Intermediate field null for production manner and this manner of the raw materials chemical compound and these raw materials chemical compounds in order to produce karushitorioru and that derivative

摘要

Starting compounds for preparing calcitriol (1$g(a), 25-dihydroxycholecalciferol) and its derivatives showing, as compared with calcitriol, some modifications, particularly in the C-17 lateral chain, a method for preparing these starting compounds and intermediate products for this method are described. The new compounds have the general formula (I), wherein R?1 stands for a hydrogen atom, an alkyl, silyl, acyl, aryl, alkoxycarbonyl or alkoxyalkyl group whose meaning is more closely defined in the description and either a) A stands for a methylene group and R the residue -(CH2?)n?-CH2?-CR?2R?3OH (n = 1, 2, 3, 4, 5, 6, 7), wherein R?2 and R?3 stand independently for a hydrogen atom, a C1-4? alkyl group or R?2 and R?3 stand for a cyclopropyl to cyclohexyl ring or b) A stands for a direct bond and R a carbaldehyde residue. The new compounds are prepared from the known compound (20S)-20-hydroxymethyl-1,1-4-pregnadien-3-one by isomerization to the 1,5-dien-3-one and then, in case a) conversion of the 20-hydroxymethyl group to a 20-sulfonyloxymethyl group, reduction of the 3-keto group to the hydroxy group, construction of the side chain, oxidation to the 7-keto compound, epoxidation in the 1,2 position, conversion of the 7-ketone to the corresponding tosylhydrazide and reduction of the 7-tosylhydrazide with lithium aluminium hydride. In case b), the 20-hydroxymethyl group is protected by a protective group which is readily split off, the 5,7-diene is prepared as in a), the protective group is split off and the 20-hydroxymethyl compound is oxidized to the corresponding aldehyde.