| 摘要 |
1,171,129. Steroids related to ecdysone. ZOECON CORP. 4 Nov., 1966 [4 Nov., 1965; 26 Jan., 1966 (2) ; 26 May, 1966], No. 49534/66. Heading C2U. Compounds of the Formula (I) are prepared by selectively oxidizing compounds of the Formula (II) to give the corresponding 6- ketones, oxidizing the 20-hydroxymethyl group of these by treatment with a dialkylcarbodiimide or dicyoloalkylcarbodiimide and dimethyl sulphoxide in the presence of a strong acid and an organic base to give compounds of the Formula (III), treating these with a lithium derivative of a compound HC#C-YR<SP>2</SP> to give compounds of the Formula (IV) and catalytically hydrogenating these. (in which each of A and B is H or alkyl ; R<SP>1</SP> is H or OH; R<SP>2</SP> is H or tetrahydropyranyloxy; and Y is C 1-6 alkylene or alkylidene). The tetrahydroxypyranyl ether, when present, and the alkylidenedioxy group may then be acid hydrolysed to give ecdysone and related compounds. A 14α-hydroxy group may be introduced in a 14α-H compound by treatment with SeO 2 and a 5α-H compound may be epimerized to the 5#-H compound by treatment with a base. Compounds of the Formula (II) are prepared by reducing an appropriate alkyl 6-keto- 22,23 - bisnorchol - 7 - enoate to the corresponding 6-ol with tri-tert.-butoxide aluminium hydride followed by reduction of the carbalkoxy function with LiAlH 4 .
|
