Kinetic Solvent Isotope Effect in the Hydrolysis of Sulphonic Anhydrides.

Christensen, Niels Jørgen; Wanger, Marianne; Carter, Robert E.; Corrodi, H.; Eriksson, G.; Blinc, R.; Paušak, S.; Ehrenberg, L.; Dumanović, J.

doi:10.3891/acta.chem.scand.21-0899

Cited by 5 publications

(4 citation statements)

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“…24 Lower KSIE values for arenesulfonic anhydrides, than for the corresponding chloride, have also been observed for hydrolyses in water or deuterium oxide. 4,6,7 Again, the lower KSIE values observed for anhydrides are consistent with lowered demand for nucleophilic assistance in the presence of a better leaving group.…”

Section: Discussionmentioning

confidence: 62%

“…We have previously reported 1 a parallel study of the solvolyses of an alkanesulfonic anhydride: methanesulfonic anhydride (3). There have only been a few mechanistic studies involving substitution reactions of sulfonic anhydrides, 1-5 some of which 1, [3][4][5] involve their solvolysis reactions. Christensen 3 showed that the solvolyses of arenesulfonic anhydrides in aqueous acetone and dioxane were 100-400 fold faster than the corresponding solvolyses of the arenesulfonyl chloride.…”

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confidence: 99%

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Rate and Product Studies in the Solvolyses of Two Arenesulfonic Anhydrides

Kevill

Ryu

2007

Journal of Chemical Research

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The specific rates of solvolysis of benzenesulfonic anhydride (1) and p-toluenesulfonic anhydride (2) have been measured conductometrically at −10°C in 34 solvents for 1 and 33 solvents for 2. Studies at higher temperatures have allowed extrapolated values in additional solvents to be calculated. All of the values, for 35 solvents for 1 and for 37 solvents for 2, have been used in an extended Grunwald–Winstein equation treatment using NT and YOTs values. Activation parameters in several solvents and kinetic solvent isotope effects (MeOH/MeOD) have been determined for both substrates. Product selectivity values ( S) have been determined for binary mixtures of water with ethanol, methanol, or 2, 2, 2-trifluoroethanol. The results from the kinetic and product studies are compared to those previously reported for methanesulfonic anhydride (3). An SN2 mechanism is proposed for the solvolytic displacement reactions of the three substrates in all of the solvents used in the investigation.

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Section: Discussionmentioning

confidence: 62%

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confidence: 99%

Rate and Product Studies in the Solvolyses of Two Arenesulfonic Anhydrides

Kevill

Ryu

2007

Journal of Chemical Research

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“…1.7 in methanol [ 11 ], consistent with a third order mechanism ( Section 2.1 ). Other anhydrides show lower KSIE values: e.g., in methanol for acetyl tosylate (CH 3 COOTs, KSIE = 0.99 at −39.6 °C [ 50 ]), benzoyl tosylate (PhCOOTs, KSIE = 1.1 at −10 °C [ 11 ]), and other anhydrides (PhSO 2 ) 2 O, Ts 2 O, Ms 2 O) KSIE = 1.35–1.4 at −10 °C [ 51 , 52 ]); in mixed organic/water mixtures of 1.2–1.3 for solvolyses of various aromatic sulfonic acid anhydrides at 22.5 °C [ 53 ]. These results are consistent with changes within the S N 2-S N 1 spectrum.…”

Section: Resultsmentioning

confidence: 99%

Calculated Third Order Rate Constants for Interpreting the Mechanisms of Hydrolyses of Chloroformates, Carboxylic Acid Halides, Sulfonyl Chlorides and Phosphorochloridates

2015

IJMS

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Hydrolyses of acid derivatives (e.g., carboxylic acid chlorides and fluorides, fluoro- and chloroformates, sulfonyl chlorides, phosphorochloridates, anhydrides) exhibit pseudo-first order kinetics. Reaction mechanisms vary from those involving a cationic intermediate (SN1) to concerted SN2 processes, and further to third order reactions, in which one solvent molecule acts as the attacking nucleophile and a second molecule acts as a general base catalyst. A unified framework is discussed, in which there are two reaction channels—an SN1-SN2 spectrum and an SN2-SN3 spectrum. Third order rate constants (k3) are calculated for solvolytic reactions in a wide range of compositions of acetone-water mixtures, and are shown to be either approximately constant or correlated with the Grunwald-Winstein Y parameter. These data and kinetic solvent isotope effects, provide the experimental evidence for the SN2-SN3 spectrum (e.g., for chloro- and fluoroformates, chloroacetyl chloride, p-nitrobenzoyl p-toluenesulfonate, sulfonyl chlorides). Deviations from linearity lead to U- or V-shaped plots, which assist in the identification of the point at which the reaction channel changes from SN2-SN3 to SN1-SN2 (e.g., for benzoyl chloride).

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“…values compared to corresponding values for displacement from carbon (15) are consistent with this hypothesis. A similar model was proposed by Bunton and Frei (33) for the hydrolysis of aryl sulfonates and by Christensen (34,35) (38) in order to accommodate the stereochemical implication of the bipyramidal transition state. On this evidence the above hypothesis is not unreasonable and the k.s.i.e.…”

Section: Discussionmentioning

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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Kinetic Solvent Isotope Effect in the Hydrolysis of Sulphonic Anhydrides.

Cited by 5 publications

References 0 publications

Rate and Product Studies in the Solvolyses of Two Arenesulfonic Anhydrides

Rate and Product Studies in the Solvolyses of Two Arenesulfonic Anhydrides

Calculated Third Order Rate Constants for Interpreting the Mechanisms of Hydrolyses of Chloroformates, Carboxylic Acid Halides, Sulfonyl Chlorides and Phosphorochloridates

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

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