| 摘要 |
The invention comprises (1) a process for the preparation of steroids of the formula <FORM:1117594/C2/1> (wherein R1 is H, a - or b -CH3, or = CH2; and R2 and R3 are each H or C1- 6 acyloxy) by halogenation with chlorine or bromine in an inert organic solvent of corresponding steroids containing in rings A and B the D 3,5-3-acyloxy grouping, hydrolysis of the adduct formed, and dehydrohalogenation of the obtained 6b -halogeno - D 4 - 3 - ketone; and (2) as novel steroids, 6b - chloro - 16 - methylene - 17a -acetoxy - progesterone of m.p. 144-146 DEG C., 6b - bromo - 16 - methylene - 17a - acetoxy-progesterone of m.p. 148-149 DEG C. (decomp.), 16 - methylene - 6 - dehydro - 17a - caproyloxy-progesterone of m.p. 143-144 DEG C. and 16-methyl - D 4,6,16 - pregnatriene - 3,20 - dione of m.p. 217-218 DEG C. In a modification of the above process for the preparation of the last-named steroid, the 3,20-di-enol-acetate of 16a - methyl - progesterone is brominated and the product hydrolysed and dehydrobrominated to yield the required product. Examples are given, and the hydrolysis of 17a ,21-diacetoxy-pregna - 4,6 - diene - 3,20 - dione to the corresponding diol and the acetylation of this to 21 - acetoxy - D 4,6 - pregnadien - 17a - ol - 3,20-dione is also described. 3,17a - Dicaproyloxy - 16 - methylene - D 3,5-pregnadien -20-one is prepared from 16b -methyl-16a , 17a -epoxy-progesterone and caproic anhydride. Reference has been directed by the Comptroller to Specification 963,427. |
