Naturally Occurring Glycerol Ethers

The occurrence of at least three a-glycerol ethers, batyl al&hol, chimyl alcohol, and selachyl alcohol, in the unsaponifiable matter of oils from various marine animals, especially fish liver oils, has been well established (2).Recently batyl alcohol has been isolated also from other sources, which makes it appear that glycerol ethers occur much more widely in the animal organism.than-wasoriginally suspected.Kind and Bergmann (3) obtained the alcohol from the unsaponifiable matter of the reef-building gorgonia, Plexaura jkxuosa.Bergmann and Stansbury (4) demonstrated that "astral," isolated by Kossel and Edlbacher as early as 1915 (5) from the starfish, Asterias rubens, is identical with batyl alcohol.The isolation of batyl alcohol from the yellow bone marrow of cattle by Holmes, Corbet, Geiger, Kornblum, and Alexander (6), from the spleen of pigs by Prelog, Ruzicka, and Stein (7), and from arteriosclerotic arteries of human beings by Hardegger, Ruzicka, and Tagmarm (8) proved the occurrence of this type of substance also in higher animals.Both enantiomorphs of batyl alcohol and chimyl alcohol were synthesized in t,his Laboratory several years ago (1) by condensation of the sodium salts of d(/)-acetone glycerol and Z( -)-acetone glycerol with n-octadecyl iodide and -&-hexadecyl iodide and subsequent removal of the protecting acetone group by acid hydrolysis.d-a-(n-Octadecyl) glycerol and d-a-(n-hexadecyl) glycerol prepared from Z( -)-acetone glycerol were found to be identical with natural batyl alcohol and chimyl alcohol respectively, thus proving for both natural products the d configuration.On catalytic reduction of selachyl alcohol d-batyl alcohol was obtained (9).Selachyl alcohol, therefore, also belongs to the d series.The steric relationship of these ethers was assigned according to the principle used for the classification of cr-monoglycerides (10) and glycerophosphates.Although the constitution and the configuration of the natural selachyl alcohol were proved beyond doubt, we felt that its synthesis was desirable, since, in analogy to the wide-spread and plentiful occurrence of oleic acid in nature, it seems to occur much more widely than any of the other glycerol * First communication, "Configuration of the natural, batyl, chimyl, and selachyl alcohols,"(1).