— 183 — 



compounds which should in theory be looked for, yields «-terpineol and 

 the terpenes of the dipentene series (cis- and transterp'me). Wallach 1 ), 

 however, has worked out a method, which he has often applied with 

 success, based upon the reaction, under heat, of dilute alkali-solutions by 

 hydrochlorides, in which the chlorine is in tertiary linkage. 



When this reaction was applied to caryophyllene dihydrochloride, 

 m. p. 69 to 70°, it was found practicable to replace the potash by quick- 

 lime, and this materially reduced the probability of a rearrangement. The 

 test was applied at a temperature of about 90°, and with about 100 g. 

 hydrochloride from 26 to 30 hours were required to complete the con- 

 version. About 40 to 45% hydrocarbon, 35 to 40°/o alcohol and 5% glycol 

 are formed, the loss being accounted for by the distillation in vacuo. The 

 hydrocarbon obtained in this manner boiled at 121° (8 mm.) and possessed 

 the following properties: 



I. B. p. 257 to 258°, d 15 o 0,9137, d 20 o 0,9117, « D — 35°28', n D20 o 1,49441. 



II. B. p. 258 to 259°, d 20 o 0,9113, a D — 35° 43', n D20O 1,49479. 



The molecular refraction is 65,17 (I.) and 65,24 (II.); calculated for 

 C 15 H 24 /T 64,45. 



This hydrocarbon (as well as the one obtained from the dihydrochloride 

 by the splitting-off of hydrochloric acid with sodium acetate or ethylate), 

 absorbs only two atoms of bromine. No other derivative was obtainable. 

 In all probability both fractions consist of the same hydrocarbon. 



The alcohol (or perhaps mixture?) obtained in the reaction had an 

 odour of cedar wood, and after repeated fractionation was found to possess 

 the following properties: B. p. 134 to 137° (5 mm.), d 20 o 0,9677, « D — 8° 30', 

 "d2oo 1,50299, mol. refr. found 67,82, calculated for Ci 5 H 26 66,32, for 

 C 15 H 26 0/f 68,03. 



0,1234 g. subst.: 0,3659 g. C0 2 , 0,1300 g. H 2 0. 

 Found Calculated for 



Ci 5 H 24 Ci 5 H 26 



C 80,87°/o 81,81 °/o 81,08°/o 



H 11,59% 10,90% 11,71%. 



Even at a considerably reduced temperature the alcohol was not 

 converted into the crystalline form, and it is therefore not identical 

 with Wallach's caryophyllene alcohol (Semmler's isocaryophyllene hydrate). 

 With concentrated formic acid it gives off water very readily, forming 

 a tricyclical sesquiterpene: b. p. 258 to 259°, di 5 o 0,9199, « D — 32°33 f , 

 n D20 o 1,49701. 



The molecular refraction does not show clearly whether the tricyclical 

 system of the hydrocarbon is already present in the alcohol or whether 

 it is formed only in the course of further process of splitting-off water, 



*) Liebigs Annalen 350 (1906), 153. 



