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In the present work, we have synthesized sulfone-bridged tetraphenyl porphyrin, 2D polymer 'P' (C44H28N4OySx)n through a one-pot reaction of tetra(p-bromophenyl) porphyrin, S with sulfur powder in DMF. The polymer 'P' has been further reacted with erythrosine B for the fabrication of composite photocatalyst, C (C65H37N4NaOySx)n using donor– acceptor conjugation protocol. Herein, both compounds (P & C) have been well characterized by MAS 13C-NMR, XPS, IR, powder XRD, TGA, SEM-EDX, UV-Vis spectra, and Cyclic Voltammetry. Due to the low HOMO-LUMO band gap energy, the applicability of the composite photocatalyst (C, 2.1 eV) has been studied in terms of oxidation of sulfide to sulfoxide. The present work shows a promising route for the development of sulfone-bridged 2D porphyrin covalent organic framework (COF) and its composite photocatalyst as well as its usage in photocatalytic sulfoxidation reaction. [ABSTRACT FROM AUTHOR]

Polycyclic heteroaromatics (PHAs) are a highly versatile class of functional materials, especially applicable as efficient luminophores in organic light‐emitting diodes (OLEDs). Those constructed by tethered phenyl surrounding the main group center attract extensive attention due to their excellent OLED device performance. However, the development of such a class of emitters is often limited to boron, nitrogen‐doped π‐conjugated heterocycles. Herein, we proposed a novel kind of blue emitter by constructing a donor‐acceptor molecular configuration, utilizing a dual sulfone‐bridged triphenylamine (BTPO) core and mono/di‐diphenylamine (DPA) substituents. The twisted D−A molecular structures and appropriate donor strength facilitate the effective separation of natural transition orbitals, endowing the emitters with charge‐transfer dominant hybridized local and charge‐transfer characteristics for the excited states. Both BTPO‐DPA and BTPO‐2DPA own small S1–T1 splitting energy, thus demonstrating blue thermally activated delayed fluorescence. The more symmetrical structure and enhanced CT features brought by additional DPA moiety confer BTPO‐2DPA with a shorter delayed fluorescence lifetime, a higher fluorescence quantum yield and narrower emission. Therefore, BTPO‐2DPA based OLED devices exhibit superior blue electroluminescence performance, with external quantum efficiencies reaching 12.31 %. [ABSTRACT FROM AUTHOR]

Sulfur(VI)‐based functional groups are popular scaffolds in a wide variety of research fields including synthetic and medicinal chemistry, as well as chemical biology. The growing interest in sulfur(VI)‐containing molecules has motivated the scientific community to explore new methods to synthesize and modify them. Here, photocatalysis plays a key role granting access to new types of reactivity under mild reaction conditions. In this Perspective, we present a selection of works reported in the last six years focused on the photocatalytic assembly and reactivity of sulfones, sulfonamides, and sulfoximines. We addressed the key synthetic intermediates for each transformation, while discussing limitations and strength points of the protocols. Future directions of the field are finally presented. [ABSTRACT FROM AUTHOR]

Sulfone group plays a pivotal role in narrowing emission spectra, while, precise modification with sulfone group for carbonyl‐based narrowband emitters that maintain high color purity remains challenging. Herein, a comprehensive exploration of the function of the sulfone group is performed with various sulfur valences and positions fused into traditional carbonyl‐based narrowband emission unit QAO, namely SpiroS‐QAO, SpiroSO2‐QAO, SpiroO‐QAO, and SpiroOSO2‐QAO. A rigid molecular skeleton with a spiro structure as an intramolecular lock enables the four emitters to exhibit narrowband emissions. After full oxidization of sulfur, the emission band of SpiroSO2‐QAO is further narrowed, with full width at half maximum of 32 nm, compared to that of 43 nm for sulfane‐decorated SpiroS‐QAO, which is attributed to the suppressed C─S bond‐length variation by the introduction of sulfone group. Nearly identical spectra of SpiroO‐QAO and SpiroOSO2‐QAO suggest that the sulfone group should be directly linked to the emission core to maximize its function. Maximum external quantum efficiencies of 30.8%, 30.3%, and 29.2% are achieved for SpiroO‐QAO, SpiroOSO2‐QAO, and SpiroS‐QAO‐based sensitized organic light‐emitting diodes with highly efficient thermally activated delayed fluorescence assistant host. These results offer a comprehensive understanding of the sulfone group embedded into the narrowband emission core with respect to the narrowing emission band. [ABSTRACT FROM AUTHOR]

Herein, we report an efficient and sustainable manganese‐catalyzed α‐C−H bond alkylation methodology to synthesize branched sulfones via a hydrogen borrowing pathway. The air‐stable and phosphine‐free Mn‐catalyst, (NNN)Mn(II)Cl2 was synthesized by using an earth‐abundant, commercially available, and inexpensive precursor MnCl2.4H2O, and a stable NNN pincer i. e. [N‐((benzimidazole‐2‐yl)methyl)quinoline‐8‐amine] ligand system. Taking benzyl phenyl sulfones as substrates, and benzyl alcohol derivatives as alkylating agents, a range of branched sulfones were synthesized in 40–82 % isolated yields using (NNN)Mn(II)Cl2 complex as the catalyst under open‐air conditions. Control experiments and deuterium incorporation studies have also been conducted to investigate the possible reaction mechanism and to provide evidence for the hydrogen borrowing pathway. [ABSTRACT FROM AUTHOR]

A transition‐metal‐free protocol is proposed for the selective oxidation of flavones, providing various sulfoxide/sulfone‐flavonoids in excellent yields. This strategy features excellent selectivities, high yields and broad substrate scope. The combination of oxone (2KHSO5 ⋅ KHSO 4⋅ K2SO4) as the sole oxidant and NaHCO3/Na2CO3 as the buffer play an important role in the process, in which the amounts of oxone and reaction temperatures are the key to the outstanding selectivities and high efficiency of the reaction. It should be noteworthy that a class of novel sulfone‐flavonols is also synthesized through triple oxidation. Moreover, the glycosylation of sulfone‐flavonols has been realized. [ABSTRACT FROM AUTHOR]

