Conversion of propargyl alcohol derivatives to alpha,beta-unsaturated ketone or alkyne derivatives comprises reaction with an acidic cation-exchange resin in an organic solvent

摘要

Process for converting propargyl alcohol derivatives (I) into alpha , beta -unsaturated ketones (II) or alpha , beta -unsaturated alkynes (III) comprises contacting (I) at 20-140 deg C with an acidic cation-exchange resin in an organic solvent in the absence of carboxylic acids and optionally in the presence of a small amount of water. Process for converting compounds of formula (I) into compounds of formula (II) or (III) comprises contacting (I) at 20-140 deg C with an acidic cation-exchange resin in an organic solvent in the absence of carboxylic acids and optionally in the presence of a small amount of water: R1 = H, alkyl or phenyl; R2, R3, R4 = H or a quaternary, tertiary, secondary or primary C atom that can form part of a 5- or 6-membered ring or the D ring of a steroid; the dotted line denotes a single or double bond. Independent claims are also included for the following: (1) 3-methoxy-17 alpha -(1-propynyl)-1,3,5(10),15-estratetraen-17 beta -ol (Ia); (2) 3-methoxy-17 alpha -(1-propynyl)-1,3,5(10),14,16-estrapentaene; (3) 3-methoxy-17 alpha -(phenylethynyl)-1,3,5(10),14,16-estrapentaene; (4) 3-methoxy-21-butyl-19-nor-1,3,5(10),14,16-pregnapentaen-20-one; and (5) 3-methoxy-21-phenyl-19-nor-1,3,5(10),14,16-pregnapentaen-20-one.