, Leipzig 1914. — 3) Comp. Report October 1912, 149. — 4) Comp... 
Report October 1912, 149. ; 
