

136 Report of Schimmel § Co. 1922. 



be assumed that the compound of the m. p. 70 to71° results as an intermediary product 

 in the preparation of pinolglycol-2-chlorohydrin from pinene dichlorohydrin (m. p. 139°). 



The dichlorohydrin of the m. p. 124 to 126° was optically active ([a]rig — 28,2°) 

 and was apparently 2,8-dichloromenthane-l,6-diol. With dilute aqueous potassium 

 hydroxide it yielded optically active pinolglycol-2-chlorohydfin (m. p. 131°), some 

 i-pinolglycol-2-chlorohydrin (m. p. 104°), and a trace of pinol oxide. The third di- 

 chlorohydrin, m. p. 155°, was present only in a very small quantity and was likewise 

 optically active ([«]h e — 59.5°); it is perhaps a derivative of ^-pinene, a little of which' 

 may possibly have been present in the pinene used. 



The viscous, oily body (see above), when treated with a 10 per cent, potassium 

 hydroxide solution, yielded pinolglycol (m. p. 124°), which was evidently formed from 

 pinol oxide and furthermore from a dichlorohydrin. 



Fractional distillation in vacuo of the oily primary product which remained undissolved 

 in water yielded, besides some unchanged pinene, some tricyclene dichloride, Ci Hi 6 Cl 2 , 

 m. p. 169 to 172°, identified by conversion into camphane, m. p. 154 to 155°. 



In a third paper on pinene 1 ), L. Ruzicka and R. Trebler 2 ) were able to disprove 

 the formula (I) for nitrosopinene, as suggested by Wallach 3 ). It had been Wallach's 

 intention to explain, by aid of his formula for nitrosopinene, various cases of iso- 

 merism which occur in connection with various derivatives of nitrosopinene. The 

 nitrosopinene obtained from the nitrosochloride is different from the nitrosopinene 

 prepared from the former rid pinylamine, pinocarveol, pinocarvone. Likewise, the 

 amine formed on reduction of the oxime is not identical with pinylamine. In order 

 to explain these differences in the oximes and amines, Wallach had suggested that 

 when nitrous acid acts on pinylamine a migration of the endocyclic double linking 

 into the semicyclic position takes place. Ruzicka and Trebler proved now that on 

 ozonisation nitrosopinene yields an ozonide which on splitting up is transformed into 

 formaldehyde (or formic acid) and iwnitrosonopinone (II, semicarbazone, m. p. 220°). 

 From the ozonide of acetylpinylamine there results, by the same treatment, the acetyl 

 derivative of «-aminonopinone, m. p. 120 to 121°. It follows from these reactions that 

 in nitrosopinene (III) and pinylamine the double bond is in semicyclic position and 

 that both bodies are derivatives of /^-pinene. This new formula for nitrosopinene is 

 in accord with Bredt's rule according to which camphor derivatives, on stereochemical 

 grounds, are non-capable of existance, whenever a double bond proceeds from a carbon 

 atom which is in common with two rings. 



Since pinene nitrosochloride is optically inactive, the two oximes, in the opinion 

 of the authors, must be geometrical isomerides. 



CH S CH 2 



C CO C 



C C:NOH CH C:NOH CH ; C : NOH 



C(CH 3 ), C(CH 3 ) 2 i C(CH 3 ) 2 j 



CH 2 CH 2 CH 2 CH 2 _JCH 2 



CH CH CH 



(I) Nitrosopinene (II) Jsonitrosonopinone. (Ill) Nitrosopinene. 



(Old, incorrect formula). 



As to the preparation of pinene nitrosochloride, see p. 137 of this Report. 



l ) Cf. Bericht (Germ, ed.) 1921, 106. — 2 ) Helvet. chim, acta, 4 (.1921), 566. — *) Liehig's Annalen 389 (1912), 185. 



