GB556735A - Manufacture of new ketones of ring-d-homo-steroids - Google Patents

Abstract

556,735. Ring-D-homo steroid compounds. SOC. OF CHEMICAL INDUSTRY IN BASLE. March 14, 1941, No. 3510. Convention date, March 14, 1940. [Class 2 (iii)] Ketones of the ring-D-homo steroid series are prepared by treating with an oxidizing agent a saturated or unsaturated secondary alcohol of this series, if desired with temporary protection of any double linkages or other substituents capable of being oxidized which may be present. Substituents mentioned esterified or etherified hydroxyl groups, free tertiary or primary hydroxyl groups, substituted or unsubstituted hydrocarbon groups such as alkyl, alkenyl, alkinyl, alkylene, acyl or ketol groups, also keto groups which may be present in the form of their enol derivatives, free or substituted carboxyl, amino or thiol groups. Parent materials for use in the present invention are prepared by the process described in Specification 556,734. Oxidizing agents mentioned include such chemical, electrochemical or biochemical agents known for the purpose of converting secondary alcohols into ketones. Preferred agents comprise those described in Specifications 461,335 and 517,133. The compounds produced by the present invention have the action of the sexual hormones or of the suprarenal cortical hormones. In examples (1) a glacial acetic acid solution of 3-oxy-17α - benzoxy-D-homo-androstane is treated with chromic acid in glacial acetic acid to obtain 3-keto-17α-benzoxy-D-homo-androstane. There may also be used as starting material a# <SP>5</SP>-3:17α-dioxy-D-homo-androstene 17α-mono ester in which case there is obtained the corresponding #<SP>4</SP>-3-keto-17α oxy-D-homo androstene. In the above cases where chromic acid is used as the oxidizing agent, protection of the nuclear double bond is desirable. If, however there is used as the oxidizing agent a ketone in the presence of a metal alcoholate or phenolate, or heating with a metal such as copper under reduced pressure, or tritylation and thermal elimination of the triarvlmethane residue or a biochemical or electrochemical method, protection of the double linkage is unnecessary. Similarly saturated and unsaturated 3:17α-diketo-D-homo-androstanes can be obtained from saturated and unsaturated 3:17α - dioxy - D - homo - androstanes, 3 - oxy - 17α - keto - D - homo - androstanes or 3 - keto - 17α - oxy- D-homo-androstanes. The dioxy compounds can be oxidized partially to saturated or unsaturated 3-keto-17α-oxy-D homo-androstanes, by the method of exchange of oxidation stages. (2) A solution of # <SP>5</SP>-3:17α- dioxy-17α-methyl-D-homo-androstene in toluene - cyclohexanone mixture is treated with aluminium tertiary butylate to give #<SP>4</SP>-3- keto-17α-oxy-17α- methyl - D- homo - androstene. In an analogous manner compounds saturated or unsaturated in the nucleus and containing in the 17α - position (3) # <SP>5</SP>-3-oxy-17α-acetyl-D-homo-androstene in benzene solution is dehydrated by removal of part of the benzene, when acetone and aluminium isopropylate are added and refluxed to give #<SP>4</SP>-3-keto-17α-acetyl-D-homo-androstane. The same compound can be obtained by using as starting material A <SP>5</SP>-3:20-dioxy-D-homopregnene or A <SP>4</SP>-3-keto-20 oxy-D-homo-pregnene. Using as starting material # <SP>5</SP>-3-oxy-20-keto- 21-acyloxy D-homo-pregnene there is obtained #<SP>4</SP>-3:20-diketo-21-acyloxy-D-homo pregnene.