| 摘要 |
Steroid derivs. of formula (I) are new, where Q is absent or is a benzoquinone gp. of formula (Q') or (Q''), where T = H or Si(R4)3; each R4 = opt. branched 1-8C alkyl, 3-6C cycloalkyl or phenyl; R14 = H, 1-6C alkyl, opt. branched 1-6C alkoxy, halogen, NO2 or CN; B is (a) when Q is present: -CO-X-; X = NR1, O or CH2; R1 = H, Me or Et, or is absent; B is (b) -C(OSi(R4)3)=X'-; or X' = N or CH; B is (c) =C(OSi(R4)3)-X''-; or X'' = O or CH2; Z = (1) beta-H, alpha-OH; or Z = (2) alpha-H or alpha-OH and (a) -Alk-CO-R8 or -CO-R8; or (b) -Alk-OR12; Alk = opt. branched 1-12C hydrocarbon chain; R8 = H, OH, 1-12C alkyl, NR9R10 or OR11; R9, R10 = H, opt. branched 1-12C alkyl (opt. having an OH, COOH or 1-4C alkoxycarbonyl substit.), 3-6C cycloalkyl or phenyl; or NR9R10 = 5- or 6-membered satd. ring opt. contg. a further O or N heteroatom; R'' = H, alkali metal, opt. branched 1-18C alkyl or benzyl; R12 = phenyl-(1-6C)alkylcarbonyl, 5-10C cycloalkylcarbonyl, benzoyl, 1-18C alkoxycarbonyl, aminocarbonyl or 1-8C alkyl substd. aminocarbonyl, or is H provided that Alk = branched 3-8C chain; or Z = (3) =CH-(Alk)-CO-R8 or =CH-(Alk)-OR12a; (Alk) = bond or Alk as above; R12a = R12, H or 1-20C alkylcarbonyl; or Z = (4) gp. of formula (Z'), where the dashed bond replaces the 17alpha-H; or Z = (5) alpha-H and -NHCO-R13; R13 = 1-12C alkyl or -NR9R10; Z = (6) alpha-H and CN; or Z = (7) alpha-H and tetrazolyl; R' = H or Me; R'' = H or beta-Me; R''' = H, beta-Me or OH. Also claimed is a process for dehydrogenating a steroid deriv. of formula (I') which comprises reacting the cpd. with a silylating agent in the presence of a quinone to introduce a delta-1 double bond.
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