The preparation of a new class of oxaziridines containing an N-phosphinoyl group is described. The compounds were obtained by peroxyacid oxidation of N-phosphinoyl imines under basic or neutral conditions, and characterised by n.m.r. spectroscopy. Relevant 'J,,, 3J,H, and 'JCH coupling constants are reported. An X-ray structure analysis of the title compound establishes that the 2diphenylphosphinoyl group is trans to the 3-aryl ring. The P-N bond length (1.76 A) is abnormally high for an aminophosphorus(v) compound and the nitrogen atom is pyramidal (Z N = 280a). This geometry is interpreted in terms of an unusually low degree of n-bonding between nitrogen and phosphorus due to the high s-character of the nitrogen lone pair.
Novel stable N-phosphinoyl oxaziridines have been prepared and characterised by n.m.r. and mass spectrometry; they function as oxidants towards phosphines, sulphides, and alkenes.
A high-field 13C n.m.r. study of the title compounds below -80 "C has enabled measurement of the barriers to rotation around the aryl-C(0) bond. These barriers (AG* 7.7-9.5 kcal mol-'), and those for rotation around the C(0)-N bond (AG* 13.6-15.6 kcal mol-l) determined by 'H n.m.r. at higher temperatures, correlate well with Hammett 0 ' substituent parameters. The ground-state conformation has the phenyl ring twisted out of the amide plane. Some 'H and 13C chemical shift correlations are also reported.
Durch Oxidation der N‐Phosphinoylimine (III) entstehen die stabilen Oxaziridine (IV), die Thioether zu Sulfoxiden, Disulfide zu Thiosulfinaten und Cyclohexen zum Epoxid oxidieren.
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