Oxidation of Sulfides to Sulfoxides. Part 1. Oxidation Using Halogen Derivatives.

Kowalski, Piotr; Mitka, Katarzyna; Ossowska, Katarzyna; Kolarska, Zofia

doi:10.1002/chin.200524225

Cited by 3 publications

(5 citation statements)

References 1 publication

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“…The first step involves the reaction between sulfide, CEES, and bromine to form a bromosulfonium complex that is likely a reaction intermediate. 6,26,33,34…”

Section: Resultsmentioning

confidence: 99%

“…T he selective conversion of sulfides to sulfoxides without overoxidation to the sulfone is a key synthetic reaction for multiple applications. [1][2][3][4][5][6] One particularly pressing application is the decontamination of bis(2-chloroethyl) sulfide (sulfur mustard or HD), one of the highest tonnage chemical warfare agents (CWA) and one that is highly persistent in the environment. [7][8][9][10][11][12] While HD can be removed, in principle, by either oxidation or hydrolysis, oxidation is generally targeted as the hydrolysis reaction with HD is quite slow.…”

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confidence: 99%

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A solvent-free solid catalyst for the selective and color-indicating ambient-air removal of sulfur mustard

et al. 2021

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Bis(2-chloroethyl) sulfide or sulfur mustard (HD) is one of the highest-tonnage chemical warfare agents and one that is highly persistent in the environment. For decontamination, selective oxidation of HD to the substantially less toxic sulfoxide is crucial. We report here a solvent-free, solid, robust catalyst comprising hydrophobic salts of tribromide and nitrate, copper(II) nitrate hydrate, and a solid acid (NafionTM) for selective sulfoxidation using only ambient air at room temperature. This system rapidly removes HD as a neat liquid or a vapor. The mechanisms of these aerobic decontamination reactions are complex, and studies confirm reversible formation of a key intermediate, the bromosulfonium ion, and the role of Cu(II). The latter increases the rate four-fold by increasing the equilibrium concentration of bromosulfonium during turnover. Cu(II) also provides a colorimetric detection capability. Without HD, the solid is green, and with HD, it is brown. Bromine K-edge XANES and EXAFS studies confirm regeneration of tribromide under catalytic conditions. Diffuse reflectance infrared Fourier transform spectroscopy shows absorption of HD vapor and selective conversion to the desired sulfoxide, HDO, at the gas–solid interface.

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“…The first step involves the reaction between sulfide, CEES, and bromine to form a bromosulfonium complex that is likely a reaction intermediate. 6,26,33,34…”

Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

A solvent-free solid catalyst for the selective and color-indicating ambient-air removal of sulfur mustard

et al. 2021

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“…Though the exact roles of CCl4 in this electrochemical oxidation of fluorosulfide to fluorosulfoxide still need to investigate in detail, the reductive generated chlorospecies (Clor Cl•) from CCl4 was proposed to facilitate this oxidation process. [57][58][59] Further attempts to access the fluorosulfone (I) with increases of the applied potential (Ecell = 2.8-3.8 V), however, only led to the decomposition of the starting material. 60…”

Section: Scheme 2 Mechanistic Experimentsmentioning

confidence: 99%

Electrochemistry Enabled Selective Vicinal Fluorosulfenylation and Fluorosulfoxidation of Alkenes

Jiang

et al. 2021

Preprint

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Both sulfur and fluorine play important roles in organic synthesis, the life science, and materials science. The direct incorporation of these elements into organic scaffolds with precise control of the oxidation states of sulfur moieties is of great significance. Herein, we report the highly selective electrochemical vicinal fluorosulfenylation and fluorosulfoxidation reactions of alkenes, which were enabled by the unique ability of electrochemistry to dial in the potentials on demand. Preliminary mechanistic investigations revealed that the fluorosulfenylation reaction proceeded through a radical-polar crossover mechanism involving a key episulfonium ion intermediate. Subsequent electrochemical oxidation of fluorosulfides to fluorosulfoxides were readily achieved under a higher applied potential with the adventitious H2O in the reaction mixture.

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“…Developed techniques tend to have limitations like the use of strong acids, high temperatures, long reaction times, unsafe and contaminant solvents and reagents [11,12]. …”

Section: Introductionmentioning

confidence: 99%

“…Sulfoxides are mostly prepared by the oxidation of the corresponding sulfides but without a strict control of reaction conditions, such as time, temperature and the relative amount of oxidants, over-oxidation to sulfone generally occurs. Developed techniques tend to have limitations like the use of strong acids, high temperatures, long reaction times, unsafe and contaminant solvents and reagents [ 11 , 12 ].…”

Section: Introductionmentioning

confidence: 99%

Exploring the Use of a Guanine-Rich Catalytic DNA for Sulfoxide Preparation

2015

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A guanine-rich DNA oligonucleotide complexed with hemin was used to catalyze controlled oxygen transfer reactions to different sulfides for sulfoxide preparation in the presence of H2O2. Comparable activities were obtained when using fully modified L-DNA. In addition, oligonucleotide immobilization led to an active catalyst which could be successfully recovered and reused without loss of activity.

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Oxidation of Sulfides to Sulfoxides. Part 1. Oxidation Using Halogen Derivatives.

Abstract: For Abstract see ChemInform Abstract in Full Text.

Cited by 3 publications

References 1 publication

A solvent-free solid catalyst for the selective and color-indicating ambient-air removal of sulfur mustard

A solvent-free solid catalyst for the selective and color-indicating ambient-air removal of sulfur mustard

Electrochemistry Enabled Selective Vicinal Fluorosulfenylation and Fluorosulfoxidation of Alkenes

Exploring the Use of a Guanine-Rich Catalytic DNA for Sulfoxide Preparation

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