On the formation of allenes in the steroid series III.: Synthesis and reactions of 3‐methoxy‐17α‐hydroxy‐17β‐ethynyl‐1,3,5(10)‐estratriene (“epimestranol”)

Abstract

Abstract “Epimestranol” ( 6 ) has been prepared from the 16α,17‐epoxide 5 by reduction with LiAlH 4 . The structures of several by‐products have been elucidated and a mechanism for their formation is discussed. Both “mestranol” ( 3 ) and “epimestranol” failed to form p ‐tosylates and only “mestranol” could be converted into the p ‐toluenesulfinate which readily rearranged to the allenic sulfone 14 . “Epimestranol” was transformed into a mixture of the two epimeric 17‐sulfones instead of the 17α‐sulfinate.