Patent GB-428132-A (GB)
Title: The manufacture of hydrogenation products of follicle hormones
IPC: C07J75/00
Filed: 1933-10-26
Abstract: Reduction products of follicle hormones, wherein the keto group has been reduced to a secondary alcohol group, are obtained by treatment of the hormone with reducing agents under such conditions that the benzene ring is not hydrogenated.  The starting materials may be the hormones of the formul  C18H22O2, C18H20O2, or C18H18O2, the product obtained always having the formula C18H24O2.  Reduction may be by catalytically actuated hydrogen, by chemically produced nascent hydrogen, or by alcoholates.  According to examples: (1) hormone dissolved in alcohol is treated with hydrogen at 20 atmospheres and 120 DEG  C. in presence of a nickel catalyst, isomeric products of M.P. 168--170 DEG  C. and 198--202 DEG  C. are obtained; (2) hormone dissolved in amyl alcohol is treated with sodium, the mixture is diluted with water, acidified, evaporated to remove the alcohol and extracted with ether to yield a solution which is then extracted with caustic soda solution; the alkaline solution so obtained is acidified to precipitate the reduction product; (3) hormone dissolved in wet ethyl acetate is treated with amalgamated aluminium foil; (4) hormone dissolved in glacial acetic acid is treated with zinc dust in presence of a trace of palladium chloride, the product is precipitated by addition of water, dissolved in alcohol and treated with semicarbazide hydrochloride and potassium acetate to remove unchanged hormone; (5) equilin of the formula C18H20O2 dissolved in alcohol is hydrogenated at 100 DEG  C. in presence of nickel catalyst; (6) crude hormone from mares' urine is dissolved in alcohol and hydrogenated at 100--120 DEG  C. in presence of nickel-copper catalyst; (7) crude hormone extracted from placenta is dissolved in amyl alcohol, sodium is added and the reaction stopped by passage of steam which drives off the amyl alcohol; similarly substance of hormone-like action obtained from vegetable materials such as palm kernels may be treated.  Specification 346,130, [Group VI], is referred to.  The Specification as open to inspection under Sect. 91 contains also the subject-matter of Specification 428,133, and contains an additional example according to which hormone dissolved in cyclohexanol is reduced at 40 atmospheres and 140 DEG  C. in presence of nickel catalyst, and refers to a modified process in which the hormone is treated, in presence of a hydrogenation catalyst, with a compound containing hydrogen and capable of giving it off under such conditions.  Examples of such substances are cyclohexanol, tetrahydronaphthalene, isoborneol, piperidine, and hydrogenated hormones which contain a hydrogenated benzene ring. This subject-matter does not appear in the Specification as accepted.ALSO:Reduction products of follicle hormones, wherein the keto group has been reduced to a secondary alcohol group, are obtained by treatment of the hormone with reducing agents under such conditions that the benzene ring is not hydrogenated.  The starting materials may be the hormones of the formul  C18H22O2 C18H20O2, or C18H18O2, the product obtained always having the formula C18H24O2. Reduction may be by catalytically actuated hydrogen, by chemically produced nascent hydrogen, or by alcoholates.  According to examples: (1) hormone dissolved in alcohol is treated with hydrogen at 20 atmospheres and 120 DEG  C. in presence of a nickel catalyst, isomeric products of M.P. 168-170 DEG  C. and 198-202 DEG  C. are obtained; (2) hormone dissolved in amyl alcohol is treated with sodium, the mixture is diluted with water, acidified, evaporated to remove the alcohol and extracted with ether to yield a solution which is then extracted with caustic soda solution; the alkaline solution so obtained is acidified to precipitate the reduction product; (3) hormone dissolved in wet ethyl acetate is treated with amalgamated aluminium foil; (4) hormone dissolved in glacial acetic acid is treated with zinc dust in presence of a trace of palladium chloride, the product is precipitated by addition of water, dissolved in alcohol and treated with semicarbazide hydrochloride and potassium acetate to remove unchanged hormone; (5) equilin of the formula C18H20O2 dissolved in alcohol is hydrogenated at 100 DEG  C. in presence of nickel catalyst: (6) crude hormone from mares' urine is dissolved in alcohol and hydrogenated at 100-120 DEG  C. in presence of nickel-copper catalyst; (7) crude hormone extracted from placenta is dissolved in amyl alcohol, sodium is added and the reaction stopped by passage of steam which drives off the amyl alcohol; similarly substances of hormone-like action obtained from vegetable materials such as palm kernels may be treated.  Specification 346,130 is referred to.  The Specification as open to inspection under Sect. 91 contains also the subject-matter of Specification 428,133, and contains an additional example according to which hormone dissolved in cyclohexanol is reduced at 40 atmospheres and 140 DEG  C. in presence of nickel catalyst, and refers to a modified process in which the hormone is treated, in presence of a hydrogenation catalyst, with a compound containing hydrogen and capable of giving it off under such conditions.  Examples of such substances are cyclohexanol, tetrahydronaphthalene, isoborneol, piperidine, and hydrogenated hormones which contain a hydrogenated benzene ring. This subject-matter does not appear in the Specification as accepted.