STEROIDS AND RELATED PRODUCTS: XXI. THE SYNTHESIS OF 17α-Bromo-6α -METHYLPROGESTERONE

Abstract

The synthesis fo 17a-bromo-6a-inethylprogesterone, from pregnenolone acetate, is reported. The product is a potent luteoid with marked oral activity. In the course of this investigation, a useful x ariation of the synthesis of 6a-methylprogesterone, from pregnenolone, was devised. The rearrangement of a 5p,Bp-epoxide to a 6-ketone, upon chromatography on a l u n~i~l u m oxide "\Voelrn", was observed.

Flavonoids. IV. A novel Clemmensen reduction. The direct conversion of 2-alkylisoflavones to 2-alkyl-3-isoflavenes

“…In order to further substantiate this point, an unambiguous synthesis of the '-isoflavene 4a was carried out. This synthesis utilized 7-tetrahydropyranyloxy-4'-methoxyisoflavone (5),2 and entailed an exhaustive borohydride reduction,2 a mild acid-catalyzed dehydra-(4) Absorption bands in the spectra of 4 have been assigned to the following structural features of 7-acetoxy-4'-methoxy-A2-isoflavene (4b). The 1660-cm-1 band is attributed to the vinyl ether group [OCH=C(Ar)CHs].…”

“…Some Light-Absorption Properties of A3-Isoflavenes. -As can be seen in Figure 1, the ultraviolet spectrum of the Clemmensen product 4 is strikingly similar to those recorded for the other Clemmensen products 2a-c. A clue for 2 unsaturation lay in comparing the spectra of the Clemmensen products by graphical (5) The facile dehydration of 4-alkylisoflavanols (derived from Grignard addition to an isofiavanone) has been described in the preceding publication.…”