A new polyimine polymer (PL) containing sulphone functional groups was prepared from polycondensation of Schiff base (L) with terephthaloyl chloride at a very moderate condition. The polymer metal complexes were then synthesized from the reaction of polymer with metal salts. Scanning electron microscope (SEM), Fourier‐transform infrared spectroscopy (FTIR), X‐ray diffraction analysis (XRD), thermal gravimetric analysis (TGA), derivative thermogravimetry (DTG), proton nuclear magnetic resonance (1H NMR), and CHNS elemental analysis have been used to characterize all the synthesized materials. The excellent thermal stability of PL was specified by TGA. The optical features were assessed with the UV‐visible technique. The polymer complexes represent absorbance at the same wavelength as L and PL. The synthesized polymer metal complexes have a band gap varying from 3.19 (CuPL) to 2.77 (CdPL) eV. The inherent viscosities for the synthesized polymer is 0.4490 dL/g in DMF at 25 °C, indicating their moderate molecular weight. [ABSTRACT FROM AUTHOR]

An efficient three‐component reaction of biaryl ynones, sodium metabisulfite and aryldiazonium tetrafluoroborates is developed. The reaction occurs at room temperature without any additives, thus offering a sustainable approach to access sulfonyl‐containing spiro[5,5]trienones. This protocol features mild conditions, broad substrate scope and high functional group compatibility, furnishing the target products in moderate to good yields. Mechanistic studies indicate that the reaction undergoes a 6‐exo‐trig dearomative spirocyclization process which is initated by an aryl radical with the insertion of sulfur dioxide. [ABSTRACT FROM AUTHOR]

The generation of a low HOMO-LUMO energy gap makes organic polymer-based composites an important class of materials with outstanding catalytic efficiency. The present work describes the simple and direct synthesis of an excellent photocatalyst, PC (C26H16NO7S)n via doping of erythrosine-B dye on sulfone infused poly(2-amino thiophenol) assembly (PA, (C6H4NO2S)n). The O 1 s spectrum displays peaks at 531.8 eV and 533.3 eV, representing the O=C and O–C groups of the in-situ generated fluorescein loaded on PA surface. Through absorption study (Tauc's plot), the optical band gap (Eg) for polymer PA (2.9 eV) and photocatalyst PC (2.1 eV) has been calculated. Further, due to the efficient absorbance in the range of 400–600 nm with a low optical band gap, the applicability of the catalyst, PC has been checked in photocatalytic C–H activation in thiophene, and the generation of C–C bond with p-nitro aryldiazonium salt. [ABSTRACT FROM AUTHOR]

A series of novel sulfone derivatives were synthesized and screened in vitro for their cytotoxicity and antifungal activity with annotated primary mechanism of action (MOA). We prioritized sulfones with high (4-(bromodichloromethylsulfonyl)benzoic acid 4, 4-(difluoromethylsulfonyl)benzoic acid 12), little (3-[4-(bromodichloromethylsulfonyl)phenyl]propanoic acid 8, difluoromethyl 4-methylphenyl sulfone 11, 4-(difluoromethylsulfonyl)benzoic acid 12), or no cytotoxicity of 4-(4-(dichloromethylsulfonyl)benzoic acid 3) and 3-[4-(dichloromethylsulfonyl)phenyl]propanoic acid 7 against mammalian cell lines. 3 was found to be the most potent sulfone against Candida albicans (Rlog=7.25 at 128–256 µg/mL). The mutation in the CNB1 gene (1) increased the sensitivity of the C. albicans biofilm to 3; (2) reduced ergosterol production and therefore generated higher susceptibility to 4. Sulfone 4 at 128 µg/mL increased cellular RH-123 fluorescence in the wild-type cells of C. albicans, except CNB1/cnb1∆. Moreover, the uptake of sulfones into the cell was unaffected regardless of the presence or absence of RH-123, and the uptake of sulfones was strictly cell/strain dependent. Both RH123 and sulfones cumulatively competed with one another for access to transporters. Calcineurin played a role in this mechanism. [ABSTRACT FROM AUTHOR]

An efficient and feasible of the novel highly selective DNA–PK inhibitor AZD7648 was introduced. The route includes the following characteristics: (1) Intermediate (E)-N-hydroxy-N'-(4-methyl-5-nitropyridin-2-yl)formimidamide (4) was prepared from commercially available 4-methyl-5-nitropyridine-2-amine by "one-pot" method, and 7-methyl-[1,2,4]triazolo[1,5-a]pyridin-6-amine (6) was prepared in two steps with an improved yield of 55.5%; (2) Building block 2-chloro-7-methyl-9-(tetrahydro-2H-pyran-4-yl)-7,9-dihydro-8H-purin-8-one (11) was changed to 7-methyl-2-(methylsulfonyl)-9-(tetrahydro-2H-pyran-4-yl)-7,9-dihydro-8H-purin-8-one (17), obtained from 4-chloro-2-methylthiopyrimidine-5-carboxylate. This substitution avoided the formation of disubstituted products and eliminated the need for silica chromatography for purification. (3) The Buchwald–Hartwig cross-coupling reaction was replaced by a nucleophilic aromatic substitution reaction (SNAr) thus avoiding the expensive Pd catalyst and simplifying the work-up process. (4) This route achieves compliance with the strategy of "control from the root design" in organic process research and development, with the principles of efficient application of green and sustainable chemistry. [ABSTRACT FROM AUTHOR]

