Oxidation of tertiary benzamides by 5,10,15,20-tetraphenylporphyrinatoironIII chloride-tert-butylhydroperoxide

Organic & Biomolecular Chemistry
L Constantino, Jim Iley

Abstract

Tertiary benzamides are oxidized by the 5,10,15,20-tetraphenylporphyrinatoiron(III) chloride-Bu'(t)OOH system at the alpha-position of the N-alkyl groups. The major products are N-acylamides, although small amounts of secondary amides, the products of dealkylation, are also formed. Plots of initial rate versus initial substrate concentration for these reactions are curved, suggesting formation of an oxidant-substrate complex. The reaction rates are almost insensitive to the substituent in the benzamide moiety, but there is a kinetic deuterium isotope effect of 5.6 for the reaction of the N,N-(CH(3))(2) and N,N-(CD(3))(2) compounds. Comparison of the reaction products from N-alkyl-N-methylbenzamides reveals that, for all compounds studied except N-cyclopropyl-N-methylbenzamide, oxidation of the alkyl group is preferred, strongly so (by a factor of ca. 8) for N-allyl-N-methylbenzamide. In contrast to microsomal oxidation, there is no steric hindrance to oxidation of an isopropyl group. Thus, we propose that these reactions proceed via hydrogen atom abstraction to form an alpha-carbon-centred radical and we attribute the observed diminished reactivity of the N-cyclopropyl group to its known reluctance to form a cyclopropyl radical...Continue Reading

Citations

Mar 24, 2011·European Journal of Pharmaceutics and Biopharmaceutics : Official Journal of Arbeitsgemeinschaft Für Pharmazeutische Verfahrenstechnik E.V·Julia Christina Kasper, Wolfgang Friess
Feb 12, 2008·Journal of Medicinal Chemistry·Wolfgang FriebolinElisabeth Davioud-Charvet
Mar 25, 2010·Journal of Medicinal Chemistry·Nicole I WenzelElisabeth Davioud-Charvet

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