GB1191347A - 03-Alkyl-10-Methylgon-4-En-3-Ones and their Derivatives - Google Patents

Abstract

1,191,347. 13 - Alkyl -10 - methylgon - 4 - en - 3-ones. AMERICAN HOME PRODUCTS CORP. 16 May, 1967 [19 May, 1966 (2)], No. 22581/67. Heading C2U. The invention comprises (A) compounds of formula wherein R is H or acetylthio, R<SP>1</SP> is alkyl of more than one carbon atom, and X is hydroxymethylene, acyloxymethylene, carbonyl (optionally substituted alkyl, alkenyl or alkynyl)-(hydroxy or acyloxy) - methylene, (acetyl) - (hydroxy) - methylene, (acetyl) - (acyloxy) - methylene, 1<SP>1</SP>- hydroxyethyl - methylene acetylmethylene, acyloxyacetyl-methylene, (acyloxyacetyl)-(hydroxy)-methylene, ethylidene-methylene, (carboxyethynyl) - (hydroxy) - methylene or (2 - carboxyethyl) - (hydroxy) - methylene γ-lactone, with the proviso that when R<SP>1</SP> is Et then X is other than (ethynyl)-(hydroxy)-methylene, 1<SP>1</SP> - hydroxyethyl - methylene, acetylmethylene, hydroxymethylene, (acetyl) - (hydroxy) -methylene, (acetyl) - (acetoxy) - methylene, acetoxyacetyl-methylene or (acetoxyacetyl) - (hydroxy)- methylene, and derivatives of these compounds, wherein the 3-oxo group is protected; and (B) a process for preparing 13-alkyl-10-methylgon-4- en-3-ones (I) from 13-alkyl-3,10-unsubstitutedgon-4-enes (II) by the sequence II # 13- alkyl - gon - 5(10) - en - 4 - one (III) # 13- alkyl-10-cyano-gonan-4-one#4-protected 13- alkyl - 10 - cyano - gonan - 4 - one (IV) # 4- protected 13 - alkyl - 10 - methyl - gonan - 4 - one, (V)#13 - alkyl - 10 - methyl - gonan - 4 - one # 3 - hydroxymethylene - 13 - alkyl - 10 - methyl - gonan - 4 - one # 3 - hydroxyimino - 13 - alkyl - 10 - methyl - gonan - 4 - one # 4 - hydroxy - 13 - alkyl - 10 - methyl - gon - 4 - en - 3 - one # 4 - alkanesulphonyloxy - 13 - alkyl - 10 - methyl - gon - 4 - en - 3 - one # 4 - alkanesulphonyloxy - 13 - alkyl - 10 - methyl - gonan - 3 - one # I. The step II # III may be effected thus: II # 4 - hydroxy - 5 - bromo - 13 - alkyl - gon - 4 - ene # 4 - oxo - 5 - bromo- 13 - alkyl - gon - 4 - ene # III. The step IV # V may proceed via 4-protected 13- alkyl - 10 - iminomethyl - gonan - 4 - one. Compounds I are also obtainable by the sequence 13- alkyl - gon - 5(10) - en - 3 - ol # 13 - alkyl - 5,10 - methano - gonan - 3 - ol # 13 - alkyl - 5,10 - methano - gonan - 3 - one # I. Many interconversions of compounds I are described. The compounds I are stated to possess androgenic, anabolic, progestational, antiandrogenic and antiestrogenic activities and may be made up with carriers into pharmaceutical compositions for oral, parenteral and rectal administration.