Photoresponsive fluorescent compounds have been widely used to prepare the encryption inks for modern information security. In this study, a photoresponsive fluorescent material based on dithienylethene DTE-PIO4 was synthesized by oxidizing the two sulfur atoms to sulfones. Its solution presented a distinctive fluorescence switching performance when compared with the traditional "turn-off" mode fluorescent dithienylethene, while irreversible "turn-off" fluorescence switching was observed in PMMA films and solid state upon exposure to 254 nm UV light. Remarkably, the PMMA ink was successfully prepared by incorporation with DTE-PIO4, which indicated the great potential in the fields of optical information storage and ink printing. Further research on information encryption has also been demonstrated through the blending of DTE-PIO4 with DTE-PI in PMMA medium. [ABSTRACT FROM AUTHOR]

2,6-Diaryl-4H-tetrahydro-thiopyran-4-ones and corresponding sulfoxide and sulfone derivatives were designed to lower the major toxicity of their parent anti-kinetoplatidal diarylideneacetones through a prodrug effect. Novel diastereoselective methodologies were developed and generalized from diarylideneacetones and 2,6-diaryl-4H-tetrahydro-thiopyran-4-ones to allow the introduction of a wide substitution profile and to prepare the related S-oxides. The in vitro biological activity and selectivity of diarylideneacetones, 2,6-diaryl-4H-tetrahydro-thiopyran-4-ones, and their S-sulfoxide and sulfone metabolites were evaluated against Trypanosoma brucei brucei, Trypanosoma cruzi, and various Leishmania species in comparison with their cytotoxicity against human fibroblasts hMRC-5. The data revealed that the sulfides, sulfoxides, and sulfones, in which the Michael acceptor sites are temporarily masked, are less toxic against mammal cells while the anti-trypanosomal potency was maintained against T. b. brucei, T. cruzi, L. infantum, and L. donovani, thus confirming the validity of the prodrug strategy. The mechanism of action is proposed to be due to the involvement of diarylideneacetones in cascades of redox reactions involving the trypanothione system. After Michael addition of the dithiol to the double bonds, resulting in an elongated polymer, the latter—upon S-oxidation, followed by syn-eliminations—fragments, under continuous release of reactive oxygen species and sulfenic/sulfonic species, causing the death of the trypanosomal parasites in the micromolar or submicromolar range with high selectivity indexes. [ABSTRACT FROM AUTHOR]

3,5-Diphenyl-4H-1,2,6-thiadiazin-4-one treated with meta-chloroperoxybenzoic acid undergoes an oxidative ring contraction to give 2-benzoyl-4-phenyl-1,2,5-thiadiazol-3(2H)-one 1,1-dioxide in a 29% yield, the structure of which is supported by single-crystal X-ray diffraction analysis and the available spectroscopic data. [ABSTRACT FROM AUTHOR]

Purely organic sulfone‐embedded materials play a significant role in thermally activated delayed fluorescence (TADF) emitters with theoretical 100 % exciton utilization for highly efficient organic light‐emitting diodes. However, intrinsic emission mechanism featuring twisted intramolecular charge transfer design strategy leads to severe structural distortion between ground state and excited state, disabling traditional sulfone‐based TADF emitters to achieve narrowband emission and high colour purity for wide colour gamut display. Recently, sulfone‐embedded narrowband TADF emitters have gradually emerged. Herein, we summarize the currently reported sulfone‐based narrowband emitters, with emphasis on the perspectives of molecular design, role of sulfone group in fused skeleton, photophysical property as well as future application prospect of this sort of materials. [ABSTRACT FROM AUTHOR]

Abstract It is a great challenge to discover novel chemical reactions suitable for biological analysis in a living system. The development of novel protein thiol blocking agents is a crucial need for exploring protein thiol functions in protein refolding, signal transduction, and redox regulation. We are always keen on seeking novel chemical reactions applied to endogenous biological macromolecules or protein thiol sensing, blocking, and labeling. In the present work, we have successfully developed a novel agent to block protein thiol by enhanced electron‐withdrawing inductive effects. This sensing and blocking process was detailedly monitored by UV‐vis, fluorescent spectra, and SDS‐Page gel separation. The spectral studies demonstrated that the agent could react ultrafastly with thiol within seconds at μM level. Furthermore, fluorescent imaging in cells and in vivo was further used for the validation of its ability to sensing and blocking thiol, providing evidence of downregulated protein thiols in Parkinson's disease. The enhanced electron‐withdrawing inductive effect strategy in this work may provide a general guideline for designing protein thiol agent.

The title compound, C16H17BrO2S, crystallizes as the erythro (RR/SS) isomer of a pair of sulfones that were diastereomeric due to chirality of the α-carbon atoms on the sulfone sulfur atom. The structural analysis was pivotal in showing that the 1,3 elimination reactions of these compounds, which lead to substituted stilbenes, occur with inversion at each asymmetric carbon atom. In the crystal, C—H...Br and C—H...O hydrogen bonds link the molecules into a tri-periodic intermolecular network.

In the title molecule, C8H7NO3S, the nitrogen atom has a planar environment, and the thiazine ring exhibits a screw-boat conformation. In the crystal, corrugated layers of molecules parallel to the ab plane are formed by N—H...O and C—H...O hydrogen bonds together with C—H...π(ring) and S=O...π(ring) interactions. The layers are connected by additional C—H...O hydrogen bonds and π-stacking interactions. Hirshfeld surface analysis indicates that the most important contributions for the crystal packing are from H...O/O...H (49.4%), H...H (23.0%) and H...C/C...H (14.1%) interactions. The volume of the crystal voids and the percentage of free space were calculated as 75.4 Å3 and 9.3%. Density functional theory (DFT) computations revealed N—H...O and C—H...O hydrogen-bonding energies of 43.3, 34.7 and 34.4 kJ mol−1, respectively. Evaluation of the electrostatic, dispersion and total energy frameworks indicate that the stabilization is dominated via the electrostatic energy contribution. Moreover, the DFT-optimized structure at the B3LYP/ 6–311 G(d,p) level is compared with the experimentally determined molecular structure in the solid state. The HOMO–LUMO behaviour was elucidated to determine the energy gap.

