Structural study of 2,4,6-triisopropylbenzenesulfonyl chloride

Laba, V. I.; Sviridova, A. V.; Нестеров, В. Н.

doi:10.1134/s1063774509010088

Cited by 5 publications

(8 citation statements)

References 13 publications

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“…The accuracy of applied theoretical methods in reproducing geometries of sulfonyl chlorides was verified by comparing the optimized geometries with experimentally determined crystal structures. Thus, the following reported X-ray structures were used as references: 4-methylbenzenesulfonyl chloride ((4-Me)-1) [42], 2,4,6-trimethylbenzenesulfonyl chloride ((2,4,6-Me 3 )-1) [14] and 2,4,6-tri(isopropyl)benzenesulfonyl chloride ((2,4,6-iPr 3 )-1) [43,44].…”

Section: Structural Features Of Arenesulfonyl Chlorides 1: Dft Calculmentioning

confidence: 99%

“…geometries with experimentally determined crystal structures. Thus, the following reported X-ray structures were used as references: 4-methylbenzenesulfonyl chloride ((4-Me)-1) [42], 2,4,6trimethylbenzenesulfonyl chloride ((2,4,6-Me3)-1) [14] and 2,4,6-tri(isopropyl)benzenesulfonyl chloride ((2,4,6-iPr3)-1) [43,44]. Comparison of the calculated and experimental geometrical parameters is presented in Figures 3 and 4 and in Tables S1-S3 in Supplementary Material (SM).…”

Section: Comparison Of the Calculated And Experimental Geometrical Pamentioning

confidence: 99%

“…Overlapping of the calculated [B3LYP-GD3/6-311+G(2d,p)//6-31+G(d), gas phase] and X-ray structures for 2,4,6-iPr 3 PhSO 2 Cl ((2,4,6-iPr 3 )-1)[43].…”

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confidence: 99%

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Nucleophilic Substitution at Tetracoordinate Sulfur. Kinetics and Mechanism of the Chloride-Chloride Exchange Reaction in Arenesulfonyl Chlorides: Counterintuitive Acceleration of Substitution at Sulfonyl Sulfur by ortho-Alkyl Groups and Its Origin

et al. 2020

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The chloride-chloride exchange reaction in arenesulfonyl chlorides was investigated experimentally and theoretically by density functional theory (DFT) calculations. The second order rate constants and activation parameters of this identity reaction were determined for 22 variously substituted arenesulfonyl chlorides using radio-labeled Et4N36Cl. The chloride exchange rates of 11 sulfonyl chlorides bearing para-and meta-substituents (σ constants from −0.66 to +0.43) in the aromatic ring followed the Hammett equation with a ρ-value of +2.02. The mono- and di-ortho-alkyl substituted sulfonyl chlorides exhibit an enhanced reactivity although both inductive and steric effects lower the reaction rate. The DFT calculations of their structures together with X-ray data showed that an increased reactivity is mainly due to a peculiar, rigid, strongly compressed and sterically congested structure. The DFT studies of the title reaction revealed that it proceeds via a single transition state according to the SN2 mechanism. The analogous fluoride exchange reaction occurs according to the addition–elimination mechanism (A–E) and formation of a difluorosulfurandioxide intermediate. The reliability of the calculations performed was supported by the fact that the calculated relative rate constants and activation parameters correlate well with the experimental kinetic data.

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Section: Structural Features Of Arenesulfonyl Chlorides 1: Dft Calculmentioning

confidence: 99%

Section: Comparison Of the Calculated And Experimental Geometrical Pamentioning

confidence: 99%

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Nucleophilic Substitution at Tetracoordinate Sulfur. Kinetics and Mechanism of the Chloride-Chloride Exchange Reaction in Arenesulfonyl Chlorides: Counterintuitive Acceleration of Substitution at Sulfonyl Sulfur by ortho-Alkyl Groups and Its Origin

et al. 2020

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“…Space requirements are also supported by X‐ray diffraction data. The highly sterically hindered 2,4,6‐ i Pr 3 ‐benzenesulfonyl chloride shows a slightly distorted benzene ring plane (±0.021 Å), which takes the form of a highly flattened “bath”. Moreover, the relative orientation of the ortho‐iso‐ propyl substituents facilitates intramolecular interaction between the oxygen atoms of the sulfo group and the hydrogens of the central carbon atoms of the iso ‐propyl ortho ‐groups (Fig.…”

Section: Resultsmentioning

confidence: 99%

“…The “positive” ortho ‐effect can be explained through the spatial requirements of the TS: ortho ‐alkyl groups limit free rotation around the C‐S bond of the sulfonyl chloride, leaving the S in a position that favors the formation of cyclic TS (Scheme ). TS of unhindered substrates, although having less steric constraints, can also be cyclic.…”

Section: Resultsmentioning

confidence: 99%

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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Experimental spectroscopic, molecular structure, electronic solvation, biological prediction and topological analysis of 2, 4, 6-tri (propan-2-yl) benzenesulfonyl chloride: An antidepressant agent

Jeelani¹,

Muthu²,

Ramesh³

et al. 2022

Journal of Molecular Liquids

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Structural study of 2,4,6-triisopropylbenzenesulfonyl chloride

Cited by 5 publications

References 13 publications

Nucleophilic Substitution at Tetracoordinate Sulfur. Kinetics and Mechanism of the Chloride-Chloride Exchange Reaction in Arenesulfonyl Chlorides: Counterintuitive Acceleration of Substitution at Sulfonyl Sulfur by ortho-Alkyl Groups and Its Origin

Nucleophilic Substitution at Tetracoordinate Sulfur. Kinetics and Mechanism of the Chloride-Chloride Exchange Reaction in Arenesulfonyl Chlorides: Counterintuitive Acceleration of Substitution at Sulfonyl Sulfur by ortho-Alkyl Groups and Its Origin

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

Experimental spectroscopic, molecular structure, electronic solvation, biological prediction and topological analysis of 2, 4, 6-tri (propan-2-yl) benzenesulfonyl chloride: An antidepressant agent

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