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Kinetics of the oxidation of phosphinic, phenylphosphinic, and phosphorous acids by N-bromoacetamide

✍ Scribed by Anu Moondra; Abha Mathur; Kalyan K. Banerji

Publisher
John Wiley and Sons
Year
1991
Tongue
English
Weight
527 KB
Volume
23
Category
Article
ISSN
0538-8066

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✦ Synopsis

The 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 P-H bond to the oxidant has been proposed.

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