Oxidation with A-Bromoacetamide

Selective Oxidation of Secondary Alcohols in Preference to Primary Alcohols [743] 

To a solution of 13.05 g (0.095 mol) of A-bromoacetamide in 233 mL of methanol, 3.6 mL of pyridine, and 12,7 mL of water, 15.00 g (0.023 mol) of 20-cyano-3a,21-dihydroxy-17-pregnen-ll-one is added. The mixture, while protected from light, is stirred overnight at room temperature. After this time, a considerable amount of crystals accumulates. To destroy the excess of A-bromoacetamide, 4.2 mL of allyl alcohol is added, followed by 4.4 mL of 6 N hydrochloric acid to neutralize the pyridine. Crystallization is completed by the addition of 900 mL of water over a period of 20 min. After the mixture has been left in an ice bath for 30 min, the crystals are filtered with suction, washed with water, and dried to furnish 14.3 g (96.5%) of 20-cyano-21-hydroxy-17-pregnene-3,ll-dione, mp 254.1-255.1 °C. 

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