Sulfonates In Water Research Articles

Nickel-Catalyzed Suzuki-Miyaura Coupling in Water for the Synthesis of 2-Aryl Allyl Phosphonates and Sulfones.

An operationally simple and green protocol using a NiSO4·6H2O/cationic 2,2'-bipyridyl ligand system as a water-soluble catalyst for the coupling of arylboronic acids with (2-haloallyl)phosphonates and (2-haloallyl)sulfones in water under air was developed. The reaction was performed at 120 °C with arylboronic acids (2 mmol) and (2-haloallyl)phosphonates or sulfones (1 mmol) in the presence of 5 mol % of the Ni catalytic system in a basic aqueous solution for 1 h, giving the corresponding 2-aryl allyl phosphonates or sulfones in good to excellent yields. This reaction features the use of an abundant transition metal as a catalyst in water and exhibits high functional group tolerance, rendering it an eco-friendly procedure.

Chemical fuel-driven transient 2D supramolecular organic frameworks (SOFs): catalysis for green synthesis.

Mimicking the dissipative assemblies found in living systems fueled by bioenergy, we present a novel chemical fuel-driven transient 2D SOF, formed via the redox reaction-driven transient self-assembly of tetraphenylene-based structural units and cucurbit[8]uril (CB[8]). The system was initiated by adding sodium dithionite (SDT) as the fuel, leading to the formation of 2D SOFs through 2 : 1 host-guest complexation between the viologen cation radical and CB[8]. These 2D SOFs then spontaneously disassemble over time as the radicals are oxidized by air. The temporal assembly and lifetimes of these transient SOFs can be controlled by adjusting the concentrations of the fuel. Moreover, the resulting transient 2D SOFs exhibited remarkable potential as catalysts for the green synthesis of benzyl sulfones in water.

Interionic hydrogen bonds induced high solubility of quinone derivatives and preliminary study on their application properties in all quinone aqueous redox flow battery

The development of highly water-soluble quinone derivatives is an important research direction for aqueous organic redox flow batteries (AORFBs) of high energy density. In this work, choline cations are substituted for sodium ions to form new ion pairs with quinone sulfonates, and the water solubility of quinone sulfonates derivatives is significantly improved due to the formed interionic hydrogen bond between the CO in anthraquinone sulfonic acid anion and -OH in choline cation. Specifically, 9,10-anthraquinone-2-disulfonic choline salt (AQSCH) and 1, 2-dihydroxy-3, 5-phenyldisulfonic acid dicholine salt (BQDS(CH)2) are synthesized by simple ion exchange and acid-base neutralization. As a result, the solubility of the quinone and anthraquinone sulfonates in water is increased by more than ten times, and the redox reversibility is not significantly affected. The charging-discharging performance of a novel pH-neutral all-quinone aqueous battery with AQSCH and BQDS(CH)2 as the anodic and cathodic active electrolytes respectively, choline chloride as the supporting electrolyte is investigated using a static H-type electrolytic cell, the obtained results verifying the feasibility of using choline as the counter cathion and solubilizer of quinone sulfonates to improve their water solubility in pH-neutral AORFBs.

Highly efficient and selective aqueous aerobic oxidation of sulfides to sulfoxides or sulfones catalyzed by tungstate-functionalized nanomaterial

A Brönsted acidic ionic solid comrising tungstate-functionaized polyorganosiloxane framework (PMO-IL-WO42−) efficiently catalysed aerobic oxidation of sulfides in aqueous medium. The catalyst can selectively produce sulfoxides or sulfones by running the reaction at room temperature or 50 °C, respectively. Because of the ionic liquid-based charged surface containing hydrophobic organic functional groups and hydrophilic sulfonic acid group, the synergestic hydrophobic/hydrophilic and redox effect of PMO-IL-WO42- as water-friendly interfacial nanocatalyst simplifies and enhances the activity and selectivity toward the target sulfoxides or sulfones in water. Moreover, the PMO-IL-WO42- nanocatalyst exhibited outstanding stability and activity and can be recycled eight reaction runs without any significant activity and selectivity loss.

