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The high resolution mass spectra of α,β‐unsaturated and α‐chloromercuri‐α,β‐unsaturated steroidal ketones
Author(s) -
Smith Howard E.,
Smith Roy G.
Publication year - 1973
Publication title -
organic mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 0030-493X
DOI - 10.1002/oms.1210070903
Subject(s) - chemistry , fragmentation (computing) , mass spectrum , ion , spectral line , analytical chemistry (journal) , medicinal chemistry , stereochemistry , organic chemistry , physics , astronomy , computer science , operating system
The high resolution mass spectra (500 eV) of some α,β‐unsaturated steroidal ketones have been studied and compared with the spectra of the corresponding α‐chloromercuri ketones. In the latter, the carbon‐mercury bond frequently remains intact at the expense of the fission of two carbon‐carbon bonds. The abundance of mercury‐containing ions allows the use of the mercury atom fingerprint in confirming ring B fragmentation of the steroid nucleus at C(6)–C(7) and C(9)–C(10) for 5α‐androst‐1‐ene‐3,17‐dione, 1,4‐androstadiene‐3,17‐dione and their 2‐chloromercuri derivatives; and at C(7)–C(8) and C(9)–C(10) for 1,4,6‐androstatriene‐3,17‐dione, 1,4,6‐androstarien‐17 β‐ol‐3‐one and their 2‐chloromercuri derivatives. 2‐Chloromercuri‐1,4,6‐androstatriene‐3,17‐dione and 2‐chloromercuri‐1,4,6‐androstatrien‐17 β‐ol‐3‐one also give an abundant ion as the result of ring C fragmentation at C(8)–C(14) and C(11)–C(12), the chloromercuri group being replaced by a hydrogen atom. This ring C cleavage gives the only recognizable distinctive fragmentation ion for 1,4,6‐pregnatriene‐3,20‐dione and 2‐chloromercuri‐1,4,6‐pregnatriene‐3,20‐dione. For most of the mercurated steroids, the low resolution mass spectra (70 eV) are reported. In these spectra, the fragmentation patterns are similar to those obtained using the higher ionization energy employed for the high resolution spectra.