— 149 — 



49.02. This chloride did not split off hydrochloric acid on standing, 

 but when treated with silver nitrate in alcoholic solution it yielded almost 

 the whole of the chlorine; with alcoholic potash, it regenerated, in 

 addition to very little fenchene, the liquid alcohol. After standing 

 for 24 hours with water it formed, however, a solid dextrorotatory 

 alcohol melting between 61,5 and 65 , which was already formed from 

 a part of the chloride on washing the latter for the purpose of freeing it 

 from phosphorus oxychloride. These experiments are intended to prove 

 that on conversion of the alcohol into the hydrochloride, an optical 

 isomerisation takes place; from the liquid isofenchyl alcohol there is 

 formed, through the chloride, the solid isofenchyl alcohol melting at 

 about 6 5 , the same as previously from fenchene by the old method 

 over fenchene hydrochloride. This shows that isofenchyl chloride and 

 fenchene hydrochloride are structurally identical. The mutual relationship 

 of the two alcohols is explained by Kondakow thus, that the liquid 

 alcohol is a racemic one, or represents a mixture ofstereomerides, of which 

 the dextrorotatory is unstable; or, finally, the liquid alcohol contains a 

 tertiary alcohol which is readily converted with phosphorus pentachloride 

 into solid secondary isofenchyl alcohol. The relationship of the solid iso- 

 fenchyl alcohol towards fenchyl alcohol is not yet cleared up. Both yield on 

 oxidation ketones, fenchone and isofenchone, with almost identical physical 

 constants, but with derivatives of different melting points; they also yield 

 on reduction different alcohols; fenchone yields quantitatively isofenchyl 

 alcohol, isofenchone a liquid alcohol of the b. p. 83 to 84 (9 mm. 

 pressure) which has already been described by Bertram and He lie. 

 Kondakow further explains in detail the probable reaction-mechanism 

 during the formation of this alcohol, which Semmler had previously 

 discussed, and he comes to the conclusion that it is probably a case 

 of a tertiary alcohol which corresponds to a new fenchone. 



Terpin. At the commencement of their experiments with regard 

 to terpene syntheses, Kay and Perkin jun. 1 ) had converted p-cyclo- 

 hexanone carboxylic ester, by treatment with methyl magnesium iodide, 

 etc., in the usual manner, into a-terpineol and terpin: — 



/CH,— CH, CH 3 MgI /CH 2 -CH 2 



CO ^CH.COOR _> HO-C-CHg ">CH.COOH 



CH, — CH 2 CH 2 — CH 2 



/CH-CH 2 ^CH- CH 2 



-> BrC.CH 3 ^CH.COOH -> CCH 3 NcH-COOH -> 



\ / \ X 



CH, — CH, CH„ — CH, 



1 ) Journ. chem. Soc. 85 (1904), 658. 



