Patent GB-427436-A (GB)
Title: The manufacture of acyl derivatives of the dihydrofollicle hormone
IPC: C07J75/00
Filed: 1933-12-22
Abstract: Acyl derivatives of dihydrofollicle hormone (described in Specification 428,132) are obtained (1) by treatment thereof with acylating agents, or (2) by subjecting acyl derivatives of the follicle hormone to the action of reducing agents or to catalytic hydrogenation, or (3) by subjecting the follicle hormone to said reduction process in an acylating medium.  The first process may be carried out in a solvent in which the mono-acyl derivative is insoluble so as to yield the mono-acyl derivative, or the solvent may be chosen so that di-acyl derivatives are obtained.  The second process yields monoacyl derivatives which may be further acylated. The hormones treated may be follicle hormone C18H22O2, equilin C18H20O2, or hippolin C18H18O2, and the dihydrofollicle hormone may be such reduction products of any of these as contain a secondary hydroxyl group in the molecule, but in which the benzene nucleus remains unchanged.  According to examples: (1) the dihydrofollicle hormone in caustic soda solution is treated with benzoyl chloride to yield a precipitate of the monobenzoyl compound, which is then recrystallized from dilute alcohol; (2) the same starting material is dissolved in pyridine and treated with benzoyl chloride to yield the di-benzoyl derivative which is precipitated on dilution with hydrochloric acid; (3) the same starting material dissolved in acetic anhydride together with sodium acetate is boiled under reflux and then poured into water to yield a precipitate which is recrystallized from dilute acetic acid, or the product of example 1 may be similarly treated to yield a benzoyl acetyl dihydrofollicle hormone; (4) benzoyl follicle hormone dissolved in alcohol is hydrogenated at 130 DEG  C. using a nickel-chromium catalyst, to yield the monobenzoyl dihydrofollicle hormone; (5) follicle hormone is dissolved in acetic anhydride together with sodium acetate and the reaction mixture to which zinc dust has been added is maintained at boiling point and then poured into water to yield a resinous precipitate of diacetyl dihydrofollicle hormone which is recrystallized from dilute alcohol.ALSO:Acyl derivatives of dihydrofollicle hormone (described in Specification 428,132) are obtained (1) by treatment thereof with acylating agents, or (2) by subjecting the acyl derivatives of the follicle hormone to the action of reducing agents or to catalytic hydrogenation, or (3) by subjecting the follicle hormone to said reduction process in an acylating medium.  The first process may be carried out in a solvent in which the mono-acyl derivative is insoluble so as to yield the mono-acyl derivative, or the solvent may be chosen so that di-acyl derivatives are obtained.  The second process yields mono-acyl derivatives which may be further acylated. The hormones treated may be follicle hormone C18H22O2, equilin C18H20O2, hippolin C18H18O2, and the dihydrofollicle hormone may be such reduction products of any of these as contain a secondary hydroxyl group in the molecule, but in which the benzene nucleus remains unchanged.  According to examples: (1) the dihydrofollicle hormone in caustic soda solution is treated with benzoyl chloride to yield a precipitate of the monobenzoyl compound, which is then recrystallized from dilute alcohol; (2) the same starting material is dissolved in pyridine and treated with benzoyl chloride to yield the di-benzoyl derivative which is precipitated on dilution with hydrochloric acid; (3) the same starting material dissolved in acetic anhydride together with sodium acetate is boiled under reflux and then poured into water to yield a precipitate which is recrystallized from dilute acetic acid, or the product of example 1 may be similarly treated to yield a benzoyl acetyl dihydrofollicle hormone; (4) benzoyl follicle hormone dissolved in alcohol is hydrogenated at 130 DEG  C. using a nickel-chromium catalyst, to yield the monobenzoyl dihydrofollicle hormone; (5) follicle hormone is dissolved in acetic anhydride together with sodium acetate and the reaction mixture to which zinc dust has been added is maintained at boiling point and then poured into water to yield a resinous precipitate of diacetyl dihydrofollicle hormone which is recrystallized from dilute alcohol.