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Volumn , Issue 7, 1998, Pages 1613-1620

Nitrosation and denitrosation of substituted N-methylbenzenesulfonamides. Evidence of an imbalanced concerted mechanism

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EID: 0346397850     PISSN: 03009580     EISSN: None     Source Type: Journal    
DOI: 10.1039/a801275j     Document Type: Article
Times cited : (20)

References (42)
  • 1
    • 0004206788 scopus 로고
    • Cambridge University Press, UK
    • D. L. H. Williams, Nitrosation, Cambridge University Press, UK, 1988.
    • (1988) Nitrosation
    • Williams, D.L.H.1
  • 28
    • 0003059838 scopus 로고
    • eds. E. Caldin and V. Gold, Chapman and Hall, London
    • (b) J. Albery, in Proton Transfer Reactions, eds. E. Caldin and V. Gold, Chapman and Hall, London, 1975, p. 263.
    • (1975) Proton Transfer Reactions , pp. 263
    • Albery, J.1
  • 30
    • 0000654579 scopus 로고
    • The magnitude of the isotope effects is similar for hydron transfer from the hydronium ion and from the carboxylic acids, which implies a more symmetrical transition state for the former than for the latter. However experimental data show much more variation in reactivity within the carboxylic acid set than between it and the hydronium ion. As one of the referees suggests this anomaly could be rationalised by considering that isotope effects between electronegative atoms are always secondary with no primary component [see (a)]. Nevertheless the secondary isotope effect of 1.25, which is obtained for denitrosation by carboxylic acid by using the fractionation factors [see (b)], is not consistent with experimental data. We think that the similarity in reactivity between carboxylic acids and the hydronium ion is due to the switch from a neutral to a cationic acid as is reported in the following references. (a) C. G. Swain, D. A. Kuhn and R. L. Schowen, J. Am. Chem. Soc., 1965, 87, 1553; (b) K. B. J. Schowen, in Transition States of Biochemical Processes, eds. R. D. Gandour and R. L. Schowen, Plenum Press, New York, 1978, ch. 6.
    • (1965) J. Am. Chem. Soc. , vol.87 , pp. 1553
    • Swain, C.G.1    Kuhn, D.A.2    Schowen, R.L.3
  • 31
    • 0000654579 scopus 로고
    • eds. R. D. Gandour and R. L. Schowen, Plenum Press, New York, ch. 6
    • The magnitude of the isotope effects is similar for hydron transfer from the hydronium ion and from the carboxylic acids, which implies a more symmetrical transition state for the former than for the latter. However experimental data show much more variation in reactivity within the carboxylic acid set than between it and the hydronium ion. As one of the referees suggests this anomaly could be rationalised by considering that isotope effects between electronegative atoms are always secondary with no primary component [see (a)]. Nevertheless the secondary isotope effect of 1.25, which is obtained for denitrosation by carboxylic acid by using the fractionation factors [see (b)], is not consistent with experimental data. We think that the similarity in reactivity between carboxylic acids and the hydronium ion is due to the switch from a neutral to a cationic acid as is reported in the following references. (a) C. G. Swain, D. A. Kuhn and R. L. Schowen, J. Am. Chem. Soc., 1965, 87, 1553; (b) K. B. J. Schowen, in Transition States of Biochemical Processes, eds. R. D. Gandour and R. L. Schowen, Plenum Press, New York, 1978, ch. 6.
    • (1978) Transition States of Biochemical Processes
    • Schowen, K.B.J.1


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.