Correction. Reactions of sulfides with t-Butyl Hypochlorite

Skattebøl, Lars; Boulette, Bernice; Solomon, Stanley C.

doi:10.1021/jo01286a630

Cited by 6 publications

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“…At first, DFT computations were performed without explicit water molecules, using only the polarizable continuum model of solvents. The attack of sulfur atom of dimethyl sulfide (1a) at the chlorine atom of HOCl (2) results in the formation of complex 3a with decrease of total energy (Figure 1), and with small increase of free energy [Scheme 1, see ΔG ‡ and ΔE ‡ data in Table S1 in the Supporting Information (SI)]. In complex 3a, the calculated distance of the S····Cl nonbonded interaction is very long, but the Cl-O bond is only slightly longer than in HOCl (Table 1).…”

Section: Attack Of Sulfur Atom Of Sulfides At Chlorine Of Hoclmentioning

confidence: 99%

“…ΔE = 0 for the separated reactants. Number of explicit water molecules is given in parenthesis SCHEME 1 Mechanism for the formation of chlorosulfonium cation (5) and λ 4 -sulfane (7) intermediates in the reaction of sulfides (1) and hypochlorous acid (2). Free energy changes (ΔG) for the reactions of Me 2 S (1a) are given in kJ mol −1 unit, in the direction of the neighboring arrow.…”

Section: Attack Of Sulfur Atom Of Sulfides At Chlorine Of Hoclmentioning

confidence: 99%

“…The mechanism of the reactions of sulfides with hypochlorites and N ‐chloroamides has been widely investigated by kinetic and nonkinetic methods. The reactions have been proposed to proceed by a polar mechanism, via the formation of chlorosulfonium cation (R 2 SCl + ) and oxychloro‐ or aminochloro‐λ 4 ‐sulfane intermediates (earlier sulfuranes, R 2 SClNu, Nu = R'O or ArSO 2 NH, Equation ).

R_{2} normalS + NuCl ⇄ ([], R_{2} {SCl}^{+}) + {Nu}^{-} \to ([], R_{2} SClNu) ⇄ R_{2} {SNu}^{+} + {Cl}^{-}

…”

Section: Introductionmentioning

confidence: 99%

“…The mechanism of the reactions of sulfides with hypochlorites [1][2][3][4][5][6][7][8] and N-chloroamides [9][10][11][12][13][14] has been widely investigated by kinetic and nonkinetic methods. The reactions have been proposed to proceed by a polar mechanism, via the formation of chlorosulfonium cation [1][2][3][4][5][6][7][8][9][10][11][12][13][14] (R 2 SCl + ) and oxychloro-or aminochloro-λ 4sulfane [4,5,7,15] intermediates (earlier sulfuranes, R 2 SClNu, Nu = R'O or ArSO 2 NH, Equation (1)).…”

Section: Introductionmentioning

confidence: 99%

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Mechanism for the reactions of sulfides with hypochlorous acid and N‐chlorosulfon‐amides: Formation of solvated chlorosulfonium cation and λ⁴‐sulfane intermediates

Ruff

Szabó

Rábai

et al. 2019

J of Physical Organic Chem

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DFT computations have been performed to study the mechanism of the reactions of sulfides with hypochlorous acid and N‐chlorosulfonamides. Sulfides can attack HOCl both at chlorine and oxygen atoms. The attack at chlorine results in the formation of chlorosulfonium cation (R2SCl+) and OH− intermediates, which transform to sulfoxide product. The high free energy of activation (ΔG‡), which is needed for the formation of ionic intermediates, is decreased considerably by solvation in protic solvents. Since the attack of sulfides at the oxygen atom of HOCl has low ΔG‡ value, the chlorination of sulfides can compete with the attack at the oxygen atom only in protic solvents. Kinetic studies showed that the reactivity of species, formed from N‐chlorosulfonamides in protic solvents, increases in the course: RSO2NCl− << RSO2NHCl < < RSO2NCl2. The chlorination of sulfides with RSO2NHCl or RSO2NCl2 results in the formation of R2SCl+ and RSO2NH− or RSO2NCl− intermediates, respectively, and the computed and experimentally derived ΔG‡ data agree in these cases. Sulfilimine (R2S═NSO2R) and sulfoxide products are formed in the reaction of R2SCl+ with RSO2NH− and water, respectively. Acyloxy‐chloro‐λ4‐sulfane intermediates are produced in the reactions of N‐chlorosulfonamides and sulfides, bearing 2‐carboxy‐phenyl group, without the intermediacy of chlorosulfonium cations. Explicit water molecules must also be included in computations for reactions proceeding with formation or destruction of ions, to get ΔG‡ values, comparable with experimental data. Supporting information may be found in the online version of this paper.

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Section: Attack Of Sulfur Atom Of Sulfides At Chlorine Of Hoclmentioning

confidence: 99%

Section: Attack Of Sulfur Atom Of Sulfides At Chlorine Of Hoclmentioning

confidence: 99%

R_{2} normalS + NuCl ⇄ ([], R_{2} {SCl}^{+}) + {Nu}^{-} \to ([], R_{2} SClNu) ⇄ R_{2} {SNu}^{+} + {Cl}^{-}

…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Mechanism for the reactions of sulfides with hypochlorous acid and N‐chlorosulfon‐amides: Formation of solvated chlorosulfonium cation and λ⁴‐sulfane intermediates

Ruff

Szabó

Rábai

et al. 2019

J of Physical Organic Chem

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“…The product from the oxidation of DBT was DBT sulfone, and t-BuOCl was transformed to t-butyl chlorite (t-BuCl). The products of the oxidation of thianes and sulfides with t-BuOCl at very low tempera tures are sulfoxides 72), 73) . Here, only DBT sulfone was determined.…”

