Patent GB-438753-A (GB)
Title: The manufacture of acyl octahydro follicle hormones
IPC: C07J1/00
Filed: 1934-11-09
Abstract: The acyl octahydro follicle hormones of the parent Specification are prepared by (1) mono or di-acylation of the octahydro hydrofollicle hormone C18H30O2; (2) catalytic hydrogenation of mono-acyl follicle hormone and its steroisomerides.  The acylation is preferably carried out in presence of a solvent, e.g. pyridine.  By regulating the conditions either mono- or di-acylation products are produced.  In the processes involving catalytic hydrogenation, the reaction is preferably conducted at elevated temperature and under super-atmospheric pressure.  Catalysts used are noble metals such as platinum black, or heavy metals such as nickel with additions of copper, manganese, chromium, and the like.  Solvents used are glacial acetic acid, ethanol, and cyclohexanol.  The term follicle hormone includes not only the follicle hormone of the formula C18H22O2, but also the unsaturated follicle hormones, equilin C18H20O2 and hippolin C18H18O2.  In examples: (1) octahydro follicle hormone is dissolved in pyridine and treated with an excess of benzoyl chloride to produce dibenzoyl-octahydro-follicle hormone; (2) octahydro follicle hormone is treated in pyridine solution with one molecule of benzoyl chloride to produce mono-benzoyl octahydro-follicle hormone; (3) follicle hormone acetate is treated with hydrogen in the presence of a nickel-chromium catalyst at high temperature and pressure; (4) follicle hormone benzoate is hydrogenated in presence of colloidal platinum to produce a mixture of the isomeric monohexahydrobenzoic esters of octahydro follicle hormone.  A sample has been furnished under Sect. 2 (5) of a mixture of the various octahydro follicle hormone acetates prepared as follows: follicle hormone is catalytically hydrogenated to yield a mixture of the various octahydro-follicle hormones which is then acetylated by heating under reflux with acetic anhydride and sodium acetate.  The product is extracted with ether the etherial solution washed with sodium carbonate, and the ether evaporated to give a resinous product.ALSO:The acyl octahydro follicle hormones of the parent Specification are prepared by (1) mono-or di-acylation of the octahydro hydrofollicle hormone C18H30O2; (2) catalytic hydrogenation of mono-acyl follicle hormone and its stereoisomerides.  The acylation is preferably carried out in presence of a solvent, e.g. pyridine.  By regulating the conditions either mono- or di-acylation products are produced.  In the processes involving catalytic hydrogenation, the reaction is preferably conducted at elevated temperature and under super-atmospheric pressure.  Catalysts used are noble metals such as platinum black, or heavy metals such as nickel with additions of copper, manganese, chromium, and the like. Solvents used are glacial acetic acid, ethanol, and cyclohexanol. The term follicle hormone includes not only the follicle hormone of the formula C18H22O2, but also the unsaturated follicle hormones, equilin C18H20O2 and hippolin C18H18O2.  In examples: (1) octahydro-follicle hormone is dissolved in pyridine and treated with an excess of benzoyl chloride to produce dibenzoyl-octahydro-follicle hormone; (2) octahydro follicle hormone is treated in pyridine solution with one molecule of benzoyl chloride to produce mono-benzoyl octahydro follicle hormone; (3) follicle hormone acetate is treated with hydrogen in the presence of a nickel-chromium catalyst at high temperature and pressure; (4) follicle hormone benzoate is hydrogenated in presence of colloidal platinum to produce a mixture of the isomeric mono-hexahydrobenzoic esters of octahydro follicle hormone.  A sample has been furnished under Sect. 2 (5) of a mixture of the various octahydro follicle hormone acetates prepared as follows: follicle hormone is catalytically hydrogenated to yield a mixture of the various octahydro follicle hormones which is then acetylated by heating under reflux with acetic anhydride and sodium acetate.  The product is extracted with ether, the ethereal solution washed with sodium carbonate, and the ether evaporated to give a resinous product.