ABSTRACT
The ring contraction of 18 alpha-mesyloxy-20 alpha-hydroxy-18,20-cyclopregn-4-en-3-one (Ib) and 18 alpha-mesyloxy-20 alpha-hydroxy-21-acetyloxy-18,20-cyclo-pregn-4-en-3-one (Id) took place upon exposure to Florisil at 25 degrees C, producing 18 alpha-acetyl-17,18-cycloandrost-4-en-3-one (IIa) and 18 alpha-acetoxyacetyl-17,18-cycloandrost-4-en-3-one (IIb) respectively. A similar ring contraction of 18 alpha, 20 alpha-dihydroxy-18,20-cyclopregn-4-en-3-one (Ia) took place upon electron impact. Deuterium labeling demonstrated that the first steps of mass spectral fragmentation of Ia were the rearrangement to IIa and the oxidative cleavage to 3,18,20-trioxo-4-pregnene (IVa).
Subject(s)
Androstenes/chemical synthesis , Cyclosteroids/chemical synthesis , Androstenes/metabolism , Animals , Cyclosteroids/metabolism , Female , Kidney/metabolism , Mass Spectrometry , Rabbits , Rats , Receptors, Steroid/metabolism , Uterus/metabolismABSTRACT
The neutral urinary excretion products of 17beta-hydroxy-2alpha, 3alpha-cyclopropano-5alpha-androstane from the rabbit, dosed orally, were investigated. Column chromatography yielded five crystalline metabolites which were identified by GLC and spectroscopic measurements. Three of these substances were hydroxylated in the 4alpha-position and one in the 6alpha-position with the cyclopropane ring intact. The fifth substance, 17beta-hydroxy-3beta-methyl-5alpha-androstan-2-one, can be derived from initial hydroxylation of the cyclopropane ring at C-2 followed by ring opening. The dosed substance and triol material was shown to be present by GLC and m.s. measurements. GLC determinations show that hydroxylation has occurred at C-4-C-6-C-2.
