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Diethylhydrogensilyl cyclic diethylsilylene derivatives in gas chromatography/mass spectrometry of hydroxylated steroids. III-Fragmentations of 5β-pregnane-17,20,21-triol derivatives

✍ Scribed by Hisao Nakatat; Masataka Ishibashi; Masahiro Itoh; Hiroshi Miyazaki


Book ID
102558026
Publisher
John Wiley and Sons
Year
1987
Tongue
English
Weight
499 KB
Volume
22
Category
Article
ISSN
1076-5174

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✦ Synopsis


A reaction of N, 0-bis-(diethylhydrogensily1)trifluoroacetamide with 5/3-pregnane-17,20,2l-triols afforded diethylhydrogensilyl (DEHS) cyclic diethylsilylene (DES) derivatives. 5P-Pregnane-3a,17a,20/3,2l-tetraol yielded the 3a,2l-bis-DEHS-17(~,20/3-DES compound, whereas the structure of the major product from its 20a isomer was assigned as the 3a,l7a-bis-DEHS-20a,2l-DES derivative, which would undergo facile isomerization to the unstable 3a,21-bis-DEHS-17a,2Oa-DES structure under electron ionization. Fragmentations of these DEHS-DES compounds are discussed on the basis of isotope labelling experiments, linked scanning data, and accurate mass measurements.