— 135 — 



camphenilone was found, also isocamphenilanaldehyde and a compound 

 (b. p. 94 to 96° at 14 mm.) of the formula C 9 Hi 6 2 ; the last-named, when 

 treated with phthalic anhydride, yielded an alcohol C 9 Hi 6 0. In addition 

 to the above, small quantities of camphene glycol and a neutral body, 

 m. p. 69°, were observed as oxidation-products. Camphylic acid dissolves 

 with exceptional ease in the usual organic solvents; it yields a chloride 

 (b. p. 110° at 17 mm.) which, when treated with bromine, gives rise to the 

 chloride of bromocamphylic acid. Bromocamphylic acid melts at 210°, 

 and when heated with aqueous soda-solution is converted into hydroxy- 

 camphylic acid, m. p. 245°. The oxidation of camphene was accomplished 

 by heating 1 mol. of the hydrocarbon with 3 mols. hydrogen peroxide 

 (in 30°/o solution) and 4 times its weight of glacial acetic acid in a reflux 

 condenser to about 60°. Several days were required to complete the 

 reaction, its termination being indicated by the fact that no further 

 camphene was deposited in the condenser. 



Several years ago, while oxidising camphene for the purpose of 

 preparing apocamphoric acid, Komppa obtained as a by-product an acid 

 which he has recently investigated more closely 1 ) and found to be identical 

 with ketopinic acid. This acid melts at 233,5 to 234,5° and yields a phenyl- 

 hydrazone melting at 146°. Its combustion is very difficult to accomplish, 

 good results being only obtained with a chromate-of-lead-asbestos tube. 



For the purpose of preparing isocamphane P. Lipp 2 ) has reduced 

 camphene ([a] D22 o — 18,94°) from pinene hydrochloride according to the 

 method of Sabatier and Senderens. In the course of his proceedings he 

 obtained two isomerides, a liquid isocamphane (b. p. 160 to 162°; d^§ 0,8524; 

 Mduo + I 15'; n D20 o 1,45733) as well as a solid modification with m. p. 65 

 to 67°. The last-named compound is obtained in an almost quantitative 

 yield from camphene from isoborneol. The author also prepared solid 

 isocamphane by reducing i-camphane by Fokin's 3 ) method with platinum 

 black and hydrogen. Finally he obtained from Z-camphene ([«] D i 9 o — 80,7°) 

 a solid d-isocamphane: OL220 +8,68°. Oxidation with permanganate of 

 potassium in a solution of acetic acid gave rise to a mixture of stereo- 

 isomer^ camphenilanic and isocamphenilanic acid, which proves that 

 camphene and isocamphane still possess the same carbon skeleton. This 

 fact was further confirmed by oxidising with nitric acid, for in the course 

 of this reaction the same oxidation-products were formed as in the oxidation 

 of camphene. The acid oxidation-products consist principally of carb- 

 oxylapocamphoric acid. The formation of this acid shows that a rear- 



*) Berl. Berichte 44 (1911), 863. 



2 ) Liebigs Annalen 382 (1911), 265. 



*) Zeitschr. f. angew. Chem. 22 (1909), 1496; Zeitschr. f. anal. Chem. 4S (1909), 337. 



