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

Stephen J. Benkovic, Patricia A. Benkovic

Research output: Contribution to journalArticle

100 Citations (Scopus)

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

Fingerprint

Sulfates
Amines
Esters
Hydrolysis
Phosphates
Alkalinity
Substitution reactions
Sulfur
4-nitrophenyl sulfate
Substrates

All Science Journal Classification (ASJC) codes

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

Cite this

Benkovic, Stephen J. ; Benkovic, Patricia A. / Studies on Sulfate Esters. I. Nucleophilic Reactions of Amines with p-Nitrophenyl Sulfate. In: Journal of the American Chemical Society. 1966 ; Vol. 88, No. 23. pp. 5504-5511.
@article{b3aa7143ad074d8e817a256a726dd873,
title = "Studies on Sulfate Esters. I. Nucleophilic Reactions of Amines with p-Nitrophenyl Sulfate",
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.",
author = "Benkovic, {Stephen J.} and Benkovic, {Patricia A.}",
year = "1966",
month = "12",
doi = "10.1021/ja00975a026",
language = "English (US)",
volume = "88",
pages = "5504--5511",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "23",

}

Studies on Sulfate Esters. I. Nucleophilic Reactions of Amines with p-Nitrophenyl Sulfate. / Benkovic, Stephen J.; Benkovic, Patricia A.

In: Journal of the American Chemical Society, Vol. 88, No. 23, 12.1966, p. 5504-5511.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Studies on Sulfate Esters. I. Nucleophilic Reactions of Amines with p-Nitrophenyl Sulfate

AU - Benkovic, Stephen J.

AU - Benkovic, Patricia A.

PY - 1966/12

Y1 - 1966/12

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=33847394326&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33847394326&partnerID=8YFLogxK

U2 - 10.1021/ja00975a026

DO - 10.1021/ja00975a026

M3 - Article

AN - SCOPUS:33847394326

VL - 88

SP - 5504

EP - 5511

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 23

ER -