70823-04-0Relevant articles and documents
Preparation method for symmetric diaryl disulfide
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Paragraph 0043; 0044; 0045; 0046, (2019/04/17)
The invention discloses a preparation method for symmetric diaryl disulfide. The preparation method comprises the following steps: using aromatic hydrocarbon as shown in a general formula (I) as a rawmaterial and reacting with chlorosulfonic acid to generate aryl chlorosulfonic acid, and reacting with sulfoxide chloride to synthesize aryl sulfonyl chloride as shown in a general formula (II); andpreparing the symmetric diaryl disulfide as shown in a general formula (III) under the action of a reducing agent through a reduction reaction by the aryl sulfonyl chloride as shown in the general formula (II). The disclosed preparation method for the symmetric diaryl disulfide has many advantages of low toxicity of the reaction raw material, short reaction time, cheap reagents and easy acquisition, convenient separation and purification and the like, and has very high application value and industrial production value.
Propanolysis of arenesulfonyl chlorides: Nucleophilic substitution at sulfonyl sulfur
Iazykov, Mykyta,Canle, Moisés,Santaballa, J. Arturo,Rublova, Ludmila
supporting information, (2017/09/08)
We have studied the mechanism of solvolysis of arenesulfonyl chlorides by propan-1-ol and propan-2-ol at 303-323 K. Kinetic profiles were appropriately fit by first-order kinetics. Reactivity increases with electron-donating substituents. Ortho-alkyl substituted derivatives of arenesulfonyl chlorides show increased reactivity, but the origin of this “positive” ortho-effect remains unclear. Likely, ortho-methyl groups restrict rotation around the C-S bond, facilitating the attack of the nucleophile. No relevant reactivity changes have been found with propan-1-ol and propan-2-ol in terms of nucleophile steric effect. The existence of isokinetic relationships for all substrates suggests a single mechanism for the series. Solvolysis reactions of all substrates in both alcohols show isokinetic temperatures (Tiso) close to the working temperature range, which is an evidence of the process being influenced by secondary reactivity factors, likely of steric nature in the TS. Solvation plays a relevant role in this reaction, modulating the reactivity. In some cases, the presence of t-Bu instead of Me in para- position leads to changes in the first solvation shell, increasing the energy of the reaction (ca. 1?kJ·mol?1). The obtained results suggest the same kinetic mechanism of solvolysis of arenesulfonyl chlorides for propan-1-ol and propan-2-ol, as in MeOH and EtOH, where bimolecular nucleophilic substitution (SN2) takes place with nucleophilic solvent assistance of one alcohol molecule and the participation of the solvent network involving solvent molecules of the first solvation shell.
Solvent network at the transition state in the solvolysis of hindered sulfonyl compounds
Iazykov, Mykyta,Rublova, Ludmila,Canlel, Moisés,Santaballa, J. Arturo
, (2016/12/22)
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- 2Cl) (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
Isotope Effects in the Solvolysis of Sterically Hindered Arenesulfonyl Chlorides
Iazykov, Mykyta,Canle L., Moisés,Santaballa, J. Arturo,Rublova, Ludmila
, p. 744 - 750 (2015/10/06)
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 SN2 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 SN2 mechanism involving the participation of solvent molecules in the TS, possibly forming a cyclic TS through a chain of solvent molecules.
MODULATORS OF CCR9 RECEPTOR AND METHODS OF USE THEREOF
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Page/Page column 57, (2010/03/02)
Provided are compounds that are modulators of CCR9 receptor activity, compositions containing the compounds and methods of use of the compounds and compositions. In certain embodiments, provided are methods for treating or ameliorating diseases associated
Efficient method for the synthesis of new [2-(alkylarylthio)ethyl]pyridines
Sviridova,Laba,Vasil'ev,Litvinov
, p. 563 - 565 (2007/10/03)
An efficient method for the synthesis of new [2-(alkylarylthio)ethyl]pyridines was developed. The method is based on one-step mono- and polyalkylchlorosulfonation of arenes with complex electrophilic reagents (RX-HSO3Cl, RX = Bu1Cl, and 1-AdBr).