— 177 — 



Phellandrene. The conversion of phellandrene into dipentene 

 which was observed years ago by Wallach 1 ) has again been noted 

 by Bacon 2 ) when boiling the oily hydrochloride of a -phellandrene 



OAO 



from oils of elemi (b. p. 62 to 63 [9 mm.]; d-^- 0,8364; n D3o° i>4-673; 

 free, from dipentene) with alcoholic potash liquor beneath a reflux- 

 condenser. The terpene which was separated out from the mixture 

 by the familiar method, when brominated in an amylalcoholic - ether- 

 eal solution, gave large quantities of dipentene tetrabromide, m. p. 124 

 (from acetic ester). 



Caryophyllene. Deussen's 3 ) paper on the compounds formed 

 by oxidation of caryophellene with permanganate of potassium has 

 induced C W. Haarmann 4 ) to publish the results of some experi- 

 ments which he made as long ago as 1905. He also obtained 

 from caryophyllene by oxidation with permanganate of potassium a 

 neutral product, m. p. 120 , but, judging from the analysis, this was 

 not a compound C 15 H 22 4 as surmised by Deussen, but a body 

 C 14 H 22 4 . This body was of a glycol- like charakter and possessed 

 the following constants: m. p. 120 , b. p. 210 (10 mm). When left 

 to stand with a methylalcoholic solution of hydroxy lam in e it yielded 

 an oxime C 14 H 23 4 N, m. p. 188,5° (from water), which indicated 

 the probable presence of a keto-group. When treated with 1 °/ sul- 

 phuric acid under heat, the glycol yielded an oily compound C 14 H 22 O s , 

 boiling at 193° (20 mm.) but from this no derivatives were obtained. 

 Oxidised with chromic acid in solution of acetic acid, the glycol pro- 

 duced a solid aldehyde, C 14 H 20 O 4 , which, when recrystallised from 

 acetone, melted at from 156 to 157 and gave a mono-hydrazone, 

 m. p. 1 6 7 , with phenyl hydrazine acetate. Oxidation of the glycol 

 with permanganate of potassium in chloroform solution at ordinary 

 temperature yielded 45% of an acid, m. p. 171 ; but from this no 

 keto-derivative could be prepared. 



The course of the oxidation process therefore renders it probable 

 that caryophyllene contains two methylene -groups, one of which can 

 be oxidised into a methyl-ketone group CH 3 CO; while the other can 

 be oxidised into the normal glycol C(OH) • CH 2 (OH) and subsequently 

 into the aldehyde C(OH) • CHO and the acid C(OH).C0 2 H. 



Alcohols. 



Heptyl Alcohols. As mentioned by us formerly, saturated ali- 

 phatic hydrocarbons and alcohols have been discovered, although not 



x ) Liebig's Annalen 239 (1887), 44. 



2 ) Philippine Journ. of sc. 4 (1909), A, no. 



3 ) Berl. Berichte 42 (1909), 376, 680; Report April 1909, 124. 



4 ) Berl. Berichte 42 (1909), 1062. 



