396 IV. WAXES, HIGHER ALCOHOLS, ETC, 



Whereas natural selachyl alcoliol has a specific rotation of —4.5° 

 ([ajp'') according to Toyama and Ishikawa/^- the synthetic d-isomer was 

 found to have a value of —4.35 at 55 °C. The natural and synthetic d- 

 acetates also showed a good agreement ([afj' = -8.6°,"*^- and [af^ = 

 - 8.6 °,^8« respectively). 



The failure of Toyama-'"*^ in his original work to observe an optical rota- 

 tion for batyl alcohol is partly to be ascribed to the varying effect of con- 

 centration on this property. It was found'' ^^ that the negative rotation ob- 

 served at a high concentration gradually diminishes on dilution of the 

 alcohol or chloroform solution until no rotation is observable at a 10% 

 concentration. When the concentration is further decreased, a dextro- 

 rotation actually obtains. The d- and Z-selachyl alcohols were found to 

 melt at 48.5 to 49.5 °C. This could not be compared with the natural 

 product, since it has been prepared only in the form of an oil. 



Although Tsujimoto and Toyama"*^^ demonstrated that there were two 

 hydroxyl groups in the free alcohols which could be acetylated, these are 

 actually esterified with long-chain fatty acids in the liver fat.*^*'"* Hil- 

 ditch-** pictured a possible di-acyl ester of ratfish liver oil as follows: 



HjCOCH2(CH2),CH:CH (CHjl^CH, 

 HC0C(CH2)7CH:CH(CH2)7CH3 

 H2C0^'^C(CH2)7CH:CH(CH2)sCH3 



Oleyl, gadole.\l ester of 

 selach,\l alcohol 



The role which the glyceryl ethers play is not fully understood. They do 

 not possess any growth-promoting action, nor do they have an antirachitic 

 action.'*"^ They seem to represent an intennediate between the tme 

 glycerides and the waxes. Lovern*^^ has shown, also, that the appearance 

 of glyceryl ethers is always accompanied by a subnormal degree of unsatura- 

 tion in the fatty acids of the oil. Such a tendency toward saturation is 

 exhibited not only by a reduction of the ester carbonyl group but also by 

 the lowering of the mean unsaturation of the fatty acids as detennined by 

 the iodine number. 



4. Colored Fats 



The so-called "colored fats" are sometimes know^n also as the colored 

 waxes (Farbwachse) or the lipochrome esters. ^'^ According to Zech- 



"2 Y. Toyama and I. Ishikawa, J. Chem. Soc. Japan, 59, 1367- L374 (1938). 



<i3 E. Andre and A. Bloch, Compt. rend., 195, 627-629 (1932). 



"4 E. Andr6 and A. Bloch, Bull. soc. chim. [5] ,2, 789-802 (1935); Compl. rend., 196, 

 618-620 (1933). 



"5 J. A. Lovern, Biochem. J., 31, 755-763 (1937). 



^'^^ L. Zechmeister, in H. Schonfeld, Chemie und Technologic der Fetle vnd Feitprodukte, 

 Vol. I, Springer, Vienna, 1936, pp. 149-193. 



