2-LOWER ALKYL-2(3-OXOLOWER ALKYL)-1,3-CYCLOPENTADIONES

摘要

1325632 Optically active bicyclic ketones and steroid ketones F HOFFMANN-LA ROCHE & CO AG 19 Jan 1971 [21 Jan 1970] 46881/72 Divided out of 1325631 Headings C2C and C2U One mole equivalent of an optically active compound II in which R1 is 1-7C alkyl, 2-7C alkenyl, 2-5C alkynyl, aryl, aralkyl, acylamino, halo, 1-7C alkenoyloxy, or 2-8C alkoxycarbonyl; R2 is H, 1-7C alkyl, aryl, aralkyl or -(CH 2 ) p R5; R5 is halo, CN, OH, 1-7C alkoxy, mesyloxy, tosyloxy or -C(=R7)R6; R6 is H, OH, 1-7C alkyl, 1-7C alkoxy, aryloxy or aryl-1-7C alkoxy; R7 is oxo, alkylenedioxy or arylenedioxy (provided that when R6 is other than H or 1-7C alkyl, R7 is oxo); m is 1-4; n = 0 or 1-4 and p is 0, 1 or 2 and one mole equivalent of an optically active compound III are prepared when two moles of a racemic mixture of a compound I are cyclized in the presence of an optically active agent in an aprotic solvent. 5-Oxo-4,5-seco steroids of Formula IV in which R10 is H or 1-7C alkyl and U represents the remainder of the B, C and D rings may be cyclized in the same way to give optically active steroids V Dehydration of these 5-hydroxy steroids gives the corresponding #4-steroids. Named products of processes, which may also involve hydrolysis of a 17-tert.-butoxy group, are (-)-19-nor-testosterone and (-)-19-nor-retrotestosterone and the corresponding enantiomeric (+ )-steroids. (-) - 3a# - Hydroxy - 7a# - methyl - perhydroindan-5-one and (+)-3aα-hydroxy-7aα- methyl-perhydroindan-5-one are claimed perse.