The purpose of the research is to study the biotransformation of fenbendazole in the body of sheep after administration of fenbendazole solid dispersion (FSD) prepared by mechanochemical technique with arabinogalactan. Materials and methods. The FSD at a dose of 2.0 mg/kg for the active substance was administered orally to sheep. Animal blood serum samples were studied by high performance liquid chromatography / tandem mass spectrometry (HPLC-TMS) to determine the concentration of fenbendazole (FBZ) and its sulfoxide and sulfone metabolites at 0, 1, 2, 4, 6, 8, 12, 24, 33, 48 and 72 hours after administered FSD and initial FBZ (substance). FBZ and its metabolite residual quantity in the organs and tissues of the sheep was determined at 1, 3, 6, 11, and 21 days after the drug administration. The prepared sample and validated method were described. Results and discussion. A significant difference was found in the metabolism, pharmacokinetics, and timing of the FBZ and its metabolite elimination after the base drug (FBZ substance) and FSD were administered to sheep in an equal dose of 2.0 mg/kg for the active substance. FBZ and its metabolites began to be detected in blood serum 2 hours after the FSD and 4 hours after the base FBZ. Pharmacokinetic parameters of FBZ and its metabolites characterize a higher drug concentration in the blood and a longer retention time in the circulation after the FSD as compared with the base drug parameters. The FBZ and its metabolite maximum concentration was found in the organs and tissues of the sheep that received the FSD on day 3 in the liver amount of 4862.3±296.2 ng/g of FBZ; 18243.5±486.1 ng/g of sulfoxide; and 2482.3±132.4 ng/g of sulfone; and tens of times lower concentration after the base FBZ on day 6. FBZ and its metabolites were not detected in the organs and tissues of the sheep on day 16 after the base FBZ, and on day 21 after the FSD.

3,5-Diphenyl-4H-1,2,6-thiadiazin-4-one treated with meta-chloroperoxybenzoic acid undergoes an oxidative ring contraction to give 2-benzoyl-4-phenyl-1,2,5-thiadiazol-3(2H)-one 1,1-dioxide in a 29% yield, the structure of which is supported by single-crystal X-ray diffraction analysis and the available spectroscopic data.

Electron‐accepting units play vital roles in constructing donor‐acceptor (D‐A) conjugated organic optoelectronic materials; the electronic structures and functions of the acceptors need to be carefully unveiled to controllably tailor the optoelectronic properties. We have synthesized two D‐A conjugated organic fluorophores, TPA‐SO and TPA‐CO, with similar molecular skeletons based on sulfone‐ or carbonyl‐containing polycyclic aromatic acceptors. Both TPA‐SO and TPA‐CO display obvious solvent polarity‐dependent photophysical properties and large Stokes shift of over 100 nm for strong intramolecular charge transfer processes. Experimental evidence indicates that the sulfone group in TPA‐SO merely serves as a strong electron‐withdrawing unit. TPA‐SO shows yellowish‐green emission with a peak at 542 nm and an absolute photoluminescence quantum yield (PLQY) of 98 % in solution, whereas the carbonyl group in TPA‐CO can act as both an electron‐withdrawing unit and spin transition convertor, so TPA‐CO displays red emission with a low absolute PLQY of 0.32 % in solution. Impressively, upon going from solution to aggregate state, TPA‐SO nanoparticles keep a high PLQY of 9.5 % and moderate biocompatibility, thus they are good nano‐agents for cellular fluorescence imaging. The results reveal that the inherent acceptor characteristic acts as a crucial effect in the photophysical properties and applications of the organic fluorophores. [ABSTRACT FROM AUTHOR]

Li‐metal batteries (LMB), although providing high energy density, face the grand challenge of identifying good electrolyte solvents for cycling. Common solvents are either only stable against lithium metal anode or only stable against LiNixMnyCo1‐x‐yO2 (NMC) cathode. There is significant effort trying to increase the cathode stability for ether electrolytes, which are in general stable against lithium metal anode. In comparison, there is much less effort trying to increase the anode stability of electrolytes that are stable against NMC cathode. One example is the sulfone‐based electrolyte. It has good cathode stability but is hindered from practical application because of (1) high viscosity and poor wetting capability and (2) poor anode stability. Here, we solve these issues by modifying the sulfone molecules using resonance and electron withdrawing effect. The viscosity is significantly reduced by delocalizing the electrons through introducing additional oxygen on the molecular backbone and applying appropriate fluorination. The resulting molecule 2,2,2‐trifluoroethyl mesylate (TFEM) has decreased Lewis basicity and less reactivity toward Li+. The electrolyte based on TFEM as single solvent enables cycling of LMB under harsh conditions of low N/P ratio (21 mg/cm2 NMC811 and 50 μm Li) with 90 % capacity retention after 160 cycles at C/3 discharge rate. [ABSTRACT FROM AUTHOR]

Julia‐Kocienski olefination, a coupling reaction between a carbonyl component and a sulfone partner, has emerged as a powerful synthetic tool in the preparation of several organic compounds. A number of interesting examples involving particularly the preparation of trisubstituted alkenes along with important observations regarding the stereoselectivity of those reactions have been recently reported. This reviewing work covers the literature for the period 2016–2022 and describes in a comprehensive way the progress and developments of Julia‐Kocienski olefination application in the synthesis of trisubstituted alkenes which serve as precursors of natural products and their analogs as well of pharmaceutically interesting/biologically important compounds. Moreover, key methodology results dealing with the investigation of the optimum conditions and stereoselectivities and new modifications and approaches are discussed. [ABSTRACT FROM AUTHOR]

1,4-Oxathiins are valued for a breadth of bioactivities and are known commercial fungicides. This article explores a novel preparation of 2,3,6-trisubstituted 1,4-oxathiin-S,S-dioxides via the reaction of benzyl 1-alkynyl sulfones and aryl aldehydes under basic conditions. A total of 20 examples possessing exclusively a trans arrangement of the 2,3-diaryl substituents are exhibited; the products demonstrate a variation of functional groups on the aryl ring attached to the heterocyclic ring system. The preparation is hindered by the base sensitivity of the products, and a ring-opened by-product typically contaminates the reaction mixture. A DFT assessment of the overall system includes a lithium counterion and offers possible pathways for the incorporation of the aldehyde, the cyclization step and the requisite proton transfers. In addition, the DFT work reveals options for the ring opening chemistry. It appears the trans 2,3-diaryl selectivity is set during the cyclization stage of the reaction sequence. The practical work uncovers a new reaction pathway to create a family of novel 1,4-oxathiin-S,S-dioxides whereas the computational work offers an understanding of the structures and possible mechanisms involved. [ABSTRACT FROM AUTHOR]

The title sulfones, 2,3-diphenyl-2,3-dihydro-4H-1,3-benzothiazine-1,1,4-trione, C20H15NO3S, and 2,3-diphenyl-2,3-dihydro-4H-pyrido[3,2-e][1,3]thiazine-1,1,4-trione, C19H14N2O3S, crystallize in space group P21/n with two molecules in each of the asymmetric units and have almost identical unit cells and extended structures. In both structures, the thiazine rings exhibit a screw-boat pucker. The intermolecular interactions observed are C—H...O-type hydrogen bonds and parallel partial π–π stacking between the fused aromatic rings (benzo- or pyrido-) of the core of the molecules within each asymmetric unit, and also connecting to molecules with translational periodicity in the a-axis direction in what can be described as columns (two per asymmetric unit) of stacked molecules with alternating chirality. The pendant phenyl groups of both molecules do not participate in aromatic ring interactions.

2,6-Diaryl-4H-tetrahydro-thiopyran-4-ones and corresponding sulfoxide and sulfone derivatives were designed to lower the major toxicity of their parent anti-kinetoplatidal diarylideneacetones through a prodrug effect. Novel diastereoselective methodologies were developed and generalized from diarylideneacetones and 2,6-diaryl-4H-tetrahydro-thiopyran-4-ones to allow the introduction of a wide substitution profile and to prepare the related S-oxides. The in vitro biological activity and selectivity of diarylideneacetones, 2,6-diaryl-4H-tetrahydro-thiopyran-4-ones, and their S-sulfoxide and sulfone metabolites were evaluated against Trypanosoma brucei brucei, Trypanosoma cruzi, and various Leishmania species in comparison with their cytotoxicity against human fibroblasts hMRC-5. The data revealed that the sulfides, sulfoxides, and sulfones, in which the Michael acceptor sites are temporarily masked, are less toxic against mammal cells while the anti-trypanosomal potency was maintained against T. b. brucei, T. cruzi, L. infantum, and L. donovani, thus confirming the validity of the prodrug strategy. The mechanism of action is proposed to be due to the involvement of diarylideneacetones in cascades of redox reactions involving the trypanothione system. After Michael addition of the dithiol to the double bonds, resulting in an elongated polymer, the latter—upon S-oxidation, followed by syn-eliminations—fragments, under continuous release of reactive oxygen species and sulfenic/sulfonic species, causing the death of the trypanosomal parasites in the micromolar or submicromolar range with high selectivity indexes.

The synthesis of gem-difluoroalkenes by photocatalytic desulfonylative coupling of alkylsulfones with α-(trifluoromethyl)styrenes is described. Photoredox Ir complex was found to be an effective catalyst for this transformation through single electron reduction of alkyl 1-phenyltetrazolyl sulfones, providing structurally diverse gem-difluoroalkene products in good yields. The resulting alkenes could be further converted into fluorinated derivatives, highlighting the potential utility of this method in the synthesis of organofluorine compounds. [ABSTRACT FROM AUTHOR]

1H NMR, DSC and TG were used for investigating nine aliphatic sulfones. The most suitable solvent – diethyl ether – was used for its purification by recrystallisation. The thermal stability of these substances was studied; it is comparable to ethylene carbonate and can be increased by using a RSO2R' with (a) longer carbon chain in any R and R' and (b) linear R and/or R' instead of branched one(s). Melting parameters of 8 sulfones were obtained for the first time and the enthalpy and temperature of (n-C4H9)2SO2 were revised. Four of 9 sulfones have melting point below the room temperature. A C4 radical possibly is optimal to get a lower m.p. Melting point decreases in a row both linear R > both branched R ≥ one branched R. Additionally, the attempts to reevaluate SO2 increment value were made. [ABSTRACT FROM AUTHOR]

A novel method for synthesis of β‐hydroxylsulfone derivatives by cobalt‐catalyzed aerobic oxysulfonylation of styrenes with sulfonyl chlorides was developed. This reaction proceeds under simple and mild conditions, employing inexpensive cobalt as the catalyst and molecular oxygen as the oxidant. It showed a broad substrate scope and provided a series of β‐hydroxylsulfone in moderate to good yields. [ABSTRACT FROM AUTHOR]

The syntheses and crystal structures of two thiazinone compounds, namely, rac-2,3-diphenyl-2,3,5,6-tetrahydro-4H-1,3-thiazine-1,1,4-trione, C16H15NO3S, in its racemic form, and N-[(2S,5R)-1,1,4-trioxo-2,3-diphenyl-1,3-thiazinan-5-yl]acetamide, C18H18N2O4S, in an enantiopure form, are reported. The thiazine rings in the two structures differ in their puckering, as a half-chair in the first and a boat pucker in the second. The extended structures for both compounds have only C—H...O-type interactions between symmetry-related molecules, and exhibit no π–π stacking interactions in spite of each having two phenyl rings.

Coal is considered one of the largest energy sources globally, but the sulfur in coal combustion seriously affects the efficient utilization of coal. Moreover, the sulfide produced by burning high sulfur coal is one of the leading causes of several diseases and environmental pollution. Incorporating photocatalytic oxidation into the extraction desulfurization system can significantly improve the efficiency of ionic liquid reactive extraction desulfurization. To further study the mechanism of desulfurization, experiment and computer simulation were used to analyze it. The experimental results show that coupling the photocatalytic reaction process and the ionic liquid extraction process can effectively remove organic sulfur in coal. The desulfurization rate of organic sulfur in the coal treated by [HO2MMim][HSO4]–H2O–H2O2–TiO2（mass ratio 5∶5∶10∶4）can reach 12.40%. In addition, an appropriate amount of water can improve the desulfurization rate of coal, but an excessive amount of aqueous solution can reduce the concentration of hydrogen peroxide and the organic sulfur desulfurization rate in coal. Materials Studio analysis shows that the hydroxyl radical (·OH) generated by photocatalytic activity has strong oxidability, and the area near the oxygen atom of ·OH is electronegative, which is easy to form S=O double bond with the positively charged S atom in thiophene via electrostatic attraction. In addition, the addition of ionic liquid makes the original lowest vacant orbital on the thiophene ring disappear. Moreover, it lowers the energy level difference between the HOMO and the LUMO, making the reaction easier to proceed with. Using COSMO analysis, it is found that the five-member heterocyclic structure of imidazole in [HO2MMim][HSO4] formed bonds with thiophene and sulfone molecules through van der Waals forces; thus, sulfide was constantly extracted into the ionic liquid phase and that adding the oxidizer can make it easier for sulfone with higher chemical potential to enter the lower chemical potential ionic solution [HO2MMim][HSO4] than thiophene.

Katalysatorkontrolle über Stereogenität höherer Ordnung vergrößert den zugänglichen stereochemischen Raum erheblich, aber Methoden zur stereoselektiven Synthese dreifach stereogener Einheiten wurden bisher nicht beschrieben. In diesem Artikel berichten wir über die stereokontrollierte Synthese von dreifach stereogenen Triptycylsulfonen, deren Atropisomerie aus einer C(sp3)−S‐Bindung resultiert. Die katalysatorkontrollierte Oxidation eines stereodynamischen Thioethers in Gegenwart einer chiralen Phosphorsäure erlaubte dabei den selektiven Zugang zu enantiomerenangereicherten Triptycylsulfoxiden. Deren anschließende enantiospezifische und diastereoselektive katalytische Oxidation zu einem dreifach stereogenen Sulfon ermöglichte es so, die stereogene C−S‐Achse zu kontrollieren. Alle drei Stereoisomere wurden mit Enantio‐ und Diastereodivergenz und einer Stereoselektivität von bis zu (−sc) : (+sc) : (ap)=94 : 6 : <1 erhalten. [ABSTRACT FROM AUTHOR]

Under heating conditions, an iron(II)‐catalyzed cascade cyanoalkylsulfonylation/cyclization reaction is developed to produce cyanoalkylsulfonylated pyrrolidones bearing with a free CN moiety. This alkyl radical disconnection and cascade annulation protocol enjoys chemo‐ and regioselectivity with the tolerance toward a range of functional groups. The reactive cyanoalkyl radical, which was originated from the ring‐opening reaction of a cyclic imine radical, was found to be capable of capturing the in‐situ generated "SO2" species from DABSO, thus leading to the production of a cyanoalkyl sulfonyl radical and the subsequent alkene annulation sequences. [ABSTRACT FROM AUTHOR]

Sulfone‐embedded heterocyclics are of great interest in organic light‐emitting diodes (OLEDs), however, exploring highly efficient narrowband emitters based on sulfone‐embedded heterocyclics remains challenging. Herein, five emitters with different sulfur valence state and molecular rigidity, namely tP, tCPD, 2tCPD, tPD and tPT, are thoroughly analysed. With restricted twisting of flexible peripheral phenyl by strengthening molecular rigidity, molecular emission spectra can be enormously narrowed. Further, introducing the sulfone group with bending vibration in low‐frequency region that suppresses high‐frequency vibration, sharp narrow full‐widths at half‐maximum of 28 and 25 nm are achieved for 2tCPD and tPD, respectively. Maximum external quantum efficiencies of 22.0 % and 27.1 % are successfully realized for 2tCPD‐ and tPD‐based OLED devices. These results offer a novel design strategy for constructing narrowband emitters by introducing sulfone group into a rigid molecular framework. [ABSTRACT FROM AUTHOR]

α-Ketothioesters are safely and efficiently synthesized from arylacetylenic sulfones and dimethyl sulfoxide (DMSO) in the presence of equivalent of water and catalytic amount of 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) under microwave irradiation. Arylacetylenic sulfones and dimethyl sulfoxide first form arenecarbonyl sulfonyl dimethylsulfonium methylides via nucleophilic addition, ring closure, and 4e ring opening. The methylides undergo a radical process to generate α-methylthio-α-sulfonylacetophenones, which further convert to α-ketothioesters through the Pummerer oxidation. Compared to the previous methods, the current method is safer and more efficient. [ABSTRACT FROM AUTHOR]

Over the past decades, 2(5H)-furanone derivatives have been extensively studied because of their promising ability to prevent the biofilm formation by various pathogenic bacteria. Here, we report the synthesis of a series of optically active sulfur-containing 2(5H)-furanone derivatives and characterize their biological activity. Novel thioethers were obtained by an interaction of stereochemically pure 5-(l)-menthyloxy- or 5-(l)-bornyloxy-2(5H)-furanones with aromatic thiols under basic conditions. Subsequent thioethers oxidation by an excess of hydrogen peroxide in acetic acid resulted in the formation of the corresponding chiral 2(5H)-furanone sulfones. The structure of synthesized compounds was confirmed by IR and NMR spectroscopy, HRMS, and single crystal X-ray diffraction. The leading compound, 26, possessing the sulfonyl group and l-borneol moiety, exhibited the prominent activity against Staphylococcus aureus and Bacillus subtilis with MICs of 8 μg/mL. Furthermore, at concentrations of 0.4–0.5 μg/mL, the sulfone 26 increased two-fold the efficacy of aminoglycosides gentamicin and amikacin against S. aureus. The treatment of the model-infected skin wound in the rat with a combination of gentamicin and sulfone 26 speeded up the bacterial decontamination and improved the healing of the wound. The presented results provide valuable new insights into the chemistry of 2(5H)-furanone derivatives and associated biological activities. [ABSTRACT FROM AUTHOR]

Alkyl/aralkyl/phenacyl thiotriazolyl isoindoline-1,3-diones were synthesized by the reaction of dipotassium cyanodithioimidocarbonate salt with hydrazine hydrate, phthalic anhydride and alkyl/aralkyl/phenacyl bromides using acetic acid and sodium acetate via a one-pot four-component synthesis. Alternatively, the same final products were also synthesized by the reaction of dipotassium cyanodithioimidocarbonate salt with hydrazine hydrate in presence of acetic acid to give intermediate 5-amino-4H-1,2,4-triazole-3-thiol [I]. This compound was further reacted with phthalic anhydride, followed by a reaction with alkyl/aralkyl/phenacyl bromides to give the title compounds in a two-step process. In this method, the yields are less compared to one-pot four-component synthesis. All the newly synthesized compounds were characterized by their spectral studies (FTIR, 1H-NMR, 13C-NMR, Mass). Further, the synthesized compounds were screened for their in-vitro anticancer activity. Compounds 5 m, 5p, 5r showed good cytotoxic assay against Hela cancer cell lines. Furthermore, compounds 5(a-t) were subjected to their docking analysis and DFT calculations. [ABSTRACT FROM AUTHOR]

Vehicular SOx emissions have a huge detrimental impact on public health, catalytic converters, and the environment. Developing strategies to remove sulfur from diesel and thus safeguard the above is imperative. A series of SnO2–MoO3 mixed oxides and mono oxides MoO3 and SnO2 were prepared by soft template method, calcined at 450 °C and successfully tested in model diesel oxidative desulfurisation (ODS). The impact of the SnO2/MoO3 mole ratio (hereinafter denoted as Sn/Mo) on catalytic efficiency was investigated, among other catalytic parameters. The obtained samples were analyzed using X-ray diffraction (XRD), Raman spectrocscopy, scanning electron microscopy (SEM), N2-physisorption and titration method for acidic properties. The study demonstrates that mixing SnO2 and MoO3 improves acidic sites, crystallinity, and morphological properties of pure SnO2. The addition of MoO3 increased oxygen vacancies and the surface area of SnO2. High acidic site densities of 49.3, 47.4, and 46.7 mEqg−1 were observed for the catalysts with 2:1, 1:1, and 1:2 Sn/Mo mole ratio, respectively. The catalytic efficiency increased with an increase in Sn content with the highest catalytic efficiency of 99.8% for the dibenzothiophene (DBT) oxidation achieved in 30 min for Sn/Mo (2:1) catalyst compared to 92 and 70% for Sn/Mo 1:1 and 1:2 catalysts, respectively. The rate constant for the reaction was 0.057 min−1, which is eight times that of MoO3; 0.007 min−1 and three times that of SnO2; 0.017 min−1. The ODS mechanism utilizing the SnO2–MoO3 catalyst was proposed. The prepared SnO2–MoO3 catalyst demonstrated a high potential for industrial desulfurisation applications.

A novel tri‐acyl chloride monomer containing reductive thioether units (T‐TDC) was prepared. It was conducted to partially replace trimesoyl chloride (TMC) and react with m‐phenylenediamine (MPD) by interfacial polymerization to prepare a series of T‐TDC/TMC/MPD copolymer thin‐film‐composite reverse‐osmosis polyamide membranes. Through this routine, the reductive thioether units was introduced into the film molecular chain to protect amide bonds from being chlorinated by oxidizing during the membrane cleaning process. The enhanced chlorine resistance of these resultant membranes was revealed by FT‐IR and XPS characterization: it could be found thioether was prior to amide oxidation, and its oxidation process can be divided into two steps (the thioether units was first converted to sulfoxide groups, and then further oxidized to sulfone groups). Through this routine, the active chlorine was consumed partially, then the amide bond was protected. The experiment result is consistent with the DFT theoretical calculation. The chlorine exposure concentration of the normalized flux and rejection decreased to 1 increased gradually with the addition of copolymerization ratio of T‐TDC, especially for the sample 20%‐TTDC‐TFC, its chlorine exposure concentration was 3 and 4 times higher respectively than that of 0%‐TTDC‐TFC when its normalized flux and rejection at 1. In addition, it can be found that the polar sulfone and sulfoxide groups can form hydrogen bonds to prevent the membrane from degrading immediately. This method provides an effective way for improving the service life of RO film. [ABSTRACT FROM AUTHOR]

The title sulfones, 2,3-diphenyl-2,3-di-hydro-4H-1,3-benzo-thia-zine-1,1,4-trione, C20H15NO3S, and 2,3-diphenyl-2,3-di-hydro-4H-pyrido[3,2-e][1,3]thia-zine-1,1,4-trione, C19H14N2O3S, crystallize in space group P21/n with two mol-ecules in each of the asymmetric units and have almost identical unit cells and extended structures. In both structures, the thia-zine rings exhibit a screw-boat pucker. The inter-molecular inter-actions observed are C-H⋯O-type hydrogen bonds and parallel partial π-π stacking between the fused aromatic rings (benzo- or pyrido-) of the core of the mol-ecules within each asymmetric unit, and also connecting to mol-ecules with translational periodicity in the a-axis direction in what can be described as columns (two per asymmetric unit) of stacked mol-ecules with alternating chirality. The pendant phenyl groups of both mol-ecules do not participate in aromatic ring inter-actions. [ABSTRACT FROM AUTHOR]

