Inhibition of Phenol Alkylations by Ethers. Kinetic Evidence for Phenol-Ether Complexes

Hart, Harold; Cassis, Frank A.; Bordeaux, John J.

doi:10.1021/ja01635a051

Cited by 6 publications

(3 citation statements)

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“…The inhibition of phenol alkylation by ethers is an example of the effect on the rate of reaction of hydrogen bonding between reactant and solvent [272]. Dioxane in proportion to its concentration was found to decrease the rate of alkylation of phenol by /-butyl chloride.…”

Section: Hydrogen-bonding Influence On Reactionsmentioning

confidence: 99%

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Solvent Influence on Rates and Mechanisms

Amis

Hinton

1973

Solvent Effects on Chemical Phenomena

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Section: Hydrogen-bonding Influence On Reactionsmentioning

confidence: 99%

“…The results of the calculations are shown in Table 5.14 [272]. Calculations were made assuming (1) dioxane served only as a diluent for the reactants, (2) dioxane forms a 1:1 complex with phenol, and (3) dioxane forms a 1-dioxane :2-phenol complex with phenol.…”

Section: Hydrogen-bonding Influence On Reactionsmentioning

confidence: 99%

Solvent Influence on Rates and Mechanisms

Amis

Hinton

1973

Solvent Effects on Chemical Phenomena

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“…It is noteworthy, in view of the particularly large influence of the hydroxy-group on the rate of solvolysis of 2-bromo-4-dibromomethylphenol in aqueous dioxan, that dioxan reduces the rate of nethylation of phenol through hydrogenbonding (Ref. 50).…”

Section: Appendix (A) Relative Magnitude Of Energy Differences Providmentioning

confidence: 99%

Hyperconjugation: intermediates and transition states in replacement and elimination

Mare¹

1984

Pure and Applied Chemistry

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A review is given of the development of experimental evidence for hyperconjugation in the form of electron-release to an unsaturated or electron-deficient centre from saturated H-C and CC bonds. This type of electron-release can contribute regioselectively to the reactivity of organic molecules, and need not involve breakage of the H-C or CC bond; under these circumstances, H-C and CC bonds make similar contributions to the observed effects of alkyl and derived groups, the relative contributions varying with reaction and solvent. In the limit, however, this form of electron-release can result in breakage of the hyperconjugating bond, and in such circumstances (as in transition states leading to proton-loss or 1,2-elimination), H-C bonds become much more effective than CC bonds because of the greater solvation of incipient protons than of incipient alkyl cations. Evidence for the corresponding hyperconjugation by H-O bonds comes especially, but not exclusively, from the relative rates of electrophilic aromatic replacements affected by H-0 and R-O groups. Recent experiments on the effects of these groups on nucleophilic replacements in aromatic side-chains show that the electron-releasing power of the H-O group is quite variable, and suggest that the impact of H-O hyperconjugation is more dependent on the reaction and the solvent than that of H-C hyperconjugation has been shown to be. Reaction pathways in the hydrolysis of R0.C6H2Br2.CHBr2 and RO.C6H3Br.CHBr2, which can lead to products both of replacement and of elimination, are discussed, and isotope effects in H-C and H-O hyperconjugation are compared.

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