New rate–product correlations for general-base catalysed reactions in alcohol–water mixtures
- 1 January 1992
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society, Perkin Transactions 2
- No. 5,p. 743-744
- https://doi.org/10.1039/p29920000743
Abstract
Selectivities (S) for solvolyses of p-nitrobenzoyl chloride (1), p-nitrobenzenesulfonyl chloride (2), p-nitrobenzyl chloride (3 Z = NO2) and p-methoxybenzyl chloride (3; Z = OMe) in alcohol–water mixtures are consistent with third-order terms in the rate law, including terms for nucleophilic attack and general-base catalysis by water and/or alcohol. The results document new rate–product correlations and new reactivity–selectivity relationships, which help to define ‘normal’ behaviour from which deviations can be identified for further investigations.Keywords
This publication has 20 references indexed in Scilit:
- Distinguishing between solvation effects and mechanistic changes. Effects due to differences in solvation of aromatic rings and alkyl groupsThe Journal of Organic Chemistry, 1991
- Separation of mass law and solvent effects in kinetics of solvolyses of p-nitrobenzoyl chloride in aqueous binary mixturesThe Journal of Organic Chemistry, 1988
- Formation and stability of ring-substituted 1-phenylethyl carbocationsJournal of the American Chemical Society, 1984
- Reactions of substituted 1-phenylethyl carbocations with alcohols and other nucleophilic reagentsJournal of the American Chemical Society, 1984
- General base catalysis of the addition of hydroxylic reagents to unstable carbocations and its disappearanceJournal of the American Chemical Society, 1984
- Effect of solvent on .beta.-arylalkyl solvolysisJournal of the American Chemical Society, 1978
- Trapping of the oxocarbonium ion intermediate in the hydrolysis of acetophenone dimethyl ketalsJournal of the American Chemical Society, 1977
- Cation-anion combination reaction. XII. Rates, equilibriums, and activation parameters for reactions of triarylmethyl cations in aqueous solutionJournal of the American Chemical Society, 1975
- Use of added sodium azide as a mechanistic probe for solovolysis reactionsJournal of the American Chemical Society, 1971
- 187. Mechanism of substitution at a saturated carbon atom. Part XXII. A kinetic demonstration of the unimolecular solvolysis of alkyl halides. (Section D) kinetics of, and salt effects in, the hydrolysis of pp′-dimethylbenzhydryl chloride in aqueous acetoneJournal of the Chemical Society, 1940