The syntheses and crystal structures of two thiazinone compounds, namely, rac-2,3-diphenyl-2,3,5,6-tetrahydro-4H-1,3-thiazine-1,1,4-trione, C16H15NO3S, in its racemic form, and N-[(2S,5R)-1,1,4-trioxo-2,3-diphenyl-1,3-thiazinan-5-yl]acetamide, C18H18N2O4S, in an enantiopure form, are reported. The thiazine rings in the two structures differ in their puckering, as a half-chair in the first and a boat pucker in the second. The extended structures for both compounds have only C--H • • • O-type interactions between symmetry-related molecules, and exhibit no π - π stacking interactions in spite of each having two phenyl rings. [ABSTRACT FROM AUTHOR]

In this study, pnictogen (Pn)‐bridged diphenyl sulfones were synthesized as motifs for photoinduced dynamic rearrangement. The newly synthesized sulfones exhibited dual fluorescence at 298 K. Density functional theory calculations revealed that the longer‐wavelength fluorescence was derived from the geometries after structural relaxation through photo‐driven pnictogen bond formation between the O atom lone pair of the sulfonyl moiety and the antibonding orbital of the Pn−C bond. This is the first report on emission dynamics driven by pnictogen bond formation upon photoexcitation. [ABSTRACT FROM AUTHOR]

A desulfonylative homocoupling of benzylic sulfone derivatives through a photoredox Ir catalyst is described. The 3,5-bis(trifluoromethyl)phenyl group is an effective substituent on sulfonyl group in this reaction, providing the structurally diverse multiply arylated ethanes in good yields. The α-deuterated or α-fluorinated sulfones, which can be readily prepared by α-functionalization, were also applicable, highlighting an avenue to synthesize medicinally important structures. [ABSTRACT FROM AUTHOR]

In this study, 2-hydroxy-4-methylthiobutyrate (2H4MTB)-containing polyhydroxyalkanoate (PHA) copolymers were biosynthesized using methionine as the 2H4MTB precursor. 2H4MTB is a novel monomer unit that contains a sulfur atom in its side chain. The 2H4MTB-containing PHA was biosynthesized by functionalizing the leucine degradation and PHA synthesis pathways in recombinant Escherichia coli. The 2H4MTB fraction in the PHA copolymer was increased up to 30.6 mol% by increasing the methionine concentration in the medium. Using purified polymers containing 10.9 mol% 2H4MTB unit, the sulfide group of the 2H4MTB side chain was oxidized with hydrogen peroxide or peracetic acid, which resulted in the conversion of sulfide to sulfoxide and sulfone groups. The oxidized polymer was relatively hydrophilic, as revealed by water contact angle measurements, and swelled slightly when soaked in water. These results suggest that the 2H4MTB unit can be used as an oxidation site to impart hydrophilicity to the PHA copolymers. [ABSTRACT FROM AUTHOR]

Domestic poultry are among the non-target species of exposure to fipronil, but limited information is available on the metabolic effects of fipronil exposure in avian. We investigated the comparative capacity of in vitro biotransformation of fipronil among chicken, duck, quail, goose, and rat. Interspecies differences in kinetic parameters were observed; the clearance rate calculations (Vmax/Km) indicated that chicken and duck are more efficient in the cytochrome P450-mediated metabolism of fipronil to sulfone than quail, goose and rat. The lower hepatic clearance of fipronil in quail, goose and rat, suggested that fipronil sulfone may serve as a biomarker to indicate fipronil exposure in these species. [ABSTRACT FROM AUTHOR]

Photoinduced tandem cyclization of alkynes with phenylsulfinic acids has been accomplished, which gives a mild strategy for the preparation of sulfone-substituted seven-membered N -heterocycles. A variety of scaled-up experiments, further transformations, and mechanistic studies were also operated in the follow-up work. [ABSTRACT FROM AUTHOR]

The direct regioselective C−H‐functionalization of simple, unfunctionalized pyridines is considered a long‐standing challenge in heterocyclic chemistry. Herein, we report a novel one‐pot protocol for the C4‐selective sulfonylation of pyridines via triflic anhydride (Tf2O) activation, base‐mediated addition of a sulfinic acid salt, and subsequent elimination/re‐aromatization. Contrary to previous approaches employing tailored blocking groups, positional selectivity can be controlled by using N‐methylpiperidine as simple, readily available external base. This method offers a highly modular and streamlined access to C4‐sulfonylated pyridines. [ABSTRACT FROM AUTHOR]

Reactions of 2-(chloromethyl)thiirane with symmetrically substituted C-bromo/nitropyrazoles in water in the presence of bases were accompanied by thiirane–thietane rearrangement to afford 4-bromo(nitro)- and 3,5-dibromo-4-bromo(nitro)-1-(thietan-3-yl)-1H-pyrazoles as convenient intermediate products for further transformations. Possible modifications of the title compounds via oxidation to 1-(1-oxo-λ4-thietan-3-yl)- and 1-(1,1-dioxo-λ6-thietan-3-yl)pyrazoles, reactions with oxygen and nitrogen nucleophiles with the formation of thietane-containing 5-methoxy- and 5-(morpholin-4-yl)-1H-pyrazoles, and reduction to 4-amino-3-bromo-5-(morpholin-4-yl)-1-(thietan-3-yl)-1H-pyrazole have been demonstrated. [ABSTRACT FROM AUTHOR]