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Electron impact induced fragmentation of 4‐alkyl derivatives of 2,6,7‐trioxa‐1‐phosphabicyclo[2.2.2]octane and the corresponding 1‐oxides, 1‐sulfides and 1‐selenides
Author(s) -
Kenttämaa Hilkka,
Enqvist Jouni
Publication year - 1980
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.1210151007
Subject(s) - fragmentation (computing) , chemistry , octane , electron ionization , alkyl , ion , chalcogen , metastability , formaldehyde , medicinal chemistry , selenium , polyatomic ion , crystallography , organic chemistry , computer science , ionization , operating system
The electron impact fragmentations of several derivatives of 2,6,7‐trioxa‐1‐phosphabicyclo[2.2.2]octane have been examined by means of high resolution and metastable ion analysis. The principal fragmentation route for bicyclophosphites, phosphates and phosphorothionates involves a loss of formaldehyde, followed by a loss of the PO 2 X and HPO 2 X groups (X = ‐, O, S). The behaviour of phosphoroselenates is quite different, due partly to the favoured loss of selenium from the molecular ion before further fragmentation. Fragmentation through CO bond breaking and a rearranged molecular ion is dependent on the exocyclic chalcogen atom (‐, O, S, Se) on phosphorus. The reactions have been rationalized in terms of 1‐ and 4‐substitutions.