K2S2O8‐Mediated Oxysulfonylation of Vinyl Azides with Sodium Sulfinates to Access β‐Keto Sulfones in Water

AbstractWith water as solvent, K2S2O8 mediated facile and efficient synthesis of β‐keto sulfones through oxysulfonylation of vinyl azides with sodium sulfinates is described. The novel procedure has the advantages of being environmentally benign, mild reaction conditions, short reaction time, easy and simple operation, wide tolerance of functional groups, which establish the practical application of this methodology.

Silver-Catalyzed Decarboxylative Allylation of Difluoroarylacetic Acids with Allyl Sulfones in Water.

A practical silver-catalyzed decarboxylative allylation of α,α-difluoroarylacetic acids with allyl sulfones is described, which provides a variety of β,β-difluorinated alkenes in good yields. Notably, the reaction proceeds smoothly in water with good functional group tolerance. The practicality and synthetic value of this process was demonstrated by scaled-up experiment and elaboration of the products via reduction or Heck reaction. Primary mechanism investigations suggest that a radical process might be involved.

Electrochemical sulfonylation of alkenes with sulfonyl hydrazides: a metal- and oxidant-free protocol for the synthesis of (E)-vinyl sulfones in water.

An efficient electrochemical transformation of a variety of alkenes and sulfonyl hydrazides into vinyl sulfones with a catalytic amount of tetrabutylammonium iodide in water is reported. The reaction proceeds smoothly to afford vinyl sulfones with good selectivities and yields at room temperature under air in an undivided cell. Cyclic voltammograms and control experiments have been performed to provide preliminary insight into the reaction mechanism. The key features of this reaction include using pure water as solvent, transition metal- and oxidant-free conditions, and being easily scaled up to gram-scale synthesis.

Analysis of thiophenes in seawater: Molecularly imprinted polymer thin-film extraction with desorption electrospray ionization mass spectrometry

A new method coupling molecularly imprinted polymer thin-films (MIP thin-films) with desorption electrospray ionization mass spectrometry (DESI-MS) has been developed for indirect analysis of thiophene compounds in water. MIP thin-films were prepared on non-porous glass slides using a simple drop-casting fabrication method. The resulting films were used for indirect quantitative analysis of thiophene compounds in water by sorbing thiophene oxidation products (sulfones) to MIP films, then interrogating the MIP surface by DESI-MS. Oxidation of thiophenes to sulfones in water was achieved by reaction with a mixture of H2O2/formic acid at 65 °C for 2 h. DESI source parameters were optimized, and the optimal spray solvent composition was found to be MeOH:H2O (95:5 v/v) containing 0.5 mM NaCl. Among all sulfones formed, the protonated ion and sodium adduct signals were observed only for dibenzothiophene sulfone. The method was applied to dibenzothiophene in seawater, yielding a limit of detection at 3 ng L−1 and relative standard deviations (RSDs) below 8.0%. DESI-MS response was linear (R2 = 0.9841) over the range studied 0.1–10 μg L−1. With limited sample handling and ease of sample processing, many samples can be processed simultaneously making the method suitable for high throughput of screening environmental waters for dibenzothiophene and has the potential for detection its sulfone-metabolite.

Copper-catalyzed S-methylation of sulfonyl hydrazides with TBHP for the synthesis of methyl sulfones in water

A copper-catalyzed S-methylation of sulfonyl hydrazides with TBHP for the synthesis of methyl sulfones in water.

ChemInform Abstract: Catalyst‐Free Sulfonylation of Activated Alkenes for Highly Efficient Synthesis of Mono‐Substituted Ethyl Sulfones in Water.

A catalyst-free sulfonylation reaction of activated alkenes with sulfonyl hydrazides was efficiently developed under mild and environmentally benign conditions, in water without any ligand or additive. The reaction gave a range of structurally diverse mono-substituted ethyl sulfones with excellent yields, in which the by-product was nitrogen.

