63429-81-2Relevant academic research and scientific papers
The Reaction Between Oximes and Tervalent Phosphorus Compounds: A Low-Temperature Radical Rearrangement Process
Hudson, Robert F.,Brown, Charles,Maron, A.
, p. 2560 - 2573 (2007/10/02)
Ketoximes react rapidly with X2PCl compounds where X = Ph, Me2N, EtO and X2 = OCH2CH2O at low temperatures (-60 to -80 deg C) in the presence of triethylamine to give a PIII intermediate 2, which rearranges by a unimolecular process to the corresponding N-phosphinylated imine 3.Free radicals, formed by capture of the initially produced phosphonyl radical, are detected by ESR spectroscopy, and evidence for a radical cage process is obtained from 31P CIDNP studies.Where X2 = OCH2CH2O, the PIII intermediate (2d, e) can be isolated, and the structure established from 13C NMR spectra.Kinetic measurements show compound 2e to rearrange (30 - 60 deg C) ca. 10 times more slowly than the open chain compound (X = OEt), and the negative activation entropy suggests that this particular system (2e) rearranges, in part, by a cyclic transition state.
