Solvolysis of Sulphonyl Halides. II. The Alcoholysis of Aromatic Sulphonyl Chlorides in Ethanol-Acetone and Methanol-Acetone

Jenkins, FE; Hambly, AN

doi:10.1071/ch9610205

Cited by 7 publications

(13 citation statements)

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“…When a specific sulfonyl chloride is considered, the reaction rate varies in the order: methanolysis > ethanolysis > iso ‐propanolysis. The presence of ortho ‐methyl groups accelerates the process in agreement with earlier observations …”

Section: Resultssupporting

confidence: 92%

“…The reactivity of sulfonyl chlorides significantly depends on the nucleophile concentration (Figs. –6), as predicted for S N 2 processes . Assuming the reaction order on the nucleophile relates to the number of solvent molecules participating in the TS, our results suggest the TS involves two nucleophile molecules in methanolysis and three for iso ‐propanolysis (Table ).…”

Section: Resultssupporting

confidence: 74%

“…Nucleophilic substitution at sulfur of the sulfonyl group has been a frequent matter of debate because of the ambiguity of the solvolysis mechanism, often considered as bimolecular, with different transition state (TS) symmetries, involving catalytic assistance of the solvent, a possible molecular rearrangement during the nucleophilic attack, and so on. A number of common mechanistic criteria for solvolytic processes of arenesulfonyl chlorides points to a typical S N 2‐nucleophilic substitution mechanism: similar secondary and solvent isotope effect, effect of the change of nucleophile, and solvent effect …”

Section: Introductionmentioning

confidence: 99%

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Solvent network at the transition state in the solvolysis of hindered sulfonyl compounds

Iazykov

Rublova

Canle

et al. 2016

J of Physical Organic Chem

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Alcoholysis rates of unhindered benzenesulfonyl chlorides (X‐ArSO2Cl, X = H‐; 4‐Br‐; 4‐Me‐) are similar in methanol; the same behavior is also observed in ethanol, whereas the reactivity order in iso‐propanol is 4 Me‐ < H‐ < 4‐Br‐. On the other hand, alcoholysis of sterically hindered arenesulfonyl chlorides (X‐ArSO2Cl) (X = 2,4,6‐Me3‐3‐NO2‐; 2,6‐Me2‐4‐tBu‐; 2,4,6‐Me3‐; 2,3,5,6‐Me4‐; 2,4,6‐iPr3‐; 2,4‐Me2‐; 2,4,6‐(OMe)3‐) in all studied alcohols show a significant increase in reactivity, the so‐called positive steric effect. Most of the substrates showed a reaction order b ~ 2 with respect to the nucleophile in methanol and ethanol, and b ~ 3 in iso‐propanol. The correlation between reactivity and the Kirkwood function (1/ξ) gives negative sensitivity (U) for all systems. All substrates showed high sensitivity to media nucleophilicity that depends on ΣσX. Obtained results suggest the alcoholysis of benzenesulfonyl chlorides proceeds through SN2 mechanism where the transition state (TS) involves the participation of 2–3 alcohol molecules; such a TS can be cyclic, in the case of unbranched alcohols, or linear, for alcohols with bulkier hydrocarbon groups like iso‐propanol. To include the number of alcohol molecules playing such a role in the TS, the following terminology is proposed: cSN2sn for SN2 reactions involving n solvent molecules in a cyclic (c) TS, where “s” stands for the solvent and “n” is either the closest integer or half‐integer to the reaction order relative to the solvent or, in computational studies, the proposed number of solvent molecules taking part in the TS, whereas SN2sn is proposed when the TS is not cyclic. Copyright © 2016 John Wiley & Sons, Ltd.

