Diphenyl Sulfide Research Articles

Highly Stable Poly(diphenyl sulfide piperidine) Anion Exchange Membrane Grafting with Flexible Side-Chain Cationic Group for Water Electrolysis

Highly Stable Poly(diphenyl sulfide piperidine) Anion Exchange Membrane Grafting with Flexible Side-Chain Cationic Group for Water Electrolysis

Organoelectrocatalytic cyclopropanation of alkenyl trifluoroborates with methylene compounds

Cyclopropanes are not only privileged motifs in many natural products, agrochemicals, and pharmaceuticals, but also highly versatile intermediates in synthetic chemistry. As such, great effort has been devoted to the cyclopropane construction. However, novel catalytic methods for cyclopropanation with two abundant substrates, mild conditions, high functional group tolerance, and broad scope are still highly desirable. Herein, we report an intermolecular electrocatalytic cyclopropanation of alkenyl trifluoroborates with methylene compounds. The reaction uses simple diphenyl sulfide as the electrocatalyst under base-free conditions. And thus, a broad scope of various methylene compounds as well as vinyltrifluoroborates is demonstrated, including styrenyl, 1,3-dienyl, fluorosulfonyl, and base-sensitive substrates. Preliminary mechanistic studies are presented, revealing the critical role of the boryl substituent to facilitate the desired pathway and the role of water as the hydrogen atom source.

Synergistic catalytic effect of titanium and iron incorporated to spherical MCM-41 in selective catalytic oxidation of diphenyl sulphide with H2O2

Spherical mesoporous silicas of MCM-41 type modified with titanium, iron or both these metals were prepared by co-condensation method and tested in the role of catalysts for selective oxidation of diphenyl sulphide with H2O2 to diphenyl sulphoxide and diphenyl sulphone. The monometallic catalysts containing titanium or iron were found to be active catalysts of diphenyl sulphide mainly to diphenyl sulphoxide. A very significant increase in catalytic activity was observed for the bimetallic samples, containing both titanium and iron. Moreover, in the case of bimetallic catalysts with higher titanium loading, diphenyl sulphone is a dominating reaction product. The increased activity of the bimetallic catalysts has been related to the synergistic operation of titanium and iron in conversion of hydrogen peroxide into reactive species, which in the next step oxidise diphenyl sulphoxide.

Nasturtium leaf compounds, diphenyl disulfide and lyral, against Atta sexdens (Hymenoptera: Formicidae) and their symbiotic fungi.

Social insect pests, particularly leaf-cutting ants, present a considerable challenge in terms of control. Leaf-cutting ants are significant agricultural, forestry, and pasture pests, and understanding their behavior and defense mechanisms is essential for managing their colonies effectively. While toxic ant baits are a primary control method, the limited availability of effective insecticides and concerns over their hazardous nature has spurred the search for alternative solutions, particularly natural compounds, which aligns with the goals of forest certification groups. In the light of previous evidence demonstrating the efficacy of nasturtium leaves (Tropaeolum majus L. (Brassicales: Tropaeolaceae)) in suppressing leaf-cutting ant colonies, this study investigates 2 active components of nasturtium leaf extracts: diphenyl disulfide and lyral. We tested their impact on Atta sexdens (L.) (Hymenoptera: Formicidae), the most prevalent leaf-cutter ant species in Brazil, and their symbiotic fungus, Leucoagaricus gongylophorus (Möller) Singer (Agaricales: Agaricaceae). We conducted experiments with increasing concentrations of diphenyl disulfide and lyral, assessing their effects on the symbiotic fungus and on forager workers and gardeners of A. sexdens colonies. Our findings revealed no fungicidal activity, and ant mortality was minimal in both topical and ingestion bioassays with the exception of gardeners topically exposed to diphenyl sulfide. Furthermore, the compounds did not affect leaf ingestion, but diphenyl disulfide did increase interactions among foragers. These results suggest that neither diphenyl disulfide nor lyral are the primary contributors to the suppression of leaf-cutting ant colonies by nasturtium leaves. However, they may enhance the formicidal activity of other compounds present in nasturtium leaves.

Introducing the sulfone group as a cellulose-binding site to improve the hydrolysis performance of the solid acid

To clarify the role of the specific sulfur-containing functional groups of solid acids in the hydrolysis of cellulose, it is necessary to prepare a solid acid bearing relatively single sulfur-containing functional groups apart from the –SO3H group. However, diphenylsulfone cannot be polymerized through Friedel-Crafts alkylation, limiting the possibility of preparing sulfone-based solid acids. Therefore, diphenyl sulfide was crosslinked through Friedel-Crafts alkylation, followed by sulfonation and oxidation. The results showed that the sulfone group was successfully introduced onto the solid acid, and the density of –SO3H groups increased by 80.88 % through this strategy. The sulfone group is a strong adsorption site for cellulose, and its introduction leads to a decrease in apparent activation energy. Cellulose conversion and glucose selectivity are as high as 77.54 % and 97.13 %, respectively. Unexpectedly, the stability of the functional groups and carbon skeleton is significantly improved due to the conjugation effect of the sulfone group.

Extraction of Dibenzyl Disulfide from Transformer Oils by Acidic Ionic Liquid.

In recent years, dibenzyl disulfide (DBDS) in transformer oils has caused many transformer failures around the world, and its removal has attracted more attention. In this work, nine imidazolium-based ionic liquids (ILs) were applied as effective, green desulfurization extractants for DBDS-containing transformer oil for the first time. The results show that the desulfurization ability of the ILs for DBDS followed the order of [BMIM]FeCl4 > [BMIM]N(CN)2 > [BMIM]SCN > [BMIM](C4H9O)2PO2 > [BMIM]MeSO4 > [BMIM]NTf2 > [BMIM]OTf > [BMIM]PF6 > [BMIM]BF4. Especially, [BMIM]FeCl4 ionic liquid had excellent removal efficiency for DBDS, with its S partition coefficient KN (S) being up to 2642, which was much higher than the other eight imidazolium-based ILs. Moreover, the extractive performance of [BMIM]FeCl4 increased with an increasing molar ratio of FeCl3 to [BMIM]Cl, which was attributed to its Lewis acidity and fluidity. [BMIM]FeCl4 ionic liquid could also avail in the desulfurization of diphenyl sulfide (DPS) from model oils. The experimental results demonstrate that π-π action, π-complexation, and Lewis acid-base interaction played important roles in the desulfurization process. Finally, the ([BMIM]FeCl4) ionic liquid could be recycled five times without a significant decrease in extractive ability.

A new anchoring group to fabricate single-molecule junctions: diphenyl sulfide

A new anchor (–SPh) was confirmed with the ability to enable reproducible molecular junction formation.

Synthesis and Structure of Diphenyl Oxide–Diphenyl Sulfide (Co)polyarylene Diphthalides and Their Copolymers with Styrene

Synthesis and Structure of Diphenyl Oxide–Diphenyl Sulfide (Co)polyarylene Diphthalides and Their Copolymers with Styrene

Silica-titania mesoporous silicas of MCM-41 type as effective catalysts and photocatalysts for selective oxidation of diphenyl sulfide by H2O2

Abstract Spherical Ti-MCM-41, synthetized by co-condensation method, presented very promising activity in catalytic and photocatalytic oxidation of diphenyl sulfide with H2O2 to obtain diphenyl sulfoxide and diphenyl sulfone. Mesoporous silica materials with various titanium content were analyzed with respect to chemical composition (inductively coupled plasma optical emission spectrometry), structure properties (X-ray diffraction), textural properties (low-temperature N2 adsorption–desorption), morphology (scanning electron microscopy), forms and aggregation introduced titanium species (diffuse reflectance spectroscopy, Raman spectroscopy), and surface acidity (NH3-TPD). Titanium introduced in the samples was present mainly in the form of highly dispersed species, presenting catalytic and photocatalytic activities in diphenyl sulfide oxidation with H2O2. Efficiency of the reaction increased with an increase in titanium loading in the samples and was significantly intensified under UV irradiation. The role of various Ti species in diphenyl sulfide oxidation was presented and discussed.

Sisal-derived acid-char molybdenum catalyst for reductive deoxygenation of sulfoxides

The deoxygenation of sulfoxides is a rather important reaction from both synthetic and biological points of view, due to the potential of sulfides as intermediates in a variety of processes. Homogenous Mo-based catalysts successfully perform the reduction of diphenyl sulfoxide to diphenyl sulfide with high yields but present the well-known limitations regarding recovery and recycling. Thus, in the present work, two new supported catalysts were prepared through the immobilization of molybdenum precursor species (dichlorodioxodi(aquo)molybdenum(VI) and sodium molybdate), onto a sisal-derived acid-char (S13.5), obtained from rope industry wastes by acid-mediated carbonization. The heterogeneous Mo-based materials were characterized by IR spectroscopy, elemental analysis, ICP, solid state NMR, XPS, and SEM, and were evaluated as catalysts for the reduction of sulfoxides to sulfides in the presence of phenylsilane as reducing agent under different reaction conditions. The influence of various experimental parameters, including reducing agent type and amount, solvent type, and acid promoter were investigated. Catalytic studies revealed that both catalysts deoxygenate sulfoxides at 120 °C in toluene solution with high yields (up to 97%). The MoO2Cl2 derived catalyst shown to be highly efficient in the reduction of diaryl, alkylaryl, dibenzyl, and dialkyl sulfoxides to the corresponding sulfoxides using phenylsilane as reductant and no need of acid promoter.

Periodate-Mediated Aerobic Oxidation of Sulfides over a Bifunctional Porphyrin-polyoxometalate Catalyst: Photosensitized Singlet Oxygen Oxidation of Iodate to Periodate.

Regeneration of terminal oxidants by molecular oxygen in metal-catalyzed oxidations of organic substrates has the advantage of avoiding the use of stoichiometric amounts of hazardous and/or expensive reagents to meet (some of) the green chemistry requirements. In the present study, photosensitized singlet oxygen oxidation of iodate to periodate has been used to regenerate the oxidant in polyoxometalate (POM)-catalyzed oxidation of sulfides to sulfoxides with periodate in water. To the best of our knowledge, it is the first report on singlet oxygen oxidation of iodate to periodate. In order to determine the contribution of photooxidation and oxidation pathways in the formation of sulfoxide, the oxidation of diphenyl sulfide with a very low reactivity toward aerobic photooxidation was studied; a sevenfold increase in the conversion of the sulfide to the diphenyl sulfoxide was observed for the reaction conducted in the presence of H2TMPyP-PW12O40/IO3-/O2/hν compared to that in the presence of H2TMPyP-PW12O40/O2/hν. Also, under the same conditions, a ca. 1.5-fold increase was observed in the case of methyl phenyl sulfide, which shows high reactivity toward both the oxidation and photooxidation reactions. A porphyrin-POM nanocomposite formed by the electrostatic immobilization of meso-tetra(N-methylpyridinium-4-yl)porphyrin (H2TMPyP) on PW12O40 was employed for the one-pot oxidation and photooxidation reactions. Field-emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), diffuse-reflectance UV-vis spectroscopy, thermal gravimetric analysis, and Fourier transform infrared were used to characterize the formation of the hybrid compound. An average particle size of 42 nm was estimated for H2TMPyP-PW12O40 from XRD peak broadening using the Scherrer equation. Also, FESEM images showed the formation of nearly spherical nanoparticles with a size of ca. 200 nm. The redshift of the Soret band of H2TMPyP upon immobilization on POM was attributed to strong N-H···O hydrogen-bond interactions between POM and porphyrin.

A Generic Platform for Upcycling Polystyrene to Aryl Ketones and Organosulfur Compounds.

Polystyrene (PS) is one of the least recycled large-volume commodity plastics due to bulkiness of foam products and associated contaminants. PS recycling is also severely hampered by the lack of financial incentive, limited versatility, and poor selectivity of existing methods. To this end, herein we report a thermochemical recycling strategy of "degradation-upcycling" to synthesize a library of high-value aromatic chemicals from PS wastes with high versatility and selectivity. Two cascade reactions are selected to first degrade PS to benzene under mild temperatures, followed by the derivatization thereof utilizing a variety of acyl/alkyl and sulfinyl chloride additives. To demonstrate the versatility, nine ketones and sulfides of cosmetic and pharmaceutical relevance were prepared, including propiophenone, benzophenone, and diphenyl sulfide. The approach is also amenable to sophisticated upcycling reaction designs and can produce desired products stepwise. The facile and versatile approach will provide a scalable and profitable methodology for upcycling PS waste into value-added chemicals.

A Generic Platform for Upcycling Polystyrene to Aryl Ketones and Organosulfur Compounds

AbstractPolystyrene (PS) is one of the least recycled large‐volume commodity plastics due to bulkiness of foam products and associated contaminants. PS recycling is also severely hampered by the lack of financial incentive, limited versatility, and poor selectivity of existing methods. To this end, herein we report a thermochemical recycling strategy of “degradation‐upcycling” to synthesize a library of high‐value aromatic chemicals from PS wastes with high versatility and selectivity. Two cascade reactions are selected to first degrade PS to benzene under mild temperatures, followed by the derivatization thereof utilizing a variety of acyl/alkyl and sulfinyl chloride additives. To demonstrate the versatility, nine ketones and sulfides of cosmetic and pharmaceutical relevance were prepared, including propiophenone, benzophenone, and diphenyl sulfide. The approach is also amenable to sophisticated upcycling reaction designs and can produce desired products stepwise. The facile and versatile approach will provide a scalable and profitable methodology for upcycling PS waste into value‐added chemicals.

Catalysts based on nickel salt heteropolytungstates for selective oxidation of diphenyl sulfide

Abstract Nickel salts of Keggin heteropolytungstates with the general formula Ni x A y W12−y O39or40 (A = Si/P) were synthesized and studied as bulk catalytic materials or supported ones by deposition on modified and functionalized clay minerals (pillared layered clay and porous clay heterostructure). Characterizations by Raman, 31P and 29Si-NMR, and ESEM-EDS techniques showed that pure and supported systems preserved the Ni/W ratio and the expected structural properties of heteropolyanions. These materials were evaluated as catalysts in the selective oxidation of sulfides to sulfoxides or sulfones, using aqueous hydrogen peroxide and mild reaction conditions. The bulk materials, with a higher content of Ni, displayed a remarkable catalytic behavior in the oxidation of diphenyl sulfide (Ni3PW11NiO40H, 90% conversion in 15 min at 75°C, 100% sulfone selectivity in 3 h). Supported catalysts, particularly the non-functionalized PCH (Ni2SW12O40/PCH), showed excellent activity, with also being selective in the oxidation of sulfide to sulfoxide (87% conversion, 88.9% sulfoxide selectivity). The reuse of these materials was studied in the optimum reaction conditions, resulting in similar activity and selectivity.

Hyper-Cross-Linked Polymers with Sulfur-Based Functionalities for the Prevention of Aging Effects in PIM-1 Mixed Matrix Membranes

The instability of gas permeation rates over time in PIM-1-based membranes is one of the obstacles preventing the implementation of this technology on larger scales. The addition of porous materials to the PIM-1 matrix is a known process to reduce aging effects in PIM-1-based membranes. Many porous solids of various chemical natures have been tested, ranging from inorganic to inorganic–organic hybrids to completely organic materials. Here, we report on the synthesis of two hyper-cross-linked polymers (HCPs) based on the diphenyl sulfide monomer, synthesized in either dichloromethane at 35 °C or dichloroethane at 78 °C. Two mixed matrix membranes (MMMs) were obtained from the addition of 3 wt % of either filler to PIM-1. Both the CO2 permeation rates and the CO2/N2 selectivity were measured for the pure PIM-1 membrane and for the two MMMs over a period of 400 days. PIM-1 exhibits a classic aging behavior with an 85% drop in the CO2 permeation rate with respect to the initial value. For the two MMMs, a retention of 50% of the initial CO2 permeability was instead observed after more than 400 days of aging. Despite the low surface area and low pore volume of the fillers, we show that diphenyl sulfide-based HCPs can reduce the aging rate in PIM-1 membranes.

ZnO–TiO2 Nanoparticles Coated by the Dioxomolybdenum (VI) bis-Schiff Base Complex for Catalytic Oxidation of Sulfides

The oxygenation processes for the organic compounds have great applications in fine organic fabrications. To speed up progress in the industrialization of such oxidation systems, a monometallic dioxomolybdenum (VI) bis-Schiff base complex (MoO2L2) was synthesized through coordination of easily accessible 4-hydroxyiminophenol ligand (HL) with cis-MoO22+ ion in an octahedral geometry. The structural conformation of MoO2L2 and its coordinated ligand (HL) was determined using modern spectrophotometric tools. A heterogeneous catalyst (MoO2L2@ZnO–TiO2) was successfully prepared by immobilization of MoO2L2 on the surface of ZnO–TiO2 nanostructured particles through the deprotonation of 4-OH group in its coordinated ligand. Various analytical techniques were used to examine the surface morphology and internal structure features of ZnO–TiO2 and MoO2L2@ZnO–TiO2 nanocomposites. To study the catalytic efficiency of MoO2L2 and MoO2L2@ZnO–TiO2-based catalysts, they were employed in the oxygenation process of Ph2S (diphenyl sulfide) and MePhS (methylphenyl sulfide) using the most environmentally friendly oxidant (an aqueous H2O2) under an aerobic environment. A high degree of selectivity was observed for the productivity of diphenyl sulfoxide (Ph2SO) and methylphenyl sulfoxide (MePhSO), with some contamination of overoxidation side products (Ph2SO2 and MePhSO2). The catalytic oxidative ability was not observably superior for the heterogeneous coated catalyst by ZnO–TiO2 over its homogeneous one (MoO2L2) due to the less redox activity of ZnO and TiO2 nanoparticles in the catalytic cycles for the oxygen-transfer mechanism. Both catalysts were successfully recycled, in which the homogeneous catalyst sustained its high catalytic potential for up to three cycles, while the heterogeneous catalyst was able to be reused up to six times.

Effect of the sulfur compounds structure on the SO2 conversion and capture in a bubbling fluidized-bed combustor

SO2 is the main pollutant produced by fluidized bed boiler. Most studies only consider the effect of operating parameters on SO2, while the influence of sulfur structure in coal is ignored. Combustion experiments using pure char loaded with various sulfur structures in a bench-scale bubbling fluidized bed combustor was carried out in this paper to determine the influence of different sulfur structures on SO2 conversion. Effects of excess air, bed temperature and desulfurization efficiency were also investigated. The experimental results show that the order of SO2 conversion is ferrous sulfate > 1-Dodecanethiol > pyrite > diphenyl sulfide > diphenyl sulfoxide > dibenzothiophene. Most sulfur models showed an increase in SO2 conversion with increasing temperature. When the excess air increases, the oxygen content in the furnace is increased, which is beneficial to the conversion of sulfur model to SO2. The desulfurization efficiency of ferrous sulfate and pyrite is higher than that of organic sulfur.

Self-powered perovskite photon-counting detectors.

Metal-halide perovskites (MHPs) have been successfully exploited for converting photons to charges or vice versa in applications of solar cells, light-emitting diodes and solar fuels1-3, for which all these applications involve strong light. Here we show that self-powered polycrystalline perovskite photodetectors can rival the commercial silicon photomultipliers (SiPMs) for photon counting. The photon-counting capability of perovskite photon-counting detectors (PCDs) is mainly determined by shallow traps, despite that deep traps also limit charge-collection efficiency. Two shallow traps with energy depth of 5.8 ± 0.8 millielectronvolts (meV) and 57.2 ± 0.1 meV are identified in polycrystalline methylammonium lead triiodide, which mainly stay at grain boundaries and the surface, respectively. We show that these shallow traps can be reduced by grain-size enhancement and surface passivation using diphenyl sulfide, respectively. It greatly suppresses dark count rate (DCR) from >20,000 counts per second per square millimetre (cps mm-2) to 2 cps mm-2 at room temperature, enabling much better response to weak light than SiPMs. The perovskite PCDs can collect γ-ray spectra with better energy resolution than SiPMs and maintain performance at high temperatures up to 85 °C. The zero-bias operation of perovskite detectors enables no drift of noise and detection property. This study opens a new application of photon counting for perovskites that uses their unique defect properties.

Zeolitized volcanic ashes as supports for Anderson heteropolycompound catalysts. Application in the oxidation of diphenyl sulfide

Zeolitized volcanic ashes as supports for Anderson heteropolycompound catalysts. Application in the oxidation of diphenyl sulfide

Pyrazine-bridged molybdenum(0) carbonyl and molybdenum(VI) oxide network solids as catalysts for epoxidation and sulfoxidation

The horizons of epoxidation and sulfoxidation processes may be expanded by developing new, efficient, and versatile catalysts. In the present work, three pyrazine-bridged molybdenum(0/VI)-based coordination network solids have been investigated for the epoxidation of olefins and the oxidation of sulfides. The materials studied were the Mo0-based metal-organic framework (MOF) fac-Mo(CO)3(pyz)3/2·1/2pyz (1) with a structure consisting of stacked fac-Mo(CO)3(pyz)3/2 coordination layers, the cubic phase fac-Mo(CO)3(pyz)3/2 (2) with a dense framework consisting of two interpenetrating coordination networks, and the molybdenum oxide-pyrazine hybrid material [Mo2O6(pyz)] (3) with a structure consisting of perovskite-like MoO3 layers pillared by pyz molecules. In the model reaction of cis-cyclooctene with tert-butyl hydroperoxide (TBHP) at 70 °C, quantitative yields of the epoxide were obtained within 2 h for 1, 4 h for 2, and 24 h for 3. Catalysts 1-3 were further examined for the epoxidation of other olefins, including the bio-olefins dl-limonene, methyl oleate and methyl linoleate, and the reaction scope was expanded to include the oxidation of sulfides. In the reactions of the bio-olefins, 3 was highly selective, giving only diepoxide and/or monoepoxide products. While the tricarbonyl-pyrazine-molybdenum(0) compounds displayed higher activity, by-products were obtained in the reactions of dl-limonene and methyl linoleate, namely limonene-1,2-diol and hydroxytetrahydrofuran cyclization products, respectively. Catalysts 1-3 displayed high activity for the selective oxidation of sulfides (methyl phenyl sulfide and diphenyl sulfide) to sulfones under mild conditions (35 °C).