— 184 — 



but it is highly probable that the alcohol consists of a mixture of several 

 isomerides, and this assumption also agrees with the corresponding ob- 

 servations in the dipentene and terpinene series. 



The glycol which was obtained in the course of the reaction was 

 isolated in the familiar manner. From dilute alcohol it crystallised out 

 in long needles melting at 167 to 168° (168 to 170° when heated rapidly). 



0,1420 g. subst: 0,3884 g. C0 2 , 0,1486 g. H 2 0. 



Found Calc. for Ci 5 H 2 8 2 



C 74,59°/ 75,00°/ 



H 11,62% 11,66%. 



The caryoterpine 1 ) is active and deflects the plane of polarisation in 

 the same direction as does the chloride, which warrants the surmise that 

 it is formed without transposition by direct substitution of the chlorinne 

 by hydroxyl. [«] D + 26°16' j n a 2,95 °/o chloroform-solution. It sublimes 

 very readily, separating out in long, fine needles. It is very stable against 

 permanganate, and when slightly warmed with concentrated formic acid, 

 water is split off, a mixture of alcohol and hydrocarbon being formed. 

 No second modification of the terpine was discovered. 



This caryoterpine represents the first terpine of the sesquiterpene- 

 series, but a 1,2-glycol of the sesquiterpene series had already been ob- 

 tained by Semmler and Hoffmann 2 ) by oxidising cedrene with permanganate 

 (m. p. 160°). 



Since the above paper on caryophyllene went to press, Deussen and 

 Hahn 3 ) have published an article on copaiva balsam oil. The authors 

 have carefully fractionated a sample supplied by us and have endeavoured 

 to identify the various caryophyllenes from their derivatives. They were, 

 however, only able to confirm Wallach's 4 ) observations, according to 

 which the caryophyllene of copaiva balsam oil yields the derivatives of 

 inactive caryophyllene (nitrosochloride and nitrosate). They obtained no 

 active (/?-) caryophyllene nitrosite, but a second sesquiterpene hydrocarbon 

 also appears to be present. 



In connection with this article we desire also to make known our 

 own observations with regard to the behaviour of copaiva balsam oil 

 towards hydrochloric acid. As already mentioned in our communication 



x ) We have given the name of caryoterpine to this glycol so as to bring it into harmony 

 with the denominations introduced by Wallach (terpinene-terpine, sylveterpine) and in order, 

 on the one hand, to express its genesis from caryophyllene dihydrochloride, analogous to that 

 of terpine, terpinene-terpine, and sylveterpine from the corresponding dihydrochlorides, and on 

 the other hand to emphasize the difference between it and the 1, 2-glycols formed by the 

 permanganate-oxidation of ethylene- or methene-compounds. 



2 ) Berl. Berichte 40 (1907), 3521 ; Report April 1908, 28. 



3 ) Chem. Ztg. 34 (1910), 873. 



4 ) Liebigs Annalen 271 (1892), 294. 



