— 182 — 





Caryophyllene 



from 



oil of clove stems 



(Schimmel $ C§) 



Sesquiterpene from 



caryophyllene 



dihydrochloride 



(Schimmel 8j C9) 



Sesquiterpene from 



caryophyllene 



dihydrochloride 



(Schreiner u. Kremers) 



Clovene from 



caryophyllene 



alcohol 



(Wallach) 



B.p. 



259 to 261° 



257 to 259° 



— 



261 to 263° 



d 



0,9064 (15°) 



0,9191 (15°) 



0,9191 (20°) 



0,930 (18°) 



a D 



— 7°45' 



— 35° 37' 



— 35,39° 



inactive 



n D 



1,50003 (20°) 



1,49586 (20°) 



1,49801 (20°) 



1,50066(18°) 



Mol. 

 refr. 



66,53 



65,04 



65,06 



64,77 



here be recalled that Semmler 1 ) also only succeeded in distilling the 

 santalene dihydrochloride by applying still more diminished pressure. 



A portion of the hydrochlorides, after being freed from their solid 

 constituents by freezing out, was converted into hydrocarbons by boiling with 

 sodium ethylate. B. p. 259 to 261°; d 15 o 0,9101 ; « D — 9°31' ; n D20O 1,50010. 

 The constants, therefore, again approximate those of caryophyllene, or of 

 its a-compound. We propose to return to these experiments in our next 

 Report, and we entertain the hope that they may lead to valuable revela- 

 tions of the nature of caryophyllene. 



The researches of Deussen and his collaborators 2 ) have disclosed 

 the fact that caryophyllene from oil of clove-stems consists of a mixture 

 of several sesquiterpenes, Deussen having succeeded, by the agency of 

 the additive products of nitric oxide, in specially identifying an inactive 

 ^-caryophyllene and an active /^-caryophyllene. As our investigations have 

 shown the activity of the crystalline hydrochloride which is formed by 

 the action of hydrochloric acid upon caryophyllene, it follows that this hydro- 

 chloride must be a derivative of active /^-caryophyllene. On the other 

 hand, it is probable that the liquid hydrochlorides consist for the greater 

 part of derivatives of inactive ^-caryophyllene. 



By a suitable process of conversion we have succeeded in obtaining 

 further derivatives of the hydrochloride. For the preparation of alcohols 

 and glycols of the dipentene and terpinene series a reaction is known 

 which is based upon the treatment of the hydrochlorides with dilute al- 

 kalies. In order to arrive from the hydrochlorides at the alcohols, the 

 only method which has really been made use of in the chemistry of ter- 

 penes has been the reciprocal reaction of the hydrochloride with acetate 

 of silver, but in this reaction atomic transpositions have frequently been 

 observed. For example, terpinene dihydrochloride 3 ), instead of the terpinene 



!) Berl. Berichte 43 (1910), 444; Report April 1910, 97. 



2 ) Comp. Report April 1908, 182; November 1908, 176; April 1909, 124; April 1910, 169. 



3 ) Liebigs Annalen 350 (1906), 151. 



