Steroidal anaesthetics: synthesis of 3alpha-hydroxy-5alpha-pregnane-11,20-dione-(21-14C) and 3alpha,21-dihydroxy-5alpha-pregnane-11,20-dione-(21-14C) 21-acetate.

3alpha-Hydroxy-5alpha-pregnane-11,20-dione-[21-14C] and 3alpha,21-dihydroxy-5alpha-pregnane-11,20-dione-[21-14C] 21-acetate were prepared from a common radio-labelled intermediate, 21-diazo-3alpha-hydroxy-5alpha-pregnane-11,20-dione-[21-14C] 3-nitrate, obtained by the reaction of 17beta-chlorocarbonyl-3alpha-hydroxy-5alpha-androstan-11-one 3-nitrate with diazomethane-[14C].     

The identification of 14 alpha,17 beta-dihydroxyandrost-4-en-3-one monohydrate and 14 alpha,17 beta-dihydroxyandrosta-1,4-dien-3-one monohydrate, metabolites of androstenedione in Mucor piriformis.

The microorganism Mucor piriformis transforms androst-4-ene-3,17-dione into a major and several minor metabolites. X-ray crystallographic analysis of two of these metabolites was undertaken to determine unambiguously their composition and chirality. Crystals belong to the orthorhombic space-group P2(1)2(1)2(1), with a = 7.199(4) A and a = 6.023(3) A, b = 11.719(3) A and b = 13.455(4) A, c = 20.409(3) A and c = 20.702(4) A for the two title compounds, respectively. The structures have been refined to final R values of 0.060 and 0.040, respectively.     

Metabolism of ent-kaurenol-[17-14C], ent-kaurenal-[17-14C] and ent-kaurenoic acid-[17-14C] by germinating Hordeum distichon grains

Subcellular fractions from germinated barley embryos, chloroplast preparations and whole germinating barley grains are able to carry out the conversions ent-kaurenol → ent-kaurenal → ent-kaurenoic acid → ent-hydroxykaurenoic acid, the initial steps of the biosynthetic pathway to gibberellins. Whole grains, and chloroplasts to a slight extent, incorporate radioactivity from ent-kaurenol-[17-¹⁴C] and ent-kaurenoic acid-[17-¹⁴C] into materials with similar but distinct properties from the gibberellins GA₁, GA₃, GA₄ and GA₇.