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Mass spectra of Δ 4 ‐ and 5α‐3‐ketosteroids formed during the oxidation of some 3β‐hydroxysteroids by cholesterol oxidase
Author(s) -
Smith Andrew G.,
Brooks Charles J. W.
Publication year - 1976
Publication title -
biomedical mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 0306-042X
DOI - 10.1002/bms.1200030208
Subject(s) - cholesterol oxidase , chemistry , mass spectrum , ether , trimethylsilyl , enol , oxidase test , organic chemistry , enol ether , medicinal chemistry , stereochemistry , ion , enzyme , catalysis
Abstract Thirty‐six Δ 5 ‐ and 5α‐3β‐hydroxysteroids have been oxidized with cholesterol oxidase to give the corresponding Δ 4 ‐ and 5α‐3‐ketosteroids, respectively. The mass spectral characteristics of the products (or their trimethylsilyl ether derivatives, in the case of 3‐keto‐hydroxysteroids) varied considerably, depending especially on the nature of the C‐17 sidechain. The ion of m / e 124 (or its equivalent) from cleavage of ring B was frequently a major fragment from Δ 4 ‐3‐ketosteroids, but in some instances was of insignificant abundance. Trimethylsilylation of the product of the oxidation of neoergosterol gave neoergosterone enol‐trimethylsilyl ether. Fragmentations of the sidechain oredominated in the mass spectra of the 5α‐3‐ketosteroids.