The Ce(IV)-mediated decarboxylation of N-benzyliminodiacetic acid (BIDA) produces benzaldehyde, formaldehyde, dimethylamine, benzylmethylamine, and N-benzylglycine in acidic perchlorate and acidic sulfate media. Spectrophotometric evidence of an intermediate Ce(IV)-BIDA complex is given. The data may be interpreted in terms of a mechanism which involves sequential reactions, the first of which is a reversible reaction: BIDA + Ce(IV) (k1) ⇄ (k-1) complex (k2) → products. The rapid complex formation is followed by a slower oxidative decomposition to give a free radical capable of inducing free-radical polymerization. The free radical reacts rapidly with another Ce(IV) to give an iminium ion which undergoes either hydrolysis or decarboxylation. The rate constants ki, k-1, and k2 were determined from kinetic data. At acidities between 0.10 and 2.0 M, the rates of both complex formation and complex decomposition are inversely dependent on [H+], Activation parameters were determined in perchloric acid. Evidence is given to suggest CeSO42+ as the reactive Ce(IV) species in acidic sulfate media. © 1983, American Chemical Society. All rights reserved.
S. B. Hanna and M. E. Moehlenkamp, "Metal Ion Oxidative Decarboxylations. 13.¹ Kinetics And Mechanisms Of The Oxidation Of N-Benzyliminodiacetic Acid With Cerium(IV) In Acidic Perchlorate And Acidic Sulfate Media2," Journal of Organic Chemistry, vol. 48, no. 6, pp. 826 - 832, American Chemical Society, Jan 1983.
The definitive version is available at https://doi.org/10.1021/jo00154a015
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01 Jan 1983