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Organotrihalide Complexes: α-Nucleophiles and Effective Oxidizing Agents in Decomposition Reactions of Organophosphorus Compounds in Water and Surfactant Micelles

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Abstract

We have studied the nucleophilic and oxidative reactivity of the system HOBr/BrO−, in water and in the presence of different types of surfactants, relative to 4-nitrophenyldiethylphosphate, 4-nitrophenyl- 4´-toluenesulfonate (nucleophilic substitution), and 4-nitrophenol (oxidation). As the source of "active" bromine, we used organotrihalide complexes. The micellar effects of the surfactants in nucleophilic substitution reactions are adequately described within both a pseudophase distribution model and an ion-exchange model. Just transferring the reaction from water to micelles of a cationic surfactant leads to an increase in the observed rates of reaction of the BrO− ion with esters by up to a factor of 20-30 and an increase in the rate for reaction of HOBr with nitrophenol by up to a factor of 5, while the HOBr/BrO− system is one of the most effective systems in decomposition of organophosphorus compounds.

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Authors and Affiliations

  1. L. M. Litvinenko Institute of Physical Organic and Coal Chemistry, National Academy of Sciences of Ukraine, 70 R. Luxemburg Vul., 83114, Donets'k, Ukraine

    V. A. Savelova, T. M. Prokop'eva, M. K. Turovskaya, E. A. Karpichev, V. A. Mikhailov, A. L. Kanibolotskii, N. I. Burakov & A. F. Popov

  2. Department of Chemistry and Biochemistry, University of California Santa Barbara, California, 93106, USA

    C. A. Bunton

Authors
  1. V. A. Savelova
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  2. C. A. Bunton
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  3. T. M. Prokop'eva
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  4. M. K. Turovskaya
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  5. E. A. Karpichev
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  6. V. A. Mikhailov
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  7. A. L. Kanibolotskii
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  8. N. I. Burakov
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  9. A. F. Popov
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Savelova, V.A., Bunton, C.A., Prokop'eva, T.M. et al. Organotrihalide Complexes: α-Nucleophiles and Effective Oxidizing Agents in Decomposition Reactions of Organophosphorus Compounds in Water and Surfactant Micelles. Theoretical and Experimental Chemistry 40, 300–308 (2004). https://doi.org/10.1023/B:THEC.0000049076.85204.82

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  • DOI: https://doi.org/10.1023/B:THEC.0000049076.85204.82

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