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Nickel acetate catalyzed autoxidation of benzoin

Hammond, George S. and Wu, Chin-Hua S. (1973) Nickel acetate catalyzed autoxidation of benzoin. Journal of the American Chemical Society, 95 (25). pp. 8215-8222. ISSN 0002-7863. doi:10.1021/ja00806a001.

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The autoxidation of benzoin in methanol catalyzed by nickel acetate is first order in each of benzoin and the catalyst and independent of the partial pressure of oxygen. The stoichiometry and product analysis demonstrate that benzoin reacts with oxygen to give benzil and hydrogen peroxide. A primary isotope effect of k_B/k_D = 7 has been observed. The rates of oxidation, relative to benzoin, of 4,4'-dichloro-, 4,4'-dimethyl-, and 4,4'-dimethoxybenzoin were respectively 2.4, 0.40, and 0.21. We suggest that the reaction involves equilibration of nickel acetate with a nickel acetate-benzoin complex. The rate-limiting step of the reaction involves abstraction of an α-hydrogen atom of the benzoin by an acetoxy group. Some intermediate must then react very rapidly with oxygen. Substituent effects indicate that in the slow step some net negative charge is introduced into the substrate group.

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Additional Information:© 1973 American Chemical Society. Received July 7, 1973. This work was supported by a grant from the National Science Foundation. We are indebted to Professor Harry B. Gray for his helpful discussion. The technical assistance of Mr. Steve Hammond for some polarographic oxygen monitoring experiments is also acknowledged.
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Caltech Arthur Amos Noyes Laboratory4755
Issue or Number:25
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Official Citation:Nickel acetate catalyzed autoxidation of benzoin George S. Hammond and Chin-Hua S. Wu Journal of the American Chemical Society 1973 95 (25), 8215-8222 DOI: 10.1021/ja00806a001
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:55388
Deposited By: Tony Diaz
Deposited On:03 Mar 2015 23:49
Last Modified:10 Nov 2021 20:45

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