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O-nucleophilic features of amidoximes in acyl group transfer reactions

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Abstract

Analysis of kinetic behavior of isomeric Z-amidoximes and their Z-ions in reactions with 4-nitrophenyl-4-toluenesulfonate, diethylphosphate, and diethylphosphonate was performed in the framework of Bronsted relationship. The reactivity of amidoximate anions with respect to the mentioned substrates is comparable to that of typical α-nucleophiles, oximate ions. The α-effect decreased with the growing basicity of amidoximate ions, and for compounds with pK a>12.0 it was totally lacking. The high nucleophilic activity of neutral amidoximes and their anionic forms was ascribed to the cyclic structure of the transition state involving two kinds of assistance: general acidic, and basic catalysis. A unique feature of amidoximes as α-nucleophiles consists in their ability to perform efficient cleavage of ecotoxic substrates in a wide pH range, from basic to acid media.

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Authors and Affiliations

  1. Litvinenko Institute of Physical Organic and Coal Chemistry, National Academy of Sciences of the Ukraine, 83114, Donetsk, Ukraine

    T. M. Prokop’eva, Yu. S. Simanenko, E. A. Karpichev, V. A. Savelova & A. F. Popov

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  1. T. M. Prokop’eva
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  2. Yu. S. Simanenko
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  3. E. A. Karpichev
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  4. V. A. Savelova
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  5. A. F. Popov
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Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 11, 2004, pp. 1665–1677.

Original Russian Text Copyright © 2004 by Prokop’eva, Simanenko, Karpichev, Savelova, Popov.

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Prokop’eva, T.M., Simanenko, Y.S., Karpichev, E.A. et al. O-nucleophilic features of amidoximes in acyl group transfer reactions. Russ J Org Chem 40, 1617–1629 (2004). https://doi.org/10.1007/s11178-005-0068-3

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  • DOI: https://doi.org/10.1007/s11178-005-0068-3

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