132 



Report of Schimmel § Co. 1922. 



of the bisnitroso group. Since, however, the nitrosite, on treatment with caustic 

 potash, gives rise to a body C20H31N3O4 (m. p. 163 to 164°), and since it. interacts 

 with amines, with formation of nitrolamines — C(:NOH) — C(NHR)= and splitting-off 

 of N0 2 H, Wallach 1 ) at a time was of opinion that terpinene nitrosite is bimolecular, 

 at least in the solid state, and that the grouping N0 2 was attached to the carbon 

 atom by the usual- nitrite-linking C— ONO, as in the genuine nitrosites. This view is 

 not shared by H. Wieland and F. Reindel 2 ). The behaviour of dicz/dopentadiene and 



— C C — of ethylene shows that on addition of nitrogen trioxide N 2 3 to un- 



1 



<N 2 2 ) 



i fc- 



NO, saturated bodies pseudonitvosites (&isnitroso-nitro compounds) are formed, 

 N °2 of the structure as given by the annexed formula. Equally terpinene = 

 — zl 1 ' 3 -dihydrocymene containing a grouping of two conjugated double- 

 bonds, is no exception to this rule. By catalytic hydrogenation of terpinene nitrosite 

 (m. p. 153 to 154°), Wieland and Reindel obtained, besides a monovalent base, a 

 diamine which was found to be 1,2-diaminohexahydrocymene and which was identified 

 by its dibenzoyl compound (I, m. p. 165°) and the hydrochloride of the monobenzoylated 

 diamine (m. p. about 290°, turning brown). Hence, terpinene nitrosite undergoes a 

 partial reduction to 1,2-diaminohexahydrocymene, and both the NO- as well as the 

 N0 2 -group are linked to the carbon atom by their nitrogen. By this reaction the 

 structured formula (II) is established beyond doubt, where the authors have replaced 



:C NH 



the : C : NOH-group by the group \ / in order to indicate the insolubility in alkali. 



The interaction with alcoholic potash studied by Wallach 3 ) and yielding the nitrite 

 must be considered to be an intramolecular alkylation, and formula (III) must be 

 attributed to the reaction product. The body CioHi50 6 N 3 obtained by Amenomija 4 ) 

 by action of nitric acid on terpinene nitrosite is, in the opinion of the authors, 

 1 , 2, 2-trinitrotetrahydrocymene. 



CH S CH 3 CH 3 



C-NHCOQH5 C-N0 2 C— N0 2 CH 3 



CH 2 

 CH 2 



CH— NHCOC 6 H 5 CH 2 

 CH 2 CH 2 



NH CH< 



CH 



CH 2 



N- 



O 



/ 



CH. 



CH 

 CH(CH 8 ) 2 



(I) Dibenzoyl-1,2-diaminohexa- 

 hydrocymene. 



CH. 

 CH(CH S ) 2 



(II) Terpinene nitrosite. 



CH 

 C CH< 



CH(CH 3 ) 2 



C NH 



CH 



c 



1 



(Hi) CH(CH 3 ) 2 



Reaction product from terpinene nitrosite. 



On moslene, see p. 51 of this Report. 



Verbenene. — In a prior publication, Blumann and Zeitschel 5 ) had proved that 

 verbenol (I) splits off water readily on treatment with acid reagents and yields a doubly- 

 unsaturated bicyclic terpene CioHu, verbenene. The authors prove now 6 ) that verbenene, 

 which is isomeric with ^-cymene and which can be transformed into that terpene, 

 possesses the structure of a dehydro-«-pinene (II). By oxidation by means of alkaline 

 permanganate solution, verbenene was degradated to cis-norpinic acid (III) by which 

 the intactness of the tetracyclic system was proved. The conjugated position of tne 



x ) Liehig's Anrtalen 356 (1907), 223. See also Beport April 1907, 142. — 2 ) Liehig's Annalen 424 (1921), 

 92. — 3 ) loc. clt. — *) Berl. Beriehte 38 (1905), 2020. — 5 ) Cf. Report October 1913, 105. — 6 ) Berliner 

 Berichte 54 (1921), 887. 



