Abstract
AbstractThe oxidation of phosphinic, phenylphosphinic, and phosphorous acids by N‐bromoacetamide (NBA) in acid solution, results in the formation of corresponding higher oxyacids of phosphorus. The reaction is first order with respect to NBA, second order in the oxyacid and inverse first in hydrogen ions. The oxidation of deuteriated phosphorus oxyacids showed the presence of a substantial primary kinetic isotope effect. The reaction failed to induce polymerization of acrylonitrile. Added acetamide has no effect on the reaction rate. It has been shown that the ‘inactive’ tautomer of the phosphorus oxyacids, RHP(O)OH, participates in the oxidation process. A rate‐determining step involving transfer of a hydride ion from the PH bond to the oxidant has been proposed.
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