Studies on Sulfate Esters. II. Carboxyl Group Catalysis in the Hydrolysis of Salicyl Sulfate

Stephen J. Benkovic

doi:10.1021/ja00975a027

Studies on Sulfate Esters. II. Carboxyl Group Catalysis in the Hydrolysis of Salicyl Sulfate

Stephen J. Benkovic

Chemistry

Research output: Contribution to journal › Article › peer-review

27 Scopus citations

Abstract

The pH-rate profile for the hydrolysis of salicyl sulfate reveals hydronium ion and intramolecular carboxyl group catalysis. In contrast the rate of hydrolysis of p-carboxyphenyl sulfate is accelerated only by hydronium ion. The acid-catalyzed hydrolysis of aromatic sulfates is viewed as an A1 mechanism on the basis of activation entropies and D₂O solvent isotope and substituent effects. Intramolecular carboxyl group participation is discussed in terms of general acid or specific acid nucleophilic catalysis and compared to other examples involving similar behavior including salicyl phosphate.

Original language	English (US)
Pages (from-to)	5511-5515
Number of pages	5
Journal	Journal of the American Chemical Society
Volume	88
Issue number	23
DOIs	https://doi.org/10.1021/ja00975a027
State	Published - Dec 1966

All Science Journal Classification (ASJC) codes

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

Access to Document

10.1021/ja00975a027

Cite this

@article{e28ca24ad2514870967711962286988d,

title = "Studies on Sulfate Esters. II. Carboxyl Group Catalysis in the Hydrolysis of Salicyl Sulfate",

abstract = "The pH-rate profile for the hydrolysis of salicyl sulfate reveals hydronium ion and intramolecular carboxyl group catalysis. In contrast the rate of hydrolysis of p-carboxyphenyl sulfate is accelerated only by hydronium ion. The acid-catalyzed hydrolysis of aromatic sulfates is viewed as an A1 mechanism on the basis of activation entropies and D2O solvent isotope and substituent effects. Intramolecular carboxyl group participation is discussed in terms of general acid or specific acid nucleophilic catalysis and compared to other examples involving similar behavior including salicyl phosphate.",

author = "Benkovic, {Stephen J.}",

year = "1966",

month = dec,

doi = "10.1021/ja00975a027",

language = "English (US)",

volume = "88",

pages = "5511--5515",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "23",

}

TY - JOUR

T1 - Studies on Sulfate Esters. II. Carboxyl Group Catalysis in the Hydrolysis of Salicyl Sulfate

AU - Benkovic, Stephen J.

PY - 1966/12

Y1 - 1966/12

N2 - The pH-rate profile for the hydrolysis of salicyl sulfate reveals hydronium ion and intramolecular carboxyl group catalysis. In contrast the rate of hydrolysis of p-carboxyphenyl sulfate is accelerated only by hydronium ion. The acid-catalyzed hydrolysis of aromatic sulfates is viewed as an A1 mechanism on the basis of activation entropies and D2O solvent isotope and substituent effects. Intramolecular carboxyl group participation is discussed in terms of general acid or specific acid nucleophilic catalysis and compared to other examples involving similar behavior including salicyl phosphate.

AB - The pH-rate profile for the hydrolysis of salicyl sulfate reveals hydronium ion and intramolecular carboxyl group catalysis. In contrast the rate of hydrolysis of p-carboxyphenyl sulfate is accelerated only by hydronium ion. The acid-catalyzed hydrolysis of aromatic sulfates is viewed as an A1 mechanism on the basis of activation entropies and D2O solvent isotope and substituent effects. Intramolecular carboxyl group participation is discussed in terms of general acid or specific acid nucleophilic catalysis and compared to other examples involving similar behavior including salicyl phosphate.

UR - http://www.scopus.com/inward/record.url?scp=28944445688&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=28944445688&partnerID=8YFLogxK

U2 - 10.1021/ja00975a027

DO - 10.1021/ja00975a027

M3 - Article

AN - SCOPUS:28944445688

SN - 0002-7863

VL - 88

SP - 5511

EP - 5515

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 23

ER -

Studies on Sulfate Esters. II. Carboxyl Group Catalysis in the Hydrolysis of Salicyl Sulfate

Abstract

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this