The Correlation of Solvolysis Rates and the Classification of Solvolysis Reactions into Mechanistic Categories

Winstein, S.; Grunwald, Ernest; Jones, Howard

doi:10.1021/ja01150a078

Cited by 405 publications

(215 citation statements)

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“…The extended Grunwald-Winstein equation (eqn 1) [1][2][3][4] is very useful for the correlation of solvolysis reactions: log(k/k 0 ) RX …”

Section: Introductionmentioning

confidence: 99%

“…In equation (1), k and k 0 represent the specific rates of solvolysis of a substrate (RX) in a given solvent and in the standard solvent (80% ethanol), respectively; the parameter l represents the sensitivity towards changes in the solvent nucleophilicity (N T ) [3]; the parameter m represents the sensitivity towards changes in the solvent ionizing power (Y X for a leaving group X) [4]; and c represents a constant (residual) quantity.…”

Section: Introductionmentioning

confidence: 99%

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Application of the Extended Grunwald-Winstein Equation to Solvolyses of n-Propyl Chloroformate

Kyong

Won

Kevill

2005

IJMS

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Application of the extended Grunwald-Winstein equation to solvolyses of n-propyl chloroformate in a variety of pure and binary solvents indicates an addition-elimination pathway in the majority of the solvents but an ionization pathway in the solvents of highest ionizing power and lowest nucleophilicity. For methanolysis, a solvent deuterium isotope effect of 2.17 is compatible with the incorporation of general-base catalysis into the substitution process. Activation parameters are consistent with the duality of mechanism. Very modest positive salt effects are observed on adding chloride or bromide salts to the ethanolysis.

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“…The extended Grunwald-Winstein equation (eqn 1) [1][2][3][4] is very useful for the correlation of solvolysis reactions: log(k/k 0 ) RX …”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Application of the Extended Grunwald-Winstein Equation to Solvolyses of n-Propyl Chloroformate

Kyong

Won

Kevill

2005

IJMS

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“…Earlier researchers reported that 4-methoxybenzoyl chloride (3) 6-11 is followed by unimolecular reaction mechanism and 4-nitrobenzoyl chloride (4) 12 is proceeded through bimolecular pathway. Both substrates have one substituent on para-position which is not involved a steric hindrance effect at the carbonyl carbon of the reaction center.…”

Section: 5mentioning

confidence: 99%

Kinetic and Theoretical Consideration of 3,4- and 3,5-Dimethoxybenzoyl Chlorides Solvolyses

Park

Kevill²

2013

Bulletin of the Korean Chemical Society

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The solvolysis rate constants of 3,4-(1) and 3,5-dimethoxybenzoyl (2) chlorides were measured in various pure and binary solvents at 25.0 o C, and studied by application of the extended Grunwald-Winstein (G-W) equation, kinetic solvent isotope effect in methanolysis and activation parameters. The solvolysis of 1 was interpreted as the unimolecular pathway due to a predominant resonance effect from para-methoxy substituent like 4-methoxybenzoyl chloride (3), while that of 2 was evaluated as the dual mechanism, with unimolecular or bimolecular reaction pathway according to the character of solvent systems (high electrophilic/nucleophilic) chosen, caused by the inductive effect by two meta-methoxy substituents, no resonance one. In the solvolyses of 1 and 2 with two -OCH 3 groups, the resonance effect of para-methoxy substituent is more important to decide the mechanism than the inductive effect with other corresponding evidences.

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“…For bimolecular (S N 2 and/or E2) reactions, an additional term involving the sensitivity ( l ) to changes in solvent nucleophilicity ( N ) is added to equation 1, to give equation 2 [7]. …”

Section: Introductionmentioning

confidence: 99%

On the Importance of the Aromatic Ring Parameter in Studies of the Solvolyses of Cinnamyl and Cinnamoyl Halides

D’Souza

Darrington

Kevill

2010

Organic Chemistry International

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In solvolysis studies using Grunwald-Winstein plots, dispersions were observed for substrates with aromatic rings at the α-carbon. Several examples for the unimolecular solvolysis of monoaryl benzylic derivatives and related diaryl- or naphthyl- substituted derivatives have now been reported, where the application of the aromatic ring parameter (I) removes this dispersion. A recent claim suggesting the presence of an appreciable nucleophilic component to the I scale, has now been shown, in a review of the solvolysis of highly-hindered alkyl halides, to be unlikely to be correct. Attention is now focused on the application of the hI term for the solvolysis of compounds containing a double bond in the vicinity of any developing carbocation. Available specific rates of solvolysis (plus some new values) at 25°C of cinnamyl chloride, cinnamyl bromide, cinnamoyl chloride, p-chlorocinnamoyl chloride, and p-nitrocinnamoyl chloride are analyzed using the simple and extended (including the hI term) Grunwald-Winstein equations.

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The Correlation of Solvolysis Rates and the Classification of Solvolysis Reactions into Mechanistic Categories

Cited by 405 publications

References 0 publications

Application of the Extended Grunwald-Winstein Equation to Solvolyses of n-Propyl Chloroformate

Application of the Extended Grunwald-Winstein Equation to Solvolyses of n-Propyl Chloroformate

Kinetic and Theoretical Consideration of 3,4- and 3,5-Dimethoxybenzoyl Chlorides Solvolyses

On the Importance of the Aromatic Ring Parameter in Studies of the Solvolyses of Cinnamyl and Cinnamoyl Halides

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