312 IV. WAXES, HIGHER ALCOHOLS, ETC. 



previously found in sperm head oil.^^ Hilditch-^ reported the possible 

 occurrence of linoleyl alcohol in the oil from the sperm whale, while Ueno 

 and Koyama^ found an unsaturated decenol in sperm blubber. An un- 

 saturated Cio alcohol of unkno^\Tl structure has likewise been isolated from 

 the liver oil of the Japanese crab, tarabakani {Paralithoides camtschatica 

 Tilesius).^^ The elementary composition would suggest the formula 

 C10H18O2. 



Only two of the alcohols have been found exclusively in plant sources. 

 Green, Hilditch, and Stainsby'*'' have demonstrated the presence of 11- 

 eicosenol, CH3(CH2)7CH:CH(CH2)9CH20H and 13-docosenol, CHsCCHa),- 

 CH:CH(CH2)iiCH20H, in the seeds of Simmondsia chinensis (calif ornica) , 

 or goat-nut, which is known as jojoba oil. Hexacosenol has also been re- 

 ported in jojoba oil.^ 



Oleyl alcohol can be changed from the cis configuration to the trans form 

 (elaidyl alcohol) by the action of the nitrogen oxides in a manner similar to 

 that in which oleic acid is transformed into elaidic acid. The latter alcohol 

 is solid at room temperature (m.p., 35-35. 5°C.). Although the elaidyl 

 alcohol cannot be resolved from the mixture after its formation from ole}^! 

 alcohol, it has been synthesized by the reduction of ethyl elaidate.''^'''^ 



(b) Methods of Synthesis. The newer methods of synthesis of the higher 

 aliphatic alcohols are simple and readily adaptable to commercial use; 

 hence, the alcohols are no longer a laboratory curiositj^ but a product as 

 readily available as are the fatty acids. 



The first method employed for the synthesis of alcohol was that of 

 Simonini,^" which invoh^es treating the silver salts of the fatty acids with 

 iodine. The alcohol which results has one less carbon than the original 

 acid. The application of this procedure for the preparation of pentadecanol 

 from palmitic acid is illustrated below. ^^ 



CH3(CH2),4C-0Ag4-l2 " 2 Agl 4-CO2+ CH3(CHj),4C-0-CH2(CH2),3CHj 



Silver Peiitadofanxl 



palinitatp palmitatc 



P 



CH3(CH3)„C-0-CH2(CH2),3CH3+H20 CH3{CH2),3CH20H + CHjfCHaUC - OH 



Peutadeeaiiyl Peiita- Palmitic 



palmitate decauol acid 



« Y. Toyama and G. Akiyama, Bull. Chem. Soc. Japan, 10, 579-584 (1935); 11, 

 29-34 (1936). 



« M. Tsujimoto, ,/. Soc. Chem. hid. Japan, 32, 362-364B (1929); Chem. AbsL, 24, 

 4650 (1930). 



« T. G. Green, T. P. Hilditch, and W. J. Stainsby, /. Chem. Soc, 1936, 1750-1755 



^8 Y. Tovama, Chem. Umschau Fetle, Ole, Wachse Harze, 31, 13-17 (1924); Chem. 

 AbsL, 18, 1270 (1924). 



« E. Andre and M. T. Francois, Compt. rend., 185, 279-281, 387-388 (1927). 



50 A. Simonini, Monatsh., 13, 320-325 (1892); I4, 81-92 (1893). 



" L. Panics, Monatsh., 15. 9-16 (1894). 



