104 Report of Schimmel § Co. 1921. 



Alcohols. 



In his first communication on the determination of alcohols in the form of allo- 

 phanates A. Behal 1 ) had pointed out that Hnalool occupies a singular position among 

 the terpene alcohols, and that it does not give a crystalline allophanate with cyanic acid 

 as other alcohols do. In order to explain this peculiarity of Hnalool, A. Behal now 2 ) sup- 

 poses that the compound is not an alcohol, but an oxide of the following constitution: — 



CH 3 \ / CH 3 



®>C = CHCH 2 CH 2 C^CH 2 -^CH 2 . 

 CH/ X Cr 



This hypothesis was supported by the observation that, heated with water up to 

 210°, Hnalool changes into geraniol. The other properties of Hnalool so far known 

 would not be contradictory to Behal's view. An attempt to condense Hnalool with 

 dimethylamine in the cold was not successful. 



The author could further prepare from pure nerol (b. p. 115 to 117° [17 mm.]; 

 d 15 o 0.8832; « D ±0°; n D15D 1.47593) the allophanate (m. p. 101.5°) which on saponi- 

 fication again gave a nerol with the following constants: — b. p. 115 to 117° [17 mm.]; 

 diso 0.881; « D ±0°; n D150 1.47539. 



Condensations of n-butyl alcohol and n-butyl aldehyde have been effected by Ch. Weiz- 

 mann and St. F. Garrard 3 ). The butyl alcohol, which is also formed in the fermentation 

 of glycerin and of mannose caused by moulds, was obtained by the authors as a by- 

 product in the preparation of acetone by fermentation of starch or other carbohydrates 

 with the aid of Bacillus amylobacter. By this process, from 8 to 9 per cent, of the starch 

 are converted into acetone, 16 to 17 per cent, into n-butyl alcohol, and a small quantity 

 into isopropyl alcohol; 25 per cent, of the starch were lost in equal proportions of 

 hydrogen and carbon dioxide. The n-butyl aldehyde was prepared, partly by direct 

 oxidation of the butyl alcohol with sodium dichromate and sulphuric acid (yield only 

 30 per cent, of the theoretical), partly by the catalytic process of Bouveault 4 ) with the aid 

 of finely-distributed copper heated to 300°, from butyl alcohol (yield almost theoretical). 



n-Butyl aldehyde, which easily undergoes the "aldol" condensation, gave the respec- 

 tive aldol with a yield of 60 to 70 percent, the latter losing during distillation at ordinary 

 pressure water and forming the «-ethyl-a./?-hexene-aldehyde CH 3 CH 2 CH 2 CH:C'(C 2 H 5 )CHO 

 (b.p. 172 to 173°, semicarbazone, m. p. 132°). 



By reduction with aluminium amalgam the unsaturated aldehyde yielded «-ethyl- 

 hexyl alcohol CH 3 CH 2 CH 2 CH 2 CH(C 2 H 5 )CH 2 OH (b.p. 180 to 185°). Oxidation of the 

 aldehyde with silver oxide and barium hydroxide gave the unsaturated a-ethyl-a ; /?-hexenic 

 acid CH 3 CH 2 CH 2 CH : C(C 2 H 5 )COOH which, by reduction with zinc and sulphuric acid, 

 was transformed into «-ethylhexoic acid CH 3 CH 2 CH 2 CH 2 CH(C 2 H5)COOH (b. p. 224°; 

 amide m. p. 101.5°). 



The action of metallic sodium, in different quantities and at different temperatures, 

 on n-butyl alcohol yielded octyl alcohol, n-butyric acid, some octoic acid and traces 

 of esters, ethers and dodecyl alcohol. The quantities obtained of octyl alcohol and of 

 n-butyric acid were proportional, within narrow limits, to the amount of sodium present. 

 The temperature influenced merely the reaction velocity. The reaction proceeds in 

 the following two stages: — 



(1) CJVOH + QrVONa = C 8 H 17 OH + NaOH 



(2) C 4 H 9 -OH + NaOH = C 4 H 7 2 Na + 4H. 



!) Cf. Report 1920, 131. — 2 ) Bull. Soc. chim. IV. 25 (1919), 452. — 3 ) Jonrn. chem. Soc. 117 (1920), 324. 

 — *) Bull. Soc. chim. IV. 3 (1908), 118. 



