Patent GB-421681-A (GB)
Title: Process for the manufacture of germinal gland hormone derivatives
IPC: C07J75/00
Filed: 1933-10-26
Abstract: Reduction products of the follicle hormone (C18H22O2) of the formula <FORM:0421681/IV/1> or monoacyl-derivatives thereof are transformed into derivatives of the formula C18H28O2 by partial oxidation whereby one secondary alcohol group, probably that in ring 4, is converted into a keto group, or by oxidation to the diketone with subsequent partial reduction to the monoketone, subsequent or simultaneous saponification being necessary when working with the acyl derivatives; alternatively a reduction product of a follicle hormone hydrate of the formula <FORM:0421681/IV/2> may be subjected to a dehydration between the two OH-groups in ring 4.  The derivatives obtained have properties similar to those of male germinal gland hormones.  According to examples: (1) hexahydrohormone hydrate, (C18H30O3) is dehydrated by treatment with sulphuric or other acid, alkalies, or acid or basic salts and the product taken up in ether and the ether evaporated, and is recrystallized by dilution of an alcoholic solution; (2) the same starting material is fused with phthalic anhydride or other anhydride or acid halogenide and the reaction mass extracted with ether, the solution shaken with sodium carbonate solution and the part contained in the soda solution saponified and extracted with ether; (3) the same substance is dissolved in concentrated sulphuric acid and the reaction mixture poured on ice and the crude product recrystallized as in (1); (4) the reduction product of formula C18H30O2 is oxidized with chromic and sulphuric acids to obtain a diketone which is dissolved in alcohol or glacial acetic acid, treated with hydrogen in presence of platinum oxide, filtered, and water added to precipitate the desired product; in place of catalytically activated hydrogen, nascent hydrogen may be used; (5) the compound C18H28O2 is oxidized in aqueous suspension with a measured quantity of permanganate or other mild oxidizing agent to yield two isomeric products of the formula C18H28O2; (6) a monobenzoate of the formula C18H29O. (OCOC6H5) is oxidized with Beckmann's oxidation mixture, the mixture is diluted with water, and the precipitate extracted with ether and saponified; other monoacyl derivatives may be similarly treated. p ALSO:Reduction products of the folliele hormone (C18H22O2) of the formula <FORM:0421681/VI/1> or monoacyl-derivatives thereof are transformed into derivatives of the formula C18H28O2 by partial oxidation whereby one secondary alcohol group, probably that in ring 4, is converted into a keto group, or by oxidation to the diketone with subsequent partial reduction to the monoketone, subsequent or simultaneous saponification being necessary when working with the acyl derivatives; alternatively a reduction product of a follicle hormone hydrate of the formula <FORM:0421681/VI/2> may be subjected to a dehydration between the two OH-groups in ring 4.  The derivatives obtained have properties similar to those of male germinal gland hormones.  According to examples (1) hexahydrohormone hydrate, (C18H30O3) is dehydrated by treatment with sulphuric or other acid, alkalies, or acid or basic salts and the product taken up in ether and the ether evaporated, and is recrystallized by dilution of an alcoholic solution; (2) the same starting material is fused with phthalic anhydride or other anhydride or acid halogenide and the reaction mass extracted with ether, the solution shaken with sodium carbonate solution and the part contained in the soda solution saponified and extracted with ether; (3) the same substance is dissolved in concentrated sulphuric acid and the reaction mixture poured on ice and the crude product recrystallized as in (1); (4) the reduction product of formula C18H30O2 is oxidized with chromic and sulphuric acids to obtain a diketone which is dissolved in alcohol or glacial acetic acid, treated with hydrogen in presence of platinum oxide, filtered, and water added to precipitate the desired product; in place of catalytically activated hydrogen, nascent hydrogen may be used; (5) the compound C18H30O2 is oxidized in aqueous suspension with a measured quantity of permanganate or other mild oxidizing agent to yield two isomeric products of the formula C18H28O2; (6) a monobenzoate of the formula C18H29O. (OCOC6H5) is oxidized with Beckmann's oxidation mixture, the mixture is diluted with water, and the precipitate extracted with ether and saponified; other monoacyl derivatives may be similarly treated.