GB556736A - Manufacture of carbinol compounds of ring-d-homo-steroids or esters or ethers thereof - Google Patents

Abstract

556,736. Ring-D-homo steroid compounds. SOC. OF CHEMICAL INDUSTRY IN BASLE. March 14, 1941, No. 3511. Convention date, March 14, 1940. [Class 2 (iii)] . Carbinol compounds of the ring-D-homo steroid series are prepared from ketones of this series by treatment with a reducing agent known to be capable of reducing a ketone to a secondary alcohol, if desired with temporary protection of any double linkages or substituents capable of being reduced by the process. Substituents mentioned include esterified or etherified hydroxyl groups, substituted and unsubstituted hydrocarbon groups such as alkyl, alkenyl, alkinyl, alkylene, acyl or ketol groups, free or esterified carboxyl, amino or thiol groups or further carbonyl groups in the form of their derivatives such as in the form of enol esters and ethers. Parent materials for the process of the present invention are prepared by the process of Specification 556,734. Reducing agents, chemical, biochemical or electrochemical agents and particularly those used in the processes of Specifications 428,132, 428,133, 429,747, 446,501, 447,185, 448,225, 467,107, 468,123, and 475,068. The compounds produced by this invention have the character of the sexual hormones or of the suprarenal cortical hormones. The compounds may if desired by esterified or etherified. In examples (1) #<SP>4</SP>-3:17α-diketo-D-homo-andro stene is converted by ethyl orthoformate into 3-mono-enolethyl ether and this reduced by sodium in alcohol to #<SP>4</SP>-3-keto-17-α-oxy-D- homo-androstene. The reduction may also be carried out by nascent hydrogen produced electrolytically or by means of an alkali amalgam. Other reducing agents are catalytically activated hydrogen and Grignard compounds. The 3-keto group may also be protected by the formation of a ketal or a hydrazone. The carbinol formed, may if desired be esterified. Other starting materials mentioned include 3:17 α-diketo-D-homo-androstane, 3-keto-17α- oxy - D - homo - androstane, 3 - oxy - 17α - keto - D - homo - androstane and #<SP>1</SP>.<SP>3</SP>.<SP>5</SP>- 3-oxy-17α-keto-D-homo-oestratriene. (2) #<SP>4</SP>- 3:17 - α - diketo - D - homo - androstene - 3 - mono - enol - methvl ether is treated with a Grignard reagent prepared from magnesium and methyl iodide, to give #<SP>4</SP>-3-keto-17α-oxy-17α- methyl-D-homo-androstene. Similarly there may be reduced parent compounds having in the 17- sents hydrogen or an acyl group and R<SP>1</SP> represents hydrogen on a monovalent hydrocarbon residue. The new carbinols may be converted into their esters or ethers or by treatment with hydrocyanic acid into their cyanhydrins.