— 172 



investigations, and have found that different hydrocarbons are formed 

 according to the particular agents employed for breaking up the substance 

 under examination, and according to the variations in the temperature 

 applied. When heating very carefully with sodium methylate or methyl- 

 alcoholic solution of potash, the authors obtained a sesquiterpene of the 

 following properties: b. p. 121 to 122,5° (12 mm.), d^ 0,8996, « D + 19°> 

 n D 2oo 1,4990, mol. refr. found 66,58, calc. as Ci 5 H 2 4 /2 66,16. Reaction with 

 hydrochloric acid gave rise to the well-known dihydrochloride, m. p. 69 to 

 70°. It is therefore possible to regenerate from the dihydrochloride the 

 dextrorotatory caryophyllene which is a constituent of oil of clove-stems. 



On the other hand, if pyridine or quinoline be used to split off the 

 hydrochloric acid, and the mixture boiled for 45 minutes in a reflux con- 

 denser, the result is an isomerous tricyclic caryophyllene with the follo- 

 wing constants: b. p. 122 to 123° (13 mm.), d^ 0,927, « D30O — 57°, 

 n D 2oo 1,50246, mol. refr. found 64,98, calc. for Ci 5 H 24 /f 64,45. The sesquiter- 

 pene which was prepared by Schreiner and Kremers, as well as by oursel- 

 ves, therefore consists of a mixture of bi- and tricyclic caryophyllene. 



In order to give a clearer idea of the complicated character of these 

 atomic transpositions, Semmler has prepared the subjoined schemes of the 

 molecular structure of the bodies concerned. They are based upon the 

 experience gained by Semmler in the course of his santalene-research: 



CH 2 C 



/ \H/ 

 H 2 C C 



I 1 c 

 c c 



/ \ !l\ 



H3C CH2 CH2 c 



:h 



\ /CH S 



:h 2 ? x ch 3 



CH 2 



/ 



;h 



Bicyclic regenerated caryophyllene. 



CH 2 ( 



/ \H/ 

 HC C 



II 1 < 



c c 



/\ /l\ 



H 3 C CH 2 CH 3 ( 



:h js^ 



\ /C H 



CH 2 ? X CH., 

 CH 2 



/ 



:h 



A tricyclic caryoph 



yllene. 



CH 2 



CH 



/CHs 



H 2 C 



J!/ I 



C I C Vh 

 CH 2 j CH 8 



HsC 



CC1 C1C 



CH3 CH 3 CH 



Dihydrochloride. 



CH 2 



CH 2 



/ \ , 

 H 2 C C 



CH 



CH 



\ 



CH 2 



CHs 

 CHs 



H3C CH 2 CH3 CH 



The caryophyllene which yields a blue nitrosite. 



Alcohols. 



C. Neuberg and E. Hirschberg 1 ) describe a series of «-naphthyl ure- 

 thanes of terpene alcohols, aromatic alcohols and phenols, of which the 



*) Biochem. Zeitschr. 27 (1910), 339. From a reprint kindly sent to us. 



