(Vinyloxy)chlorocyclotetraphosphazenes. The Use of Two Dimensional (31)P NMR Spectroscopy in Phosphazene Chemistry

摘要

The reactions of the lithium enolate of acetaldehyde, LiOCHCH2, with octachloro-cyclotetraphosphazene, N4P4C18, led to the series of (vinyloxy) chlorocyclotetraphohphazenes, N4P4C18-n (OCH = CH2) (n=1,2). The qualitative and quantitative analysis of the NMR spectrum of the mixture of bis isomers, N4P4C16 (OCH=CH2)2, was accomplished by a combination of J-resolved homonuclear 2-D NMR, homonuclear shift-correlated 2-D NMR spectroscopy and mixture simulation techniques. This represents the first demonstration of the use fo 2-D NMR methods to problems in phosphazene chemistry. The reaction of LiOCHCH2 is unique in the reactions of N4P4C18 in that the 2,4-N4P4C16 (OCH=CH2)2 isomers are the major products. The composition of the N3P3C13 (OCH=CH2)3 mixture was also determined in order to shed light on the stereochemical course of the lithium enolate reactions.