11-Oxygenated Steroids. XIII. Synthesis and Proof of Structure of Δ^1,4-Pregnadiene-17α,21-diol-3,11,20-trione and Δ^1,4-Pregnadiene-11β,17α,21-triol-3,20-dione

Hormones

“…This reaction proceeds via the 3,20-semicarbazone of prednisone and is very similar to the analogous conversion of cortisone to cortisol (see Section 4.8.3) [242].…”

“…1,2-Dehydrogenation yields derivatives with glucocorticoid, anti-inflammatory, and antiallergenic effects that are four to five times higher than those of cortisone. At the same time, these substances have one-third the mineralocorticoid activity of cortisone [242]. The 1,2-dehydro derivatives of cortisone and cortisol, prednisone (117) and prednisolone (118), respectively, do not have significant mineralocorticoid activity and are, therefore, widely used in general, systemic pharmacodynamic therapy, particularly as anti-inflammatory and antirheumatic agents.…”

“…Insertion of the 1,2-double bond is achieved by chemical or microbiological methods, the latter being more economical. Prednisone can be produced chemically by a process developed by the Schering Corporation from pregnane-17α,21-diol-3,11,20-trione 21-acetate (119) involving a 1,4-dibromide and subsequent hydrogen bromide elimination with pyridine [242]. Other methods use the 1,2-dehydrogenation of cortisone with selenium dioxide [243,244].…”

Microbial reduction of 1,2-diketones to optically active .ALPHA.-hydroxyketones.

“…The same procedures as those described for the reduction of non-substituted 1,2-diphenylethanedione (la) were applied, except that 100mg of le was used. The resulting 2-hydroxy-2-(2-methylphenyl)-1 -phenylethanone (9) HPLC analysis of 1,2-diarylhydroxyethanones. The pair of regioisomers and enantiomers were observed as separated peaks on HPLCunder appropriate conditions.…”

“…Preparation of 2-hydroxy-2-{4-methylphenyt)-l-phenylethanone (3). The synthetic procedures were the same as those described for the preparation of the 2-methyl isomer (9), the hydroxyethanone 3 OB, DICEL CHIRAL CEL OB; TSK, TOYO SODA TSK gel NH2-60 modified with (S)-JV-dinitrobenzoylphenylglycine.6) 9/1, the ratio of hexane/2-propanol; 8/2, the ratio of methanol/water. Twopeaks corresponding to two enantiomers.…”