Marked influence of minute amounts of water on the selectivity of alkylation site of sodium 2-naphtholate (ambident anion) in aprotic solvent

Seiji Shinkai, Toshihiko Fukunaga, Osamu Manabe, Toyoki Kunitake

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

It has been established that solvation is an integral part of most bimolecular reactions in solution. In particular, Parker1 has demonstrated that the reactivities of anionic species are dramatically affected by the solvation through hydrogen bonding with protic solvent species. The marked activation of anionic species observed in dipolar aprotic solvents has since been attributed to the desolvation effect, that is, exclusion of hydrogen bond forming molecules from the reaction center.1 On the other hand, the reaction rate in dipolar aprotic solvents has been believed to be affected little by small amounts (several millimolar) of remaining water, 2-4 since dipolar aprotic solvent molecules (i.e., hygroscopic molecules) can compete with reacting anions as acceptors for water molecules.3 It was found, however, that the rate constants for the nucleophilic reactions of oxyanions are affected by a water concentration of less than 1 M, and the plots of rate constants vs. [H2O] increased exponentially with decreasing water concentration.5-7 The influence of small amounts of water on the reaction rate is an old but still controversial problem.

Original languageEnglish
Pages (from-to)4990-4992
Number of pages3
JournalJournal of Organic Chemistry
Volume44
Issue number26
DOIs
Publication statusPublished - Jan 1 1979

Fingerprint

Alkylation
Anions
Sodium
Water
Solvation
Molecules
Reaction rates
Rate constants
Hydrogen bonds
Chemical activation

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

Cite this

Marked influence of minute amounts of water on the selectivity of alkylation site of sodium 2-naphtholate (ambident anion) in aprotic solvent. / Shinkai, Seiji; Fukunaga, Toshihiko; Manabe, Osamu; Kunitake, Toyoki.

In: Journal of Organic Chemistry, Vol. 44, No. 26, 01.01.1979, p. 4990-4992.

Research output: Contribution to journalArticle

Shinkai, Seiji ; Fukunaga, Toshihiko ; Manabe, Osamu ; Kunitake, Toyoki. / Marked influence of minute amounts of water on the selectivity of alkylation site of sodium 2-naphtholate (ambident anion) in aprotic solvent. In: Journal of Organic Chemistry. 1979 ; Vol. 44, No. 26. pp. 4990-4992.
@article{2039370cb2d94915a6881d638e6e95d9,
title = "Marked influence of minute amounts of water on the selectivity of alkylation site of sodium 2-naphtholate (ambident anion) in aprotic solvent",
abstract = "It has been established that solvation is an integral part of most bimolecular reactions in solution. In particular, Parker1 has demonstrated that the reactivities of anionic species are dramatically affected by the solvation through hydrogen bonding with protic solvent species. The marked activation of anionic species observed in dipolar aprotic solvents has since been attributed to the desolvation effect, that is, exclusion of hydrogen bond forming molecules from the reaction center.1 On the other hand, the reaction rate in dipolar aprotic solvents has been believed to be affected little by small amounts (several millimolar) of remaining water, 2-4 since dipolar aprotic solvent molecules (i.e., hygroscopic molecules) can compete with reacting anions as acceptors for water molecules.3 It was found, however, that the rate constants for the nucleophilic reactions of oxyanions are affected by a water concentration of less than 1 M, and the plots of rate constants vs. [H2O] increased exponentially with decreasing water concentration.5-7 The influence of small amounts of water on the reaction rate is an old but still controversial problem.",
author = "Seiji Shinkai and Toshihiko Fukunaga and Osamu Manabe and Toyoki Kunitake",
year = "1979",
month = "1",
day = "1",
doi = "10.1021/jo00394a059",
language = "English",
volume = "44",
pages = "4990--4992",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "26",

}

TY - JOUR

T1 - Marked influence of minute amounts of water on the selectivity of alkylation site of sodium 2-naphtholate (ambident anion) in aprotic solvent

AU - Shinkai, Seiji

AU - Fukunaga, Toshihiko

AU - Manabe, Osamu

AU - Kunitake, Toyoki

PY - 1979/1/1

Y1 - 1979/1/1

N2 - It has been established that solvation is an integral part of most bimolecular reactions in solution. In particular, Parker1 has demonstrated that the reactivities of anionic species are dramatically affected by the solvation through hydrogen bonding with protic solvent species. The marked activation of anionic species observed in dipolar aprotic solvents has since been attributed to the desolvation effect, that is, exclusion of hydrogen bond forming molecules from the reaction center.1 On the other hand, the reaction rate in dipolar aprotic solvents has been believed to be affected little by small amounts (several millimolar) of remaining water, 2-4 since dipolar aprotic solvent molecules (i.e., hygroscopic molecules) can compete with reacting anions as acceptors for water molecules.3 It was found, however, that the rate constants for the nucleophilic reactions of oxyanions are affected by a water concentration of less than 1 M, and the plots of rate constants vs. [H2O] increased exponentially with decreasing water concentration.5-7 The influence of small amounts of water on the reaction rate is an old but still controversial problem.

AB - It has been established that solvation is an integral part of most bimolecular reactions in solution. In particular, Parker1 has demonstrated that the reactivities of anionic species are dramatically affected by the solvation through hydrogen bonding with protic solvent species. The marked activation of anionic species observed in dipolar aprotic solvents has since been attributed to the desolvation effect, that is, exclusion of hydrogen bond forming molecules from the reaction center.1 On the other hand, the reaction rate in dipolar aprotic solvents has been believed to be affected little by small amounts (several millimolar) of remaining water, 2-4 since dipolar aprotic solvent molecules (i.e., hygroscopic molecules) can compete with reacting anions as acceptors for water molecules.3 It was found, however, that the rate constants for the nucleophilic reactions of oxyanions are affected by a water concentration of less than 1 M, and the plots of rate constants vs. [H2O] increased exponentially with decreasing water concentration.5-7 The influence of small amounts of water on the reaction rate is an old but still controversial problem.

UR - http://www.scopus.com/inward/record.url?scp=33744659561&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33744659561&partnerID=8YFLogxK

U2 - 10.1021/jo00394a059

DO - 10.1021/jo00394a059

M3 - Article

AN - SCOPUS:33744659561

VL - 44

SP - 4990

EP - 4992

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 26

ER -