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Section: Resultssupporting

confidence: 92%

Section: Resultssupporting

confidence: 74%

Section: Introductionmentioning

confidence: 99%

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Solvent network at the transition state in the solvolysis of hindered sulfonyl compounds

Iazykov

Rublova

Canle

et al. 2016

J of Physical Organic Chem

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“…Despite the existence of a large corpus of research on solvolytic processes near sulfonyl centers , details on the mechanism of this nucleophilic substitution remain unclear. A number of authors have proposed S N 2 or borderline S N 1–S N 2 mechanisms for this process . However, sterically hindered derivatives of aromatic sulfonic acids that contain o ‐alkyl groups show kinetic features that pose questions on the classical view of the bimolecular substitution mechanism .…”

Section: Introductionmentioning

confidence: 99%

Isotope Effects in the Solvolysis of Sterically Hindered Arenesulfonyl Chlorides

Iazykov

Canle

Santaballa

et al. 2015

Int J of Chemical Kinetics

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Solvent isotope effects in the ethanolysis of sterically hindered arenesulfonyl chlorides ruled out a proton transfer in the rate-determining step and agreed with a S N 2 mechanism involving at least a second solvent molecule in the transition state (TS). The lack of a secondary kinetic isotope effect in the o-alkyl groups allows us to disregard the possible contribution of σ -π hyperconjugation. The measured activation parameters are consistent with a S N 2 mechanism involving the participation of solvent molecules in the TS, possibly forming a cyclic TS through a chain of solvent molecules. C 2015 Wiley Periodicals, Inc. Int J Chem Kinet 47: [744][745][746][747][748][749][750] 2015

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“…Nucleophilic displacement from a tetrahedral sulfur has been treated generally as analogous to the corresponding displacement from carbon and the same terminology based on similar mechanistic distinctions has tended to be used (4)(5)(6)(7)(8)(9)(10)(11)(12)(13). T o the degree that the activation processes are similar, such a comparison is valid but in this and in the following paper we attempt to identify and evaluate the source of differences.…”

mentioning

confidence: 99%

Sulfonyl Chloride Kinetics. Part II. Solvolysis of a Series of Benzenesulfonyl Chlorides: An Unexpected Heat Capacity Variation

Robertson¹,

Rossal²

1971

Can. J. Chem.

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First order rate constants for the solvolysis of a series of 4-X-benzenesulfonyl chlorides (where X = MeO, Me, Br, and NOz) were measured by the conductance method in HzO over the approximate temperature range of 0 to 25". Pseudothermodynamic parameters, AG*, AH*, AS*, and ACp* were derived and the high accuracy of the rate constants enabled an estimation of dACp*/dT.A trigonal bipyramidal transition state is favored for the nucleophilic attack which is probably by an SN2 type mechanism. A novel explanation for the effect of 4-methoxy on ACp* involves a temperature dependent water-solute interaction, which has general applicability to the behavior of 4-methoxy substituents.On a mesurd, par la methode de la conductivite, dans I'eau et a des temperatures entre 0 et 25 "C, les constantes de vitesse du premier ordre pour la solvolyse d'une sirie de chlorures de benzenesulfonyles substituis en position 4. On en a dtrive les parametres pseudothermodynamiques AG*, AH*, AS*, et ACp* et grlce a la grande precision des mesures, on a pu estimer la valeur de dAC,*/dT.On favorise un etat de transition trigonal et bipyramidal pour I'attaque nucleophile qui est probablement un mecanisme SN2. Une nouvelle explication pour l'effet du groupement methoxy en position 4 sur ACp* implique une interaction entre l'eau et le solute qui serait dependante de la temperature; cette explication serait d'application generale chaque fois que des substituants methoxyle en position 4 seraient impliqub.

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Solvolysis of Sulphonyl Halides. II. The Alcoholysis of Aromatic Sulphonyl Chlorides in Ethanol-Acetone and Methanol-Acetone

Cited by 7 publications

References 0 publications

Solvent network at the transition state in the solvolysis of hindered sulfonyl compounds

Solvent network at the transition state in the solvolysis of hindered sulfonyl compounds

Isotope Effects in the Solvolysis of Sterically Hindered Arenesulfonyl Chlorides

Sulfonyl Chloride Kinetics. Part II. Solvolysis of a Series of Benzenesulfonyl Chlorides: An Unexpected Heat Capacity Variation

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