NATUllAL "WAXES 315 



tained at a slishtly acid pH. Much lower temperatures may be used than 

 those of Bouveault-Blanc. A yield of 90% of 1-octanol from ethyl capryl- 

 ate has been reported, as well as a satisfactory production of chaulmoogiyl 

 alcohol from the parent acid.^^ 



Another practical method, of especially wide application, for preparing 

 primary, secondary, and tertiary alcohols, is the well-known Grignard reac- 

 tion. Primary alcohols are readily synthesized by this method by treating 

 the alkyl magnesium halide with formaldehyde and hydrolyzing the inter- 

 mediate product : 



RMgBr + HCH -H^C^^ "°" 'RCHgOH + MgBrOH 



R 



One obtains an alcohol with one additional carbon besides that contained 

 in the alkyl group. 



In addition to the synthesis of oleyl alcohol by the use of sodium and a 

 reducing alcohol, ^^ a number of these methods may be employed for pre- 

 paring unsaturated alcohols from their parent unsaturated acids. One 

 may use catalytic reduction with copper-cadmium catalysts^- or a mixed 

 catalyst containing the chromites of zinc, copper, and cadmium.*^ 1- 

 Docosenol is the chief product when erucic acid is reduced with zinc chro- 

 mite, although small amounts of 1-docosanol and 1-docosene are obtained.^"* 

 Komori^'^ reported an 80% yield of unsaturated alcohols when rice fatty 

 acids were reduced in the presence of iron chromite at 320 °C. and 120 

 atmospheres. Erucyl, oleyl, and linoleyl alcohols have been produced in 

 high yield from the ethyl esters of the corresponding acids in the presence 

 of a zinc-chromium catalyst. ^^ When soybean oil is hydrogenated at 

 450 °C. using ammonium zinc chromate, or at 550 °C. in the presence of a 

 mixture of chromium trioxide and zinc oxide, highly unsaturated alcohols 

 are also produced.^^ 



(c) Properties of Alcohols. The aliphatic straight-chain alcohols melt 

 and boil at lower temperatures than do the corresponding acids. The 

 lower members up to the C12 alcohol are liquid at ordinary temperature. 



81 M. M. Dewar, U. S. Pub. Health Service, Pub. Health Bull., No. 168, 33-35 (1927). 



«2H. T. Bohnie, Fettchemie G.m.b.H., French Patent No. 819,255 (1937); Brit. 

 Patent No. 479,642 (Feb. 16, 1937). 



" W. A. Lazier, U. S. Patent No. 2,094,127 (Sept. 28, 1937). 



8^ S. Komori, /. Soc. Chem. Ind. Japan, 43, suppl., 122-125 (1940); Chem. AbsL, 34, 

 5411 (1940). 



8s S. Komori, /. Soc. Chem. Ind. Japan, 43, suppl., 428-430 (1940); Chem. AbsL, 35, 

 4345(1941). 



86 S. Komori, /. Soc. Chem. Ind. Japan, 43, suppl., 46-47 (1939); Chem. Abst., 33, 

 7273 (1939). 



8'Y. Sinozaki and S. Sumi. /. Agr. Chem. Soc. Japan, 14, 1113-1116, 1117-1122 

 (1938). Y. Sinozaki, S. Sumi, and S. Adati, ibid., I4, 1123-1128; 1129-1134 (193Hj; 

 Chem. Abst., 33, 8044-8045 (1939). 



