Solvation Effects in Hydrolysis of 2-Toluenesulfonyl Halides in Aqueous Dioxane. Catalysis with Water Molecules in Cyclic Transition States

Иванов, С. Н.; Kislov, V. V.; Gnedin, B. G.

doi:10.1023/b:rugc.0000025175.58238.e4

Cited by 3 publications

(2 citation statements)

References 8 publications

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“…The kinetics and mechanism of the hydrolysis of aliphatic and aromatic sulfonyl chlorides have been previously investigated in detail. , Our objectives here were simply to establish whether TNBO 2 Cl behaves as a typical aryl sulfonyl chloride and (in the case of PhSO 2 Cl) to extend the range of reaction conditions to include the conditions we employed in our kinetic studies of the oxidation reaction (namely to employ I = 1.0 and to extend the pH above pH 11). The rate of hydrolysis of ArSO 2 Cl can be described by the following rate law: −d false[ ArSO 2 Cl false] / d t = k obs false[ ArSO 2 Cl false] = false( k 0 + k OH false[ OH − false] false) false[ ArSO 2 Cl false] We have interpreted the rate law as hydrolysis by H 2 O ( k 0 ) and by OH − ( k OH ).…”

Section: Discussionmentioning

confidence: 99%

Reactive Sulfur Species: Kinetics and Mechanism of the Oxidation of Aryl Sulfinates with Hypochlorous Acid

2009

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The mechanism of oxidation of ArSO(2)(-) (PhSO(2)(-) and 5-sulfinato-2-nitrobenzoic acid = TNBO(2)(1-/2-)) with HOCl/OCl(-) has been investigated using the kinetic method. In contrast to previous reports for PhSO(2)(-) (for which it was suggested that OCl(-) and not HOCl was the reactant), the reaction proceeds through a conventional pathway: nucleophilic attack by ArSO(2)(-) on HOCl with concomitant Cl(+) transfer to give a sulfonyl chloride intermediate (ArSO(2)Cl), which we have identified spectrophotometrically. Remarkably, the rate constant for the reaction of HOCl with ArSO(2)(-) is on the order of 10(9) M(-1) s(-1), larger than the rate constants for corresponding thiolates, and is nearly diffusion-controlled. In contrast, the rate constant for the reaction of OCl(-) with ArSO(2)(-) is approximately 7 orders of magnitude smaller.

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Section: Discussionmentioning

confidence: 99%

Reactive Sulfur Species: Kinetics and Mechanism of the Oxidation of Aryl Sulfinates with Hypochlorous Acid

2009

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“…DFT computations on the transition state for hydrolysis of a series of benzenesulfonyl chlorides with seventeen explicit water molecules present in the structure were reported and employed the B3LYP/6-311G(d,p) level after screening a range of functionals and basis sets [122]. Additional studies on the transition state for hydrolysis of various sulfonyl halides have also been reported [123,124]. Also having highly favorable thermodynamics is the reaction of an epoxide, such as 2-methyloxirane (27), with methylamine, resulting in a computed ∆G for the reaction between S6 and S7).…”

Section: Additional Modification Reactionsmentioning

confidence: 99%

Thermodynamic Overview of Bioconjugation Reactions Pertinent to Lysine and Cysteine Peptide and Protein Residues

Lopandic,

Merza,

Honek

2023

Compounds

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Bioconjugation reactions are critical to the modification of peptides and proteins, permitting the introduction of biophysical probes onto proteins as well as drugs for use in antibody-targeted medicines. A diverse set of chemical reagents can be employed in these circumstances to covalently label protein side chains, such as the amine moiety in the side chain of lysine and the thiol functionality in cysteine residues, two of the more frequently employed sites for modification. To provide researchers with a thermodynamic survey of the reaction of these residues with frequently employed chemical modification reagents as well as reactive cellular intermediates also known to modify proteins non-enzymatically, a theoretical investigation of the overall thermodynamics of models of these reactions was undertaken at the T1 and G3(MP2) thermochemical recipe levels (gas phase), the M06-2X/6-311+G(2df,2p)/B3LYP/6-31G(d) (gas and water phase), and the M06-2X/cc-PVTZ(-f)++ density functional levels of theory (water phase). Discussions of the relationship between the reagent structure and the overall thermodynamics of amine or thiol modification are presented. Of additional interest are the observations that routine cellular intermediates such as certain thioesters, acyl phosphates, and acetyl-L-carnitine can contribute to non-enzymatic protein modifications. These reactions and representative click chemistry reactions were also investigated. The computational survey presented herein (>320 reaction computations were undertaken) should serve as a valuable resource for researchers undertaking protein bioconjugation. A concluding section addresses the ability of computation to provide predictions as to the potential for protein modification by new chemical entities, with a cautionary note on protein modification side reactions that may occur when employing synthetic substrates to measure enzyme kinetic activities.

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Hydrate-Anion Complex of Proton [H(H2O)n]+А− as the Basis of the Complex Acidity Function Н0w of Aqueous Solutions of Strong Mineral Acids in Excess of Water

Ivanov,

Kozlov,

Nikiforova

et al. 2023

Russ J Gen Chem

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Solvation Effects in Hydrolysis of 2-Toluenesulfonyl Halides in Aqueous Dioxane. Catalysis with Water Molecules in Cyclic Transition States

Cited by 3 publications

References 8 publications

Reactive Sulfur Species: Kinetics and Mechanism of the Oxidation of Aryl Sulfinates with Hypochlorous Acid

Reactive Sulfur Species: Kinetics and Mechanism of the Oxidation of Aryl Sulfinates with Hypochlorous Acid

Thermodynamic Overview of Bioconjugation Reactions Pertinent to Lysine and Cysteine Peptide and Protein Residues

Hydrate-Anion Complex of Proton [H(H2O)n]+А− as the Basis of the Complex Acidity Function Н0w of Aqueous Solutions of Strong Mineral Acids in Excess of Water

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