Steroide und steroidähnliche Verbindungen. II. Stereochemische Untersuchungen der katalytischen Hydrierung von 1β‐Methyl‐4‐(p‐methoxyphenyl)‐bicyclo[4,3,0]nonadien‐(4,6)‐Derivaten

Abstract

Durch NMR‐Untersuchungen und chemische Synthesen wird bewiesen, daß die Hydrierung von 9β‐Hydroxy‐1β‐methyl‐4‐(p‐methoxyphenyl)‐bicyclo[4,3,0]nonadien‐(4,6) 3 a im Gegensatz zu Literaturangaben zum trans‐Bicyclo[4,3,0]nonan‐Derivat 12a führt.

A Method for the Introduction of Reporter Groups into Moenomycin A, Based on Thiouronium Salt Chemistry

“…Repeating work by Schick and Hilgetag,16 we obtained 8 from 4 and thiouronium acetate 7 in 80% yield. Under the same conditions, moenomycin model compound 9 was converted into alkylation product 10 in 71% yield.…”

“…In the course of synthetic work in the steroid field, Kuo, Taub, and Wendler reported in 1965 that thiouronium salt 3 , on treatment with 2‐methylcyclopentane‐1,3‐dione ( 4 ) in aqueous solution, provided secosteroid 5 in 80−85% yield (Scheme ) 15. The method was later used by others 16,17…”

“…Under the same conditions, moenomycin model compound 9 was converted into alkylation product 10 in 71% yield. Thiouronium acetate 7 was prepared from p ‐methoxyacetophenone ( 6 ) (see Scheme ) as reported previously 16…”

“…2‐[( E )‐3‐(4‐Methoxyphenyl)‐2‐butenyl]thiouronium Acetate (7): Compound 7 was prepared as described in refs 16,19…”

Steroide und steroidähnliche Verbindungen. IV. Synthese mestranol‐ähnlicher Verbindungen mit modifiziertem B‐Ring

“…H y d r o x y -10,5d i m e t h y 1 -4 -( pm e t h o x y p h e n y 1)b i c y c l o[4,3,0] n o n e n -(4) 2a a) Durch katalytische Hydrierung von l a 27,O g (0,l Mol) l a[2], 136 ml Tetrahydrofuran und 27,O g 2proz. Palladium-Calciumcarbonat-Katalysator schuttelt man in Wasserstoffatmosphare, bis 2,24 1 (0,l Mol) Wasserstoff aufgenommen worden sind.…”