Synthesis of 2α-Halo-4-en-3-oxo-steroids

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Some 2-ethoxalyl-4-en-3-one was treated with N-halo-succinimide in pyridine to give the corresponding 2α-halo-4-en-3-one in a good yield. Direct chlorination of testosterone acetate with sulfuryl chloride (1 mole) gave a small amount of 2α-chlorotestosterone acetate in dry beozene or dry ether, and with sulfuryl chloride (excess) gave mainly 2α, 4-dichlorotestosterone acetate in dry benzene and mainly 2α, 6β-dichlorotestosterone acetate in dry ether. These observations were confirmed by the syntheses of their related compounds through the unequivocal routes.

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