Steroid Studies. XI. On the Methylation of 3-Oxosteroids. (1).

Abstract

By consecutive formylation, methylation, and deformylation, 4, 22-stigmastadien-3-one (IV) affords 2α-methyl-4, 22-stigmastadien-3-one (VII), while the same treatment of the 5α-dihydro compound (VIII) of (IV) gives the 2α-methyl derivative (XI), which agrees with the reduction product of (VII) with lithium in liquid ammonia. The same treatment of the 5β-dihydro compound (XIIIa) of (IV) forms the 4β-methyl derivative (XXa). These experimental results are consistent with the general rule that the 2-position in 3-oxo-5α-steroids and 4-position of 3-oxo-5β-steroids are active.