Diaryldiacyloxyspirosulfuranes. Part 4. A kinetic study on the mechanism of hydrolysis

E. Vass, Ferenc Ruff, István Kapovits, J. Rábai, D. Szabó

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

Kinetics of the hydrolysis of diaryldiacyloxyspirosulfuranes leading to sulfoxides have been studied under pseudo-first-order conditions in dioxane-water mixtures. It has been found that high solvent polarities and ionic strengths increase the reaction rate. The reaction is also promoted by electron-donating substituents (ρ -0.52). Strong acids have a catalytic effect on the reaction in which case the substituent effect is more pronounced (ρ -1.55). In neutral medium the deuterium solvent isotope effect is k H2O/kD2O 1.66, while in acidic medium the ratio of catalytic constants is found to be 0.56. The rate of the reaction is greatly increased with the increasing size of the spiroring (from 5 to 7) in the sulfurane. Kinetic data suggest a dissociative reaction mechanism.

Original languageEnglish
Pages (from-to)855-859
Number of pages5
JournalJournal of the Chemical Society, Perkin Transactions 2
Issue number5
Publication statusPublished - 1993

Fingerprint

Hydrolysis
Sulfoxides
Kinetics
Deuterium
Ionic strength
Isotopes
Reaction rates
Acids
Electrons
Water
1,4-dioxane

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Diaryldiacyloxyspirosulfuranes. Part 4. A kinetic study on the mechanism of hydrolysis. / Vass, E.; Ruff, Ferenc; Kapovits, István; Rábai, J.; Szabó, D.

In: Journal of the Chemical Society, Perkin Transactions 2, No. 5, 1993, p. 855-859.

Research output: Contribution to journalArticle

@article{4299a70653ac4aaa90f31dbe5ae3fef6,
title = "Diaryldiacyloxyspirosulfuranes. Part 4. A kinetic study on the mechanism of hydrolysis",
abstract = "Kinetics of the hydrolysis of diaryldiacyloxyspirosulfuranes leading to sulfoxides have been studied under pseudo-first-order conditions in dioxane-water mixtures. It has been found that high solvent polarities and ionic strengths increase the reaction rate. The reaction is also promoted by electron-donating substituents (ρ -0.52). Strong acids have a catalytic effect on the reaction in which case the substituent effect is more pronounced (ρ -1.55). In neutral medium the deuterium solvent isotope effect is k H2O/kD2O 1.66, while in acidic medium the ratio of catalytic constants is found to be 0.56. The rate of the reaction is greatly increased with the increasing size of the spiroring (from 5 to 7) in the sulfurane. Kinetic data suggest a dissociative reaction mechanism.",
author = "E. Vass and Ferenc Ruff and Istv{\'a}n Kapovits and J. R{\'a}bai and D. Szab{\'o}",
year = "1993",
language = "English",
pages = "855--859",
journal = "Journal of the Chemical Society, Perkin Transactions 2",
issn = "1470-1820",
publisher = "Royal Society of Chemistry",
number = "5",

}

TY - JOUR

T1 - Diaryldiacyloxyspirosulfuranes. Part 4. A kinetic study on the mechanism of hydrolysis

AU - Vass, E.

AU - Ruff, Ferenc

AU - Kapovits, István

AU - Rábai, J.

AU - Szabó, D.

PY - 1993

Y1 - 1993

N2 - Kinetics of the hydrolysis of diaryldiacyloxyspirosulfuranes leading to sulfoxides have been studied under pseudo-first-order conditions in dioxane-water mixtures. It has been found that high solvent polarities and ionic strengths increase the reaction rate. The reaction is also promoted by electron-donating substituents (ρ -0.52). Strong acids have a catalytic effect on the reaction in which case the substituent effect is more pronounced (ρ -1.55). In neutral medium the deuterium solvent isotope effect is k H2O/kD2O 1.66, while in acidic medium the ratio of catalytic constants is found to be 0.56. The rate of the reaction is greatly increased with the increasing size of the spiroring (from 5 to 7) in the sulfurane. Kinetic data suggest a dissociative reaction mechanism.

AB - Kinetics of the hydrolysis of diaryldiacyloxyspirosulfuranes leading to sulfoxides have been studied under pseudo-first-order conditions in dioxane-water mixtures. It has been found that high solvent polarities and ionic strengths increase the reaction rate. The reaction is also promoted by electron-donating substituents (ρ -0.52). Strong acids have a catalytic effect on the reaction in which case the substituent effect is more pronounced (ρ -1.55). In neutral medium the deuterium solvent isotope effect is k H2O/kD2O 1.66, while in acidic medium the ratio of catalytic constants is found to be 0.56. The rate of the reaction is greatly increased with the increasing size of the spiroring (from 5 to 7) in the sulfurane. Kinetic data suggest a dissociative reaction mechanism.

UR - http://www.scopus.com/inward/record.url?scp=37049069716&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=37049069716&partnerID=8YFLogxK

M3 - Article

SP - 855

EP - 859

JO - Journal of the Chemical Society, Perkin Transactions 2

JF - Journal of the Chemical Society, Perkin Transactions 2

SN - 1470-1820

IS - 5

ER -