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Ion pair catalysis of the autooxidative cleavage of benzoin in emulsion systems
Author(s) -
Franklin Thomas C.,
Ogiya Naoyuki
Publication year - 1980
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550121213
Subject(s) - benzil , chemistry , benzoin , benzaldehyde , umpolung , catalysis , aqueous solution , inorganic chemistry , acetonitrile , pyridine , hydroxide , autoxidation , reaction rate , photochemistry , organic chemistry , nucleophile
A study was made of the autooxidation of benzoin in organic‐aqueous sodium hydroxide emulsions in the presence of several quaternary ammonium salts. The rate of the reaction was found to be accelerated by these salts, probably by ion pair extraction. In pyridine and acetonitrile systems the reaction was almost exclusively the formation of benzoate. Neither benzil nor benzaldehyde were intermediates in the oxidation process. The rate law for the reaction was found to be\documentclass{article}\pagestyle{empty}\begin{document}$$ - \frac{{dPo_2 }}{{dt}} = k\left[{{\rm Po}_{\rm 2} } \right]\left[{{\rm benzion}} \right]\left[{{\rm OH}^ - } \right] + k_2 \left[{{\rm Po}_2 } \right]\left[{{\rm benzion}} \right]\left[{{\rm OH}^ - } \right][{\rm R}_4 {\rm N}^ +] $$\end{document} which led to the conclusion that the rate‐determining step in the catalyzed pathway was the reaction of oxygen with the ion pair: