Oxidation Of Phenyl Sulfides Research Articles

Incorporating a D-A-D-Type Benzothiadiazole Photosensitizer into MOFs for Photocatalytic Oxidation of Phenylsulfides and Benzylamines.

Oxidation and removal of highly toxic sulfides and amines are particularly important for environmental and human security but remain challenging. Here, incorporating an excellent photosensitizer, donor-acceptor-donor (D-A-D)-type 4,4'-(benzo[c][1,2,5]thiadiazole-4,7-diyl)dibenzoic (H2L), into metal-organic frameworks (MOFs) has been manifested to promote the charge separation, affording four three-dimensional (3D) MOFs (isostructural 1-Co/1-Zn with Co2/Zn2 units, and 2-Gd/2-Tb with Gd/Tb-cluster chains) as photocatalysts in the visible light-driven air-O2-mediated catalytic oxidation and removal of hazardous phenylsulfides and benzylamines. Impressively, structure-property correlation illustrated that the transition metal centers assembled in MOFs play an important role in the photocatalytic activity, and we can conclude that 1-Zn can be a robust heterogeneous catalyst possessing good light adsorption and fast charge separation in oxidation removal reactions of both benzylamines and phenylsulfides under visible light irradiation and room temperature with excellent activity/selectivity, stability, and reusability.

Exploring the chemical space of phenyl sulfide oxidation by automated optimization

Automated platforms allow for rapid, detailed screening of chemical systems.

Nucleophilic versus Electrophilic Activation of Hydrogen Peroxide over Zr-Based Metal-Organic Frameworks.

Zr-based metal-organic frameworks (Zr-MOF) UiO-66 and UiO-67 catalyze thioether oxidation in nonprotic solvents with unprecedentedly high selectivity toward corresponding sulfones (96-99% at ca. 50% sulfide conversion with only 1 equiv of H2O2). The reaction mechanism has been investigated using test substrates, kinetic, adsorption, isotopic (18O) labeling, and spectroscopic tools. The following facts point out a nucleophilic character of the peroxo species responsible for the superior formation of sulfones: (1) nucleophilic parameter XNu = 0.92 in the oxidation of thianthrene 5-oxide and its decrease upon addition of acid; (2) sulfone to sulfoxide ratio of 24 in the competitive oxidation of methyl phenyl sulfoxide and p-Br-methyl phenyl sulfide; (3) significantly lower initial rates of methyl phenyl sulfide oxidation relative to methyl phenyl sulfoxide (kS/kSO = 0.05); and (4) positive slope ρ = +0.42 of the Hammett plot for competitive oxidation of p-substituted aryl methyl sulfoxides. Nucleophilic activation of H2O2 on Zr-MOF is also manifested by their capability of catalyzing epoxidation of electron-deficient C═C bonds in α,β-unsaturated ketones accompanied by oxidation of acetonitrile solvent. Kinetic modeling on methyl phenyl sulfoxide oxidation coupled with adsorption studies supports a mechanism that involves the interaction of H2O2 with Zr sites with the formation of a nucleophilic oxidizing species and release of water followed by oxygen atom transfer from the nucleophilic oxidant to sulfoxide that competes with water for Zr sites. The nucleophilic peroxo species coexists with an electrophilic one, ZrOOH, capable of oxygen atom transfer to nucleophilic sulfides. The predominance of nucleophilic activation of H2O2 over electrophilic one is, most likely, ensured by the presence of weak basic sites in Zr-MOFs identified by FTIR spectroscopy of adsorbed CDCl3 and quantified by adsorption of isobutyric acid.

Synthesis, structures, and catalytic oxidation of three aqua-coordinated and oxo-bridged diruthenium(III) complexes with sulfobenzoate and 2,2′-bipyridine

Three new diruthenium(III) complexes, [Ru2O(2-sb)2(2,2′-bipy)2(H2O)2]·2.5H2O (1), [Ru2O(3-sb)2(2,2′-bipy)2(H2O)2]·9H2O (2), and [Ru2O (4-sb)2(2,2′-bipy)2(H2O)2]·9H2O (3), where sb2− is sulfobenzoate dianion and 2,2′-bipy is 2,2′-bipyridine, were synthesized using hydrothermal methods and characterized by IR, elemental analysis, thermogravimetric analysis, UV–vis, and fluorescence spectra. The single crystal X-ray analysis showed that each of these complexes has a dinuclear core stabilized by two bridging carboxylates and one bridging O2−. Variable sb2− ligands (2-sb, 3-sb, and 4-sb) in these complexes lead to diverse electronic spectroscopic behavior. The efficiency of activating methyl phenyl sulfide oxidation utilizing H2O2 in 3 equiv. was studied at 23 ± 2 °C. The effect of the amount of catalyst and solvents on activities was investigated. Under optimized reaction conditions, the major product was sulfoxide. Complex 1 gave significant conversion of 100 and 98% selectivity for sulfoxide after 4 h.

ChemInform Abstract: Selective Oxidation of Phenyl Sulfides (I) to Sulfoxides (II) or Sulfones (III) Using OxoneR and Wet Alumina.

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Sulfide oxidation with H 2O 2 catalyzed by manganese complex of N, N′, N″-tris(2-hydroxypropyl)-1,4,7-triazacyclononane

[MnL](ClO 4) 2 (L = N, N′, N″-tris(2-hydroxypropyl)-1,4,7-triazacyclononane) has been tested for catalyzing sulfide oxidation. In the presence of this complex, ethyl phenyl sulfide, butyl sulfide and phenyl sulfide are completely oxidized to the corresponding sulfoxides and sulfones with H 2O 2 as the oxidant. 2-Chloroethyl phenyl sulfide oxidation yield 2-chloroethyl phenyl sulfone and phenyl vinyl sulfone. In ethyl phenyl sulfide oxidation, effects of complex and H 2O 2 concentration and temperature on the reaction rate have been discussed. Through controlling reaction conditions, ethyl phenyl sulfoxide and ethyl phenyl sulfone may be produced selectively. The UV–Vis and electron paramagnetic resonance (EPR) studies on catalyst solution indicate that metal centre of the complex is transformed from Mn(II) to Mn(IV) after the addition of H 2O 2. At 25 °C, rate constant for ethyl phenyl sulfide oxidation is 4.38 × 10 −3 min −1.

Role of protons in methyl phenyl sulfide oxidation with hydrogen peroxide catalyzed by Ti(IV)-monosubstituted heteropolytungstates

Acid tetrabutylammonium salts of Ti(IV)-monosubstituted heteropolytungstate, PW11TiO405−, show high catalytic acitivity in the oxidation of methyl phenyl sulfide with hydrogen peroxide, while the corresponding tetrabutylammonium salts containing no protons are poor catalysts for this reaction.

ChemInform Abstract: Chemoselective Method for the Preparation of Phenyl Sulfoxides by the Oxidation of Phenyl Sulfides with 2‐Hydroperoxy‐2‐methoxypropane.

ChemInform Abstract: Chemoselective Method for the Preparation of Phenyl Sulfoxides by the Oxidation of Phenyl Sulfides with 2‐Hydroperoxy‐2‐methoxypropane.

Electrochemistry of organic sulfur compounds V. a polarographic study on the anodic oxidation of phenyl sulfides

Electrochemistry of organic sulfur compounds V. a polarographic study on the anodic oxidation of phenyl sulfides