121 



siderations upon which Bar bier and Grignard proceeded, we had 

 oxidised a pinene of high rotatory power from Greek turpentine oil 

 (b. p. 156 ; d i5 o 0,8642; n D2 o° 1,46565; Wd +4773°) and had like ~ 

 wise obtained d-pinonic acid. The constants ascertained by us for 

 both acids agree with the indications given by Barbier and Grig- 

 nard. For the lsevogyre acid we found: m. p. 69,5 to 70 and 

 [a] D — 90,36° in chloroform solution; for the dextrogyre acid: m. p. 68 

 to 69° and Md -}- 88,2° in the same solvent. We purpose, later on, 

 to publish elsewhere our investigations into these bodies. 



According to P. G o 1 u b e w x ), pinene nitroso-chloride, by treatment with 

 piperidine, can be made to yield, besides the nitrol-piperidide (m. p. 1 18 

 to 1 19°), nitroso- pinene (m. p. 134 to 13 5 ) by the splitting off of 

 hydrogen chloride. As Wallach 2 ) showed long ago, the reaction, when 

 other bases, such as diethylamine, are used, takes place chiefly in the 

 last-named direction. 



[Camphene. While oxidising crude camphene, F. W. Semmler 3 ) 

 obtained practically only a single oily ozonide C 10 H 16 O 3 , which, however, 

 could be split up in two different ways. In one case it yielded 30 /o 

 of camphenilone C 9 H 14 (m. p. 40°; d 38 o 0,9705; semicarbazone, 

 m. p. 223°) of which the oxime (m. p. 109°; b. p. 128 to 129° at 

 14 mm. press.) was converted through the nitrile into camphoceenic 

 acid (b. p. 145 to 146 at 1 1 mm. press.; d2o° 1,020; "d 1,4862). By 

 the other method there was obtained from the ozonide a syrupy sa- 

 turated hydroxy acid C 9 H 16 3 ((5-hydroxycamphenilonic acid) which by 

 means of distillation in vacuo was converted into an also saturated, well- 

 crystallising lactone C 9 H 14 2 (m. p. 95 to 95°; b. p. 126 to 128° at 

 10 mm. press.). In addition to the above method, the process of 

 splitting- off of water could be carried out in another way, resulting in a 

 mixture of a saturated and a non-saturated acid, both of them possess- 

 ing the formula C 9 H 14 2 . Now, the formation of camphenilone from 

 semicyclic camphene can be understood without further explanation, but 

 the formation of the hydroxy acid, that is to say of the lactone, can only 

 have resulted from ring-disrupture. As, moreover, no dialdehyde could 

 be isolated from the products of decomposition of the crude ozonide, 

 Semmler believes that the hydroxy acid, and also the lactone, are 

 not formed from the cycHc-unsaturated isocamphene but also from the 

 semicyclic camphene, which must consequently form the chief con- 

 stituent of the crude camphene. Ozone did not react in any way 



*) Journ. russ. phys.-chem. Ges. 40 (1908), 1015. Quoted from Chem. Zentralbl. 

 1908, II. 1865. 



2 ) Liebig's Annaien 245 (1888) 254. 



3 ) Berl. Berichte 42 (1909), 246. 



