Studies on Sulfate Esters. I. Nucleophilic Reactions of Amines with p-Nitrophenyl Sulfate

Stephen J. Benkovic, Patricia A. Benkovic

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101 Scopus citations

Abstract

The nucleophilic reactivity of a series of amines toward p-nitrophenyl sulfate exhibits a small sensitivity to the basicity of the amine (β = 0.20). The reactivity is in the order tertiary > secondary > primary amine; steric hindrance increases rapidly with α substitution. A comparison of the reactions of the same amines with p-nitrophenyl phosphate reveals a striking similarity in their nucleophilic reactivity and the mechanism of the displacement. Both appear to involve transition states which feature little bond formation between substrate and amine. The spontaneous hydrolysis of p-nitrophenyl sulfate is discussed in terms of a possible elimination of sulfur trioxide in analogy to monomeric metaphosphate formation in the hydrolysis of certain phosphate dianions.

Original languageEnglish (US)
Pages (from-to)5504-5511
Number of pages8
JournalJournal of the American Chemical Society
Volume88
Issue number23
DOIs
StatePublished - Dec 1966

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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