Mechanisms of hydrolysis of phenyl- and benzyl 4-nitrophenyl- sulfamate esters (Articolo in rivista)

Type
Label
  • Mechanisms of hydrolysis of phenyl- and benzyl 4-nitrophenyl- sulfamate esters (Articolo in rivista) (literal)
Anno
  • 2011-01-01T00:00:00+01:00 (literal)
Alternative label
  • W.J. Spillane, S. Thea, G. Cevasco, M. Hynes, C.J.A. McCaw and N. P. Maguire (2011)
    Mechanisms of hydrolysis of phenyl- and benzyl 4-nitrophenyl- sulfamate esters
    in Organic & biomolecular chemistry
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • W.J. Spillane, S. Thea, G. Cevasco, M. Hynes, C.J.A. McCaw and N. P. Maguire (literal)
Pagina inizio
  • 523 (literal)
Pagina fine
  • 530 (literal)
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  • 9 (literal)
Rivista
Note
  • ISI Web of Science (WOS) (literal)
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  • School of Chemistry, National University of Ireland, Galway, Ireland. Dipartimento di Chimica e Chimica Industriale, Università di Genova, Italy. Consiglio Nazionale delle Ricerche - Istituto di Metodologie Chimiche, Roma, Italy. (literal)
Titolo
  • Mechanisms of hydrolysis of phenyl- and benzyl 4-nitrophenyl- sulfamate esters (literal)
Abstract
  • The kinetics of hydrolysis at medium acid strength (pH interval 2–5) of a series of phenylsulfamate esters 1 have been studied and they have been found to react by an associative SN2(S) mechanism with water acting as a nucleophile attacking at sulfur, cleaving the S–O bond with simultaneous formation of a new S–O bond to the oxygen of a water molecule leading to sulfamic acid and phenol as products. In neutral to moderate alkaline solution (pH e ~ 6–9) a dissociative (E1cB) route is followed that involves i) ionization of the amino group followed by ii) unimolecular expulsion of the leaving group from the ionized ester to give N-sulfonylamine [HN SO2] as an intermediate. In more alkaline solution further ionization of the conjugate base of the ester occurs to give a dianionic species which expels the aryloxide leaving group to yield the novel N-sulfonylamine anion [-N SO2]; in a final step, rapid attack of hydroxide ion or a water molecule on it leads again to sulfamic acid. A series of substituted benzyl 4-nitrophenylsulfamate esters 4 were hydrolysed in the pH range 6.4–14, giving rise to a Hammett relationship whose reaction constant is shown to be consistent with the E1cB mechanism. (literal)
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