Premium
NMR and 14 N NQR spectra. Structure of the crystalline products from the nitrosation of phosphorylacetaldehydes
Author(s) -
Pavlov Valeriy A.,
Smith John A. S.,
Zjablikova Tatjana A.
Publication year - 1992
Publication title -
magnetic resonance in chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0749-1581
DOI - 10.1002/mrc.1260300806
Subject(s) - chemistry , nitrone , oxime , tautomer , monomer , solvent , enol , nitroso , aldehyde , molecule , nitrosobenzene , proton nmr , nuclear magnetic resonance spectroscopy , nitrosation , nmr spectra database , stereochemistry , organic chemistry , spectral line , polymer , catalysis , physics , astronomy , cycloaddition
14 N NQR and NMR spectroscopy were used to show that, in the solid phase, the products of nitrosation of phosphorylacetaldehydes are a mixture of dimers of 1‐(dialkoxyphosphoryl)‐1‐nitrosoethen‐2‐ols and dialkoxyphosphorylacetaldnitrones. The stabilization of the nitrone form is probably made possible by a high degree of conjugation and by the way the dimeric molecules are packed in the crystal, which causes them to be held in fixed positions. When the dimeric 1‐(dialkoxyphosphoryl)‐1‐nitrosoethen‐2‐ols and dialkoxyphosphorylacetaldnitrones are dissolved, they undergo aldo‐enol, nitroso‐oxime and nitrone‐oxime tautomerism, converting gradually into monomeric aldehyde oximes which exist in E‐ and Z‐isomeric forms. The ratios of dimeric nitroso‐enol, nitrone‐enol and monomeric aldehyde oxime forms can be measured by NMR and depend on the solvent, concentration and temperature.