GLYCEUYL ETHERS 393 



The glyceryl ethers were discovered by Tsujimoto and Toyama'^^ to be 

 components of the non-saponifiable extract of liver oils of the elasmobranch 

 fishes, such as the shark and the ray. Their presence in these oils was 

 later confirmed by Nakamiya.^" Whereas the total non-saponifiable frac- 

 tion is low in the liver fats of the skate {Rata maculata) and of several other 

 fishes (2% and under, consisting mostly of cholesterol), Hilditch'^^ points 

 out the high content of this fraction (10%) in the liver oil of the grey dog- 

 fish (Squalus acanthias); in the sharks examined by Tsujimoto, ^'•'** the non- 

 saponifiable portion consisted mainl}^ of selachyl with some chimyl and 

 batyl alcohols. Almost all of the non-saponifiable fraction of raffish liver 

 oil (Chvmaera monstrosa), which amounts to 37% of the total fat,-^'* consists 

 of selachyl alcohol; small amounts of the other glyceryl ethers are also 

 present. In the case of the shark, where the unsaponifiable matter totals 

 anywhere from 50 to 80%, considerable amounts of selachyl, batyl, and 

 chimyl alcohols are found, but the major component is squalene. How- 

 ever, the occurrence of the glyceryl ethers is not limited to the elasmo- 

 branch family, as they have been reported in the Japanese crab {Para- 

 lithoides camtschatica Tilesius) .^^ 



The importance of batyl alcohol is further emphasized by recent dis- 

 coveries of its wide distribution in nature. Kind and Bergmann^^^ have 

 reported its presence in the unsaponifiable matter of Plexaura flexuosa, 

 which is a reef-building gorgonia (coral). The compound referred to as 

 "astrol," which was isolated from star fish by Kossel and Edlbacher,^^" has 

 been shown to be batyl alcohol. *'' Several recent reports have indicated 

 the presence of batyl alcohol in higher animals. This glycerol ether has 

 been isolated from the bone marrow of cattle,*' the spleen of pigs,*'*'- and 

 from arteriosclerotic arteries of human beings.*'*^ 



The structure of the component alcohol groups was clarified by the 

 demonstration of Toyama in 1924 that the correct empirical formula for 

 batyl alcohol is C21H44O3; that for chimyl alcohol was shown shortly 

 thereafter to be Ci9H4nO.'i. Since Tsujimoto and Toyama had demon- 

 strated that selachyl can be converted to batyl alcohol on hydrogenation, 



396 ;\j Tsujimoto and Y. Tovaiua, Cheni. Utnschau, Felle, Ole, Wachse Harze, 29, 27-29, 

 35-37, 43-45 (1922). Y. Tovama, ibid., 29, 237-240, 245-247 (1922); 31, 13-17, 61-67, 

 153-155 (1924). 



3" Z. Nakamiva, Bull. hust. Phi/s. Chem. Research Tokyo, 17, No. 11, 837-852 (1938); 

 Chem. AbsL, 33, 8175-8176 (1939). 



39S M. Tsujimoto, Chem. ['mschaii, Felle, Ole, Wachse Hane, 39, 50-52 (1931). Cited 

 Ijv T. P. Hilditch, The Chemical Consliluliou of the Xalnral Fals, 2nd ed., Wiley, New 

 York, 1947; J. Soc. Chem. IncL, 51, 317-323T"(1932). 



'»^ C. A. Kind and W. Borgmann, J. Org. Chem., 7, 424-427 (1942). 



^ W. Bergmann and H. A. Stansbury, ./. Org. Chem., 8, 283-284 (1943). 



*"! H, N. Holmes, R. E. Coitx't, W. B. Geiger, N. Kornblum, and W. Alexander, 

 J. Am. Chem. Soc, 63, 2607-2609 (1941). 



402 V. Prelog, L. Kuzicka, and P. Stein, Heir. Chim. Ada, 26, 2222-2242 (1943). 



^03 E. Hardegger, L. Kuzicka, and Jl Tagmann, Heir. Chim. Ada, 26, 2205-21 (1943). 



