Substituted thienyl and thienylidene derivatives: testosterone and cyclopentanone

The reaction of 5-methoxy-2-thienyllithium and testosterone led to the formation of 3&-(5-methoxy-2-thienyl)-androst-4-en-3& 17b-diol-dilithium salt. Methanolysis of the lithium salt resulted in the formation of 3&-(5-methoxy-2-thienyl)-androst-4-en-3& 17b-diol (XIII) whereas hydrolysis of the lithium salt produced 3&- (5-methoxy-2-thienyl)-androsta-3&,5-diene-17b-diol (XII). Treatment of the diol or the diolefin with hydrachloric acid-methanol led to the formation of 4-androsten-17b-ol-D3' r -crotonic acid-y-mercapto-^-thiolactone (XIV). Treatment of 3-bromothiophene with n-butyllithium at Dry Ice-acetone temperature led to halogen-metal intercon-version. The reaction of the 3-thienyllithium and cyclo-pentanone followed by dehydration of the carbinol produced 1_(3-thieny1)-cyc1opentene (XXVIII). Treatment of XXVIII with n-butyllithium followed by magnesium bromide and then t-butylperbenzoate led to the formation of l-.(5-t-butoxy-3-thienyl)-cyclopentenefXXXI). De-t-butylation of XXXI under acidic condition resulted in the formation of 4-(l-cyclopentenyl) -2(C5H)~4hiophenone(XXXVI).