— 143 — 



published) results than Semmler 1 ). In a subsequent examination 

 the earlier results were confirmed. By the action of equal molecules 

 of nitrosite and sodium methylate or ethylate, alcoholic or aqueous 

 potash, there was formed, with separation of sodium nitrite, a body 

 C 20 H 31 N 3 O 4 , m. p. 163 to 1 64°; benzoyl derivative, m. p. 127 . 

 Semmler, who allowed two mol. potash to act on one mol. nitrite, 

 received, on the other hand, a body C 10 H 15 NO 2 , of the m. p. 85 . 

 Wallach, working under conditions such as Semmler, did not obtain 

 the body melting at 85 , but, in addition to resinous substances, the 

 body melting at 163 to 164 . The observation made by Ameno- 

 miya 2 ), that the reduction of terpinene nitrosite with zinc in acetic 

 solution yields carvenone, confirms Wallach' s assumption that under 

 such conditions carvone derivatives are formed. In repeating these 

 experiments carvenone and tetrahydrocarvylamine were found as reaction- 

 products. Good yields of carvenone were obtained when the body 

 (m. p. 163 ) formed from the nitrosite by means of alcoholic potash, 

 or when terpinene nitrol-piperidide (m. p. 154 ) were reduced in glacial 

 acetic acid solution, first at o°, and then at the temperature of the 

 waterbath. The hydrochloride of terpinene nitrol-piperidide yielded on 

 dry distillation carvacrylamine. On the strength of the now known facts, 

 Wallach assumes that the nitrosite reacts according to the formula 



CH CH 



CH 3S 

 ONO 



/CC 3 H 7 



C-.NOH CH 



whilst the formula accepted by Semmler, 



ONC\ £S -^ H 2 CH 3 



H0.N:HC/ \ / ^CH, 



C:NOH CH 2 2 



has been completely disproved. 



With regard to the constitution of terpinene, Wallach considers 

 that this question, although not yet solved, has yet been brought near 

 its solution. He considers Semmler's terpinene formula 3 ) as well as 

 the formula proposed by v. Baeyer 4 ), as out of the question. The 

 following come under consideration for illustrating the ready formation 

 of the terpinene hydrohalogen compounds: — 



CH 3-<f )>-C 3 H 7 CH 3 -^\-C 3 H 7 C H 2 = /^J^_C 3 H 7 



*) Berl. Berichte 34 (1901), 715; Report October 1901, 62. 



2 ) Berl. Berichte 38 (1905), 2730; Report April 1906, 115. 



3 ) Berl. Berichte 34 (1901), 715; Report October 1901, 62. 



4 ) Berl. Berichte 27 (1894), 453. 



