Studies on Sulfate Esters. III. A Comparison of the Solvolyses of Salicyl Sulfate and Sulfur Trioxide

Stephen Benkovic, Patricia Ann Benkovic

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

The solvolyses of o- and p-carboxyphenyl sulfates in aqueous methanol have been investigated. The hydronium ion catalyzed solvolysis of the para substrate and the carboxyl-catalyzed solvolysis of the ortho isomer yield a similar methyl sulfate/sulfate ratio; the hydronium ion catalyzed solvolysis of the o-sulfate gives a significantly lower fraction of methyl sulfate. The threefold selectivities of the former for methanol are comparable to the observed partitioning of monomeric sulfur trioxide in aqueous alcohols. Additional mechanistic evidence is obtained from the effect of various aqueous organic solvents in acclerating the carboxyl group catalyzed solvolysis of the ortho isomer. Collectively the data support transition states of considerable sulfur trioxide character for catalysis by hydronium ions and the o-carboxyl moiety. The possibility of Lewis acid-base interactions influencing the product composition as in the case of the ortho isomer is discussed. A rationale, derived in part from the results on sulfur trioxide partitioning, is proposed for the alcohol selectivity of certain phosphorylating agents and extended hypothetically to sulfating reagents.

Original languageEnglish (US)
Pages (from-to)2646-2650
Number of pages5
JournalJournal of the American Chemical Society
Volume90
Issue number10
DOIs
StatePublished - Jan 1 1968

Fingerprint

Isomers
Sulfates
Esters
Sulfur
Methanol
Lewis Bases
Alcohols
Lewis Acids
Catalysis
Ions
Organic solvents
Substrates
Chemical analysis
sulfur trioxide
hydronium ion
Acids
methyl sulfate

All Science Journal Classification (ASJC) codes

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

Cite this

@article{cdc41d6a4bc941a486b31c17741047e7,
title = "Studies on Sulfate Esters. III. A Comparison of the Solvolyses of Salicyl Sulfate and Sulfur Trioxide",
abstract = "The solvolyses of o- and p-carboxyphenyl sulfates in aqueous methanol have been investigated. The hydronium ion catalyzed solvolysis of the para substrate and the carboxyl-catalyzed solvolysis of the ortho isomer yield a similar methyl sulfate/sulfate ratio; the hydronium ion catalyzed solvolysis of the o-sulfate gives a significantly lower fraction of methyl sulfate. The threefold selectivities of the former for methanol are comparable to the observed partitioning of monomeric sulfur trioxide in aqueous alcohols. Additional mechanistic evidence is obtained from the effect of various aqueous organic solvents in acclerating the carboxyl group catalyzed solvolysis of the ortho isomer. Collectively the data support transition states of considerable sulfur trioxide character for catalysis by hydronium ions and the o-carboxyl moiety. The possibility of Lewis acid-base interactions influencing the product composition as in the case of the ortho isomer is discussed. A rationale, derived in part from the results on sulfur trioxide partitioning, is proposed for the alcohol selectivity of certain phosphorylating agents and extended hypothetically to sulfating reagents.",
author = "Stephen Benkovic and Benkovic, {Patricia Ann}",
year = "1968",
month = "1",
day = "1",
doi = "10.1021/ja01012a032",
language = "English (US)",
volume = "90",
pages = "2646--2650",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "10",

}

Studies on Sulfate Esters. III. A Comparison of the Solvolyses of Salicyl Sulfate and Sulfur Trioxide. / Benkovic, Stephen; Benkovic, Patricia Ann.

In: Journal of the American Chemical Society, Vol. 90, No. 10, 01.01.1968, p. 2646-2650.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Studies on Sulfate Esters. III. A Comparison of the Solvolyses of Salicyl Sulfate and Sulfur Trioxide

AU - Benkovic, Stephen

AU - Benkovic, Patricia Ann

PY - 1968/1/1

Y1 - 1968/1/1

N2 - The solvolyses of o- and p-carboxyphenyl sulfates in aqueous methanol have been investigated. The hydronium ion catalyzed solvolysis of the para substrate and the carboxyl-catalyzed solvolysis of the ortho isomer yield a similar methyl sulfate/sulfate ratio; the hydronium ion catalyzed solvolysis of the o-sulfate gives a significantly lower fraction of methyl sulfate. The threefold selectivities of the former for methanol are comparable to the observed partitioning of monomeric sulfur trioxide in aqueous alcohols. Additional mechanistic evidence is obtained from the effect of various aqueous organic solvents in acclerating the carboxyl group catalyzed solvolysis of the ortho isomer. Collectively the data support transition states of considerable sulfur trioxide character for catalysis by hydronium ions and the o-carboxyl moiety. The possibility of Lewis acid-base interactions influencing the product composition as in the case of the ortho isomer is discussed. A rationale, derived in part from the results on sulfur trioxide partitioning, is proposed for the alcohol selectivity of certain phosphorylating agents and extended hypothetically to sulfating reagents.

AB - The solvolyses of o- and p-carboxyphenyl sulfates in aqueous methanol have been investigated. The hydronium ion catalyzed solvolysis of the para substrate and the carboxyl-catalyzed solvolysis of the ortho isomer yield a similar methyl sulfate/sulfate ratio; the hydronium ion catalyzed solvolysis of the o-sulfate gives a significantly lower fraction of methyl sulfate. The threefold selectivities of the former for methanol are comparable to the observed partitioning of monomeric sulfur trioxide in aqueous alcohols. Additional mechanistic evidence is obtained from the effect of various aqueous organic solvents in acclerating the carboxyl group catalyzed solvolysis of the ortho isomer. Collectively the data support transition states of considerable sulfur trioxide character for catalysis by hydronium ions and the o-carboxyl moiety. The possibility of Lewis acid-base interactions influencing the product composition as in the case of the ortho isomer is discussed. A rationale, derived in part from the results on sulfur trioxide partitioning, is proposed for the alcohol selectivity of certain phosphorylating agents and extended hypothetically to sulfating reagents.

UR - http://www.scopus.com/inward/record.url?scp=33947318396&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33947318396&partnerID=8YFLogxK

U2 - 10.1021/ja01012a032

DO - 10.1021/ja01012a032

M3 - Article

AN - SCOPUS:33947318396

VL - 90

SP - 2646

EP - 2650

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 10

ER -