Oxidatively initiated phosphorylation reactions of phosphine
1991
Lam, W.W. | Toia, R.F. | Casida, J.E.
Introduction of phosphine into alcoholic solutions of m-chloroperoxybenzoic acid results in mixtures of phosphinic and phosphonic acids, monoalkyl dihydrogen phosphinates, monoalkyl hydrogen phosphonates, dialkyl hydrogen phosphonates, and trialkyl phosphates, as analyzed by 31P NMR spectroscopy and GC/MS. The requirement for peracid indicates the intermediacy of oxidatively generated reactive phosphorylating species. Steric factors appear to be important since the extent of phosphorylation varies inversely with the steric bulk of the alcohol used, i.e., ester formation with methanol > ethanol > n-propanol >> 2-propanol >>> tert-butyl alcohol. Imidazole is also N-phosphorylated under comparable conditions. Phosphine administered to rats, orally as a suspension of zinc phosphide in corn oil, is excreted in the urine as phosphinic and phosphonic acids, thereby suggesting that an analogous oxidation sequence may occur in vivo. Thus, the toxicological properties of phosphine may reflect a combination of its reactivity as a nucleophile per se and the electrophilic character of the intermediates arising on its oxidation which could lead to derivatization of critical bionucleophiles.
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