Improvements concerned with Steroids related to Ecdysone

摘要

1,174,082. Steroids related to ecdysone. ZOECON CORP. 4 Nov., 1966 [4 Nov., 1965; 26 Jan., 1966 (2); 26 May, 1966], No. 49532/66. Headings C2C and C2U. Steroid compounds of the formula (wherein R is H, OH or tetrahydropyran-2- yloxy; R2 is O or H(OH); R3 is H or OH; R4 is O or H(OH); each of R5 and R6 is H or hydrocarbon carboxylic acyl of less than 12 carbon atoms, or R5 and R6 taken together are methylene which may be mono- or di-(C 1-6 alkyl) substituted; R7 isα-H, #-H orα-OH; and Y is C 3-8 alkylene) which are novel except when R1 and R3 are OH, R2 is H(OH), R4 is O, R5 and R6 are as defined above, and R7 is H, and the novel compounds wherein R1 is acyloxy, are prepared by treating a steroid of the formula with an alkali metal salt of a compound of the formula R8CH 2 SOR9 (wherein R8 is C 2-7 alkyl which may be hydroxy- or tetrahydropyranyloxy-substituted and R9 is phenyl) to give a product containing a 17-side chain -CH(CH 3 )-CO-CH(R8)SOR9 and treating this product with Al amalgam, Zn amalgam, Zn and acetic acid or chromous chloride, to give a product containing nuclear substituents as in the starting material and a side chain -CH(CH 3 )-CO-CH 2 -R8. These 22-keto steroids may then be reduced to the 22-ols (a mixture ofα- and #-isomers), the 6-keto compounds may be obtained by oxidation of the 6-ols, and the 2,3-diols by cleavage of the 2,3- alkylidenedioxy compounds with an acid (which will also convert a tetrahydropyranyloxy group R1 into a free OH group). Compounds of the formula R8CH 2 SOR9, where R8 and R9 are as defined above are prepared by reaction of the sodium salt of the appropriate halide with sodium phenyl mercaptide to yield the corresponding sulphide which is then oxidized to the sulphoxide. Reference is made to Specifications 1,105,980 and 1,174,083.