Kazuyoshi Yagishita

The Chemistry of Ilexol. III.: Isomerization of Ilexol and its Derivatives

It has now been shown that: (a) treatment with either perchloric acid or sulfuric acid of ilexol acetate in a mixture of benzene and ethanol, and (b) treatment with platinumcatalyzed hydrogen of ilexol and ilexone, affords an isomeric alcohol designated as isoilexol, which has C30H50O, m.p. 177~178°, +41.66° (acetate, C32H52O2, m.p. 226~227°, +48.92°).Furthermore, it has been shown that: (a) treatment with hydrochloric acid and glacial acetic acid of ilexol acetate affords α-amyrin acetate, and, in addition, an acetate (Acetate A), C32H52O2, m.p. 212~213°, −22.70°, which is hydrolyzed to an alcohol (Alcohol A), C30H50O, m.p. 202~203°, −35.88°; (b) treatment with sulfuric acid and glacial acetic acid of ilexol acetate and (c) treatment with hydrochloric acid and glacial acetic acid of isoilexol acetate, affords only Acetate A respectively.The infrared and ultraviolet spectra of these isomerized compounds have been measured, and the results of which are discussed.

The Chemistry of Ilexol. II.

Ilexol, a new triterpenoid alcohol isolated from the barks of several species of the Genus Ilex, has now been oxidized with chromium trioxide to yield a ketone, designated as ilexone of C30H48O, m.p. 239.5–240.5°, and – 68.74°, which gives oxirne of m. p. 256.5–257.5°, 2,4-dinitrophenylhydrazone of m.p. 260–261°, and positive Zimmermann test.On reduction with sodium and ethanol as well as with lithium aluminum hydride, it has been shown that ilexone is regenerated to yield an alcohol proved to be identical with natural ilexol.On reduction according to the procedure of Huang-Minion, ilexone has been shown to yield an oxygen-free compound, designated as ilexene of C30H50, and m.p. 241–242°.It seems most likely that ilexol might be a triterpenoid alcohol of C30H49OH, an alcoholic hydroxyl group of which is secondary in nature, and moreover attached at C–3 in its molecule.