Section: Oxidation With T-butyl Hypochloritementioning

confidence: 99%

Development of Novel Nonhydrogenation Desulfurization Process — Oxidative Desulfurization of Distillate —

Qian

2008

J. Jpn. Petrol. Inst.

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This selective review discusses nonhydrogenation desulfurization processes, particularly oxidative desulfuriza tion, for the manufacture of ultra clean fuels. The environmental regulations for transportation fuels are becom ing more and more severe, and the statutory sulfur content in various fuels was reduced to below 10 ppm in 2005, and will be lower in the near future. However, there is considerable doubt whether conventional hydrodesulfur ization processes can provide fuels with sulfur content less than 5 ppm. This review describes recent advances in nonhydrogenation desulfurization processes, particularly oxidative desulfurization, as well as our latest research results. The review consists of three sections as follows. (I) The oxidation reactivities of various sulfurcontaining compounds present in fuels, oxidation and oxidative mechanisms for various oxidant-catalyst systems are introduced. (II) The oxidation of various practical fuels such as light gas oil, kerosene, and vacuum gas oil, and others are described; and the potential of various oxidative desulfurization processes for the fuels are evaluated. (III) Removal methods of oxidized sulfur compounds in various fuels are described.

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Direct Formylation of Enol Ethers Using Cyanuric Chloride and N,N‐Dimethylformamide

Hou

Sun

Sie

et al. 2004

J Chinese Chemical Soc

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A new method to prepare a,b-unsaturated enol aldehydes is described. 3-Ethoxymethacrolein (1) and 5-formyl-3,4-dihydro-2H-pyran (5) were effectively prepared from enol ethers and the Vilsmeier-Haack type complex, derived from cyanuric chloride and DMF. One byproduct, amidine 4, was also characterized. a,b-Unsaturated enol aldehydes, such as 3-ethoxymethacrolein (1), are useful precursors to heterocyclic compounds. 2 Breitmaier's group developed a multi-step synthesis to 2-methyl malonic dialdehyde tetraethylacetal, then hydrolyzed to give the compound 1. 2 Nair et al. have reported the Vilsmeier formylation of propionaldehyde diethyl acetal in the presence of N,N-dimethylformamide (DMF) and phosphorous oxychloride (POCl 3) to give the ethoxymethacrolein in 26% yield. 3 Although this method provides a quick entrance to the compound 1, the evolution of gaseous HCl and the difficult work-up/purification procedures are problematic. Babler's group also reported the crossed-Claisen condensation of methyl formate and propanal to give the compound 1 in 61% yield after the alkylation with ethyl bromide. 4 However, this long procedure and the extremely moisture sensitive reaction condition also limit its application. Therefore, developing a direct method to prepare 1 could be useful. Formylation of n-butyl vinyl etherCyanuric chloride (0.42 g, 2.3 mmol) suspended in DMF (165 mL, 2.1 mmol) and CH 2Cl2 (1 mL) was stirred at room temperature for 3 h. n-Butyl vinyl ether (191 mg, 1.9 mmol) was added to the slurry, and the reaction was stirred for another 48 h at room temperature. Sat. K 2 CO 3(aq) (2 mL) and water (2 mL) were poured into the reaction. The reaction mixture was extracted with CH 2Cl2 (5 mL´3). The combined Direct Formylation of Enol Ethers organic solution was washed with water (3 mL), sat. NaCl (aq) (3 mL), dried over Na 2 SO 4(s) , and concentrated to give the crude oily product. The crude product was analyzed with mass spectroscopy (FAB): m/z 129 [M + H] + , 101, 73; HRMS [M + H] + calcd for C 7 H 13 O 2 , 129.0916, found 129.0917.

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Correction. Reactions of sulfides with t-Butyl Hypochlorite

Cited by 6 publications

References 0 publications

Mechanism for the reactions of sulfides with hypochlorous acid and N‐chlorosulfon‐amides: Formation of solvated chlorosulfonium cation and λ⁴‐sulfane intermediates

Mechanism for the reactions of sulfides with hypochlorous acid and N‐chlorosulfon‐amides: Formation of solvated chlorosulfonium cation and λ⁴‐sulfane intermediates

Development of Novel Nonhydrogenation Desulfurization Process — Oxidative Desulfurization of Distillate —

Direct Formylation of Enol Ethers Using Cyanuric Chloride and N,N‐Dimethylformamide

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Correction. Reactions of sulfides with t-Butyl Hypochlorite

Cited by 6 publications

References 0 publications

Mechanism for the reactions of sulfides with hypochlorous acid and N‐chlorosulfon‐amides: Formation of solvated chlorosulfonium cation and λ4‐sulfane intermediates

Mechanism for the reactions of sulfides with hypochlorous acid and N‐chlorosulfon‐amides: Formation of solvated chlorosulfonium cation and λ4‐sulfane intermediates

Development of Novel Nonhydrogenation Desulfurization Process — Oxidative Desulfurization of Distillate —

Direct Formylation of Enol Ethers Using Cyanuric Chloride and N,N‐Dimethylformamide

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Mechanism for the reactions of sulfides with hypochlorous acid and N‐chlorosulfon‐amides: Formation of solvated chlorosulfonium cation and λ⁴‐sulfane intermediates

Mechanism for the reactions of sulfides with hypochlorous acid and N‐chlorosulfon‐amides: Formation of solvated chlorosulfonium cation and λ⁴‐sulfane intermediates