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Nitroso Group Transfer from Substituted N-Methyl-N-nitrosobenzenesulfonamides to Amines. Intrinsic and Apparent Reactivity

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    Nitroso Group Transfer from Substituted N-Methyl-N-nitrosobenzenesulfonamides to Amines. Intrinsic and Apparent Reactivity
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    Departamento de Química Física, Facultad de Química, Universidad de Santiago, 15706 Santiago, Spain, and Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, P-1749−016 Lisboa, Portugal
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    The Journal of Organic Chemistry

    Cite this: J. Org. Chem. 2001, 66, 2, 381–390
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    https://doi.org/10.1021/jo0006730
    Published January 4, 2001
    Copyright © 2001 American Chemical Society
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    Abstract

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    We have studied the nitroso group transfer from substituted N-methyl-N-nitrosobenzenesulfonamides to primary and secondary amines, observing that the rate of the reaction increases as a consequence of the presence of electron withdrawing groups on the aromatic ring of the nitrosating agents. The rate constants determined for the nitroso group transfer, ktr, give good Bronsted-type relationships between log ktr (rate constant for nitroso group transfer) and p and p . The study of the nitrosation processes of secondary amines catalyzed by ONSCN and denitrosation catalyzed by SCN-, in combination with the formation equilibrium of ONSCN, has enabled us to calculate the value of the equilibrium constant for the loss of the NO+ group from a protonated N-nitrosamine (p ), which can be defined by analogy with p . The value of p for the loss of the NO+ group from an N-methyl-N-nitrosobenzenesulfonamide was obtained in a similar way. By using values of ΔpKNO = p − p , we were able to calculate the equilibrium constant for the nitroso group transfer and characterize the transition state. On the basis of Bronsted-type correlations, we have obtained values of and ≅ 0.55, showing a perfectly balanced transition state. In terms of the Marcus theory, the calculation of the intrinsic barriers for the nitroso group transfer reaction shows that the presence of electron withdrawing groups on the aromatic ring of the N-methyl-N-nitrosobenzenesulfonamides does not cause these barriers to vary.

    Copyright © 2001 American Chemical Society

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    *

     To whom correspondence should be addressed.

    †

     Universidad de Santiago.

    ‡

     Universidad de Lisboa.

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    The Journal of Organic Chemistry

    Cite this: J. Org. Chem. 2001, 66, 2, 381–390
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jo0006730
    Published January 4, 2001
    Copyright © 2001 American Chemical Society
    Request reuse permissions

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