Verfahren zur Herstellung von 13-Alkyl-gonanverbindungen

摘要

The invention comprises a compound of formula wherein each R is H or Alkyl, R1 is a saturated or unsaturated aliphatic hydrocarbon radical and E is a predominantly o/p directing and activating substituent in electrophilic aromatic substitution and specifically those compounds wherein R is H and (1) E is methoxy and R1 is methyl, ethyl, isopropyl or cetyl; (2) E is hydroxy and R1 is methyl (a) or ethyl; (3) E is acetoxy and R1 is methyl. These compounds (except (3) which is made by acetylating 2(a)) are prepared by a process for preparing generally a compound of formula by cyclodehydration of a compound of formula wherein the phenyl group has a free o-position activated by substituent E (which is e.g. hydroxy, acyloxy, alkoxy, amino, acylamino, monoalkylamino or dialkylamino), R is H or alkyl, T is either an ethylenic bond or H2 on the C adjacent to CR2 and O = on the C in the D-ring, R1 is a saturated or unsaturated aliphatic hydrocarbon radical and Q is CH2 or CH2CH2. An exemplified preparation of a D-homosteroid is that in which E is 3-methoxy, R is H, T is H2 and O = and R1 is methyl. Starting materials.-2 - cetyl - 2 - (61 - m -methoxyphenyl - 31 - oxo) hexyl - 1,3 - a cyclopentanedione was prepared from 6-m-methoxyphenylhex - 1 - en - 3 - one and 2 - cetylcyclo pentane-1,3-dione; the latter by heating 2-cetylcyclopentane - 1,3,5 - trione semicarbazone with KOH. The cetylcyclopentanetrione was prepared from conc. HCl and ethyl 4-cetyl - 2,3,5 - trioxocyclopentyl glyoxlyate which was in turn made by condensing methyl n-heptadecyl ketone with diethyl oxalate.