Catalyst-free sulfonylation of activated alkenes for highly efficient synthesis of mono-substituted ethyl sulfones in water

A catalyst-free sulfonylation reaction of activated alkenes with sulfonyl hydrazides was efficiently developed under mild and environmentally benign conditions, in water without any ligand or additive. The reaction gave a range of structurally diverse mono-substituted ethyl sulfones with excellent yields, in which the by-product was nitrogen.

{Mo132} Nanoball as an Efficient and Cost-Effective Catalyst for Sustainable Oxidation of Sulfides and Olefins with Hydrogen Peroxide

Atom-efficient and selective oxidation of sulfides to sulfoxides and sulfones in water and epoxidation of olefins in ethanol with hydrogen peroxide catalyzed by Keplerate nanoball polyoxomolybdate {Mo132} under heterogeneous conditions are reported. The reaction yield and selectivity was affected crucially by catalyst concentration. A structurally diverse set of sulfides and olefins were transformed into desired oxidation products regardless of the electronic nature of the substituents. In spite of the heterogeneous reaction mixtures throughout the work, no difficulties with reaction progress were noted. Products were isolated easily from green media, and the catalyst could be reused several times without any appreciable decrease in catalytic activity and selectivity. Accelerated reactions under ultrasonic irradiation did not change the selectivity of the oxidation products.

DNA-based asymmetric organometallic catalysis in water

Here, the first examples of DNA-based organometallic catalysis in water that give rise to high enantioselectivities are described. Copper complexes of strongly intercalating ligands were found to enable the asymmetric intramolecular cyclopropanation of α-diazo-β-keto sulfones in water. Up to 84% ee was achieved, in the presence of salmon testes DNA as the only source of chirality, using dipyrido[3,2-a:2′,3′-c]phenazine (dppz) derivatives as ligands.

Passive sampling of perfluorinated acids and sulfonates using polar organic chemical integrative samplers

The applicability of a polar organic chemical integrative sampler (POCIS) for detection and determination of perfluorinated acids and sulfonates in water was studied under field conditions. Standard POCIS configurations (i.e., pharmaceutical and pesticide) were deployed in effluent from a wastewater treatment plant for 1, 2, and 3 weeks. Ten of 15 target compounds were found in POCIS, five of which were quantified in wastewater. Pest-POCIS appeared more effective for the sampling, while Pharm-POCIS had a more rapid uptake kinetic, which leads to faster saturation or equilibrium. The results showed that the pesticide configuration is probably more suitable for the sampling of this class of compounds. Based on average concentration in water over the sampling period and amount of compound adsorbed in the POCIS, we calculated sampling rates for five studied compounds and obtained values of 0.034 to 0.222 L day(-1).

Development and Calibration of a Passive Sampler for Perfluorinated Alkyl Carboxylates and Sulfonates in Water

Perfluorinated chemicals (PFCs) are emerging environmental contaminants with a global distribution. Due to their moderate water solubility, the majority of the environmental burden is assumed to be in the water phase. This work describes the application of the first passive sampler for the quantitative assessment of concentrations of perfluorinated alkylcarboxylates (PFCAs) and sulfonates (PFSAs) in water. The sampler is based on a modified Polar Organic Chemical Integrative Sampler (POCIS) with a weak anion exchange sorbent as a receiving phase. Sampling rates were between 0.16 and 0.37 L d(-1), and the duration of the kinetic sampling stage was between 2.2 and 13 d. A field deployment in the most urbanized estuary in Australia (Sydney Harbour) showed trace level concentrations from passive samplers (0.1-12 ng L(-1)), in good agreement with parallel grab sampling (0.2-16 ng L(-1)). A separate field comparison of the modified POCIS with standard POCIS suggests the latter may have application for PFC sampling, but with a more limited range of analytes than the modified POCIS which contains a sorbent with a mixed mode of action.

Catalyst-free approach for solvent-dependent selective oxidation of organic sulfides with oxone

Selective oxidation of sulfides was successfully performed by employing oxone (2KHSO5·KHSO4·K2SO4) as oxidant without utilization of any catalyst/additive under mild reaction conditions. Notably, the reaction can be controlled by the chosen solