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 language | English |
|---|---|
| Pages (from-to) | 4990-4992 |
| Number of pages | 3 |
| Journal | Journal of Organic Chemistry |
| Volume | 44 |
| Issue number | 26 |
| DOIs | |
| Publication status | Published - Jan 1 1979 |
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All Science Journal Classification (ASJC) codes
- Organic Chemistry
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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 journal › Article
}
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.
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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 -