Limitations of the transition state variation model. Part 2. Dual reaction channels for solvolyses of 2,4,6-trimethylbenzenesulphonyl chloride

Koo, In Sun; Bentley, T. William; Kang, Dong Hun; Lee, Ikchoon

doi:10.1039/p29910000175

Cited by 38 publications

(39 citation statements)

References 17 publications

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“…A fairly recent review favored an interpretation of a concerted S N 2 mechanism, involving an attack at sulfur by solvent. 16 Our analyses are consistent with this explanation.…”

Section: 10supporting

confidence: 82%

Rate and Product Studies of 5-Dimethylamino-Naphthalene-1-Sulfonyl Chloride under Solvolytic Conditions

Koh

Kang²

2014

Bulletin of the Korean Chemical Society

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The solvolysis rate constants of 5-dimethylamino-naphthalene-1-sulfonyl chloride ((CH 3 ) 2 NC 10 H 6 SO 2 Cl, 1) in 31 different solvents are well correlated with the extended Grunwald-Winstein equation, using the N T solvent nucleophilicity scale and Y Cl solvent ionizing scale with sensitivity values of 0.96 ± 0.09 and 0.53 ± 0.03 for l and m, respectively; the correlation coefficient value was 0.955. These l and m values can be considered to support an S N 2 reaction pathway having a transition state (TS) structure similar to that of the benzenesulfonyl chloride reaction. This interpretation is further supported by the activation parameters, i.e., relatively small positive ΔH ≠ (12.0 to 15.9 kcal·mol) and large negative ΔS ≠ (−23.1 to −36.3 cal·mol) values, and the solvent kinetic isotope effects (SKIEs, 1.34 to 1.88). Also, the selectivity values (S = 1.2 to 2.9) obtained in binary solvents are consistent with the proposed mechanism.

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“…A fairly recent review favored an interpretation of a concerted S N 2 mechanism, involving an attack at sulfur by solvent. 16 Our analyses are consistent with this explanation.…”

Section: 10supporting

confidence: 82%

Rate and Product Studies of 5-Dimethylamino-Naphthalene-1-Sulfonyl Chloride under Solvolytic Conditions

Koh

Kang²

2014

Bulletin of the Korean Chemical Society

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“…Therefore, the determination of the l and m values would provide valuable information concerning the structure of the transition state for the solvolyses. The l value of 0.93 was smaller than those recently reported for reactions proceeding through an addition-elimination mechanism (l  1.5), whereas these values were similar to those previously reported for the bimolecular solvolyses of diphenylthiophosphinyl chloride 10 (l = 1.0), allyl chloroformate 11 (l = 0.93), 9-fluorenyl chloroformate 12 (l = 0.95), and N,N,N',N'-tetramethyldiamidophosphoro-chloridate 13 (l = 1.14). This suggests an S N 2 mechanism involving nucleophilic attack by the solvent at sulfur atom of 1.…”

Section: Resultscontrasting

confidence: 44%

“…9c,d, [10][11][12][13] Recent interpretations for attack at sulfur have been in terms of bimolecular attack, but with some degree of uncertainty as to whether this is concerted or stepwise. Bentley, Jones and Koo 14 suggested that both mechanisms can operate, with the concerted mechanism favored in the more polar solvents.…”

Section: Resultsmentioning

confidence: 99%

Product-Rate Correlations for Solvolyses of 2,4-Dimethoxybenzenesulfonyl Chloride

Kim¹,

Choi²,

Park³

et al. 2014

Bulletin of the Korean Chemical Society

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The solvolysis rate constants of 2,4-dimethoxybenzenesulfonyl chloride (1) in 30 different solvents are well correlated with the extended Grunwald-Winstein equation, using the NT solvent nucleophilicity scale and YCl solvent ionizing scale, with sensitivity values of 0.93 ± 0.14 and 0.65 ± 0.06 for l and m, respectively. These l and m values can be considered to support a SN2 reaction pathway. The activation enthalpies (H  ) were 12.4 to 14.6 kcal·mol 1 and the activation entropies (S, which is consistent with the proposed bimolecular reaction mechanism. The solvent kinetic isotope effects (SKIE) were 1.74 to 1.86, which is also in accord with the SN2 mechanism and was possibly assisted using a general-base catalysis. The values of product selectivity (S) for solvolyses of 1 in alcohol/water mixtures was 0.57 to 6.5, which is also consistent with the proposed bimolecular reaction mechanism. Third-order rate constants, kww and kaa, were calculated from the rate constants (kobs), together with kaw and kwa calculated from the intercept and slope of the plot of 1/S vs.[water]/[alcohol]. The calculated rate constants, kcalc (kww, kaw, kwa and kaa), are in satisfactory agreement with the experimental values, supporting the stoichiometric solvation effect analysis.

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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 .…”

Section: Introductionmentioning

confidence: 99%

“…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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Limitations of the transition state variation model. Part 2. Dual reaction channels for solvolyses of 2,4,6-trimethylbenzenesulphonyl chloride

Cited by 38 publications

References 17 publications

Rate and Product Studies of 5-Dimethylamino-Naphthalene-1-Sulfonyl Chloride under Solvolytic Conditions

Rate and Product Studies of 5-Dimethylamino-Naphthalene-1-Sulfonyl Chloride under Solvolytic Conditions

Product-Rate Correlations for Solvolyses of 2,4-Dimethoxybenzenesulfonyl Chloride

Isotope Effects in the Solvolysis of Sterically Hindered Arenesulfonyl Chlorides

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