Kinetic study of the deiodination of m-chloroiodobenzene (to chlorobenzene and iodide ion), as effected by sodium or potassium methoxide in methanol, with initiation by thermolysis of azobisisobutyronitrile (AIBN), reveals kinetic orders 1.0 in aryl iodide and 0.5 in AIBN. The reaction is 0.86 order in potassium methoxide, but the dependence of rate on sodium methoxide concentration is less easily stated. Nitrobenzene inhibits the reaction. At high inhibitor concentrations, the kinetic order in nitrobenzene approaches -1 and concomitantly the kinetic order in AIBN approaches unity. These and related features of kinetic behavior fail to disqualify the radical chain mechanism with electron-transfer steps that has been proposed for this reaction.

Kinetics and mechanism of the radical-induced deiodination of aryl iodides by methoxide ions

TOMASELLI, Gaetano;
1992

Abstract

Kinetic study of the deiodination of m-chloroiodobenzene (to chlorobenzene and iodide ion), as effected by sodium or potassium methoxide in methanol, with initiation by thermolysis of azobisisobutyronitrile (AIBN), reveals kinetic orders 1.0 in aryl iodide and 0.5 in AIBN. The reaction is 0.86 order in potassium methoxide, but the dependence of rate on sodium methoxide concentration is less easily stated. Nitrobenzene inhibits the reaction. At high inhibitor concentrations, the kinetic order in nitrobenzene approaches -1 and concomitantly the kinetic order in AIBN approaches unity. These and related features of kinetic behavior fail to disqualify the radical chain mechanism with electron-transfer steps that has been proposed for this reaction.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/20.500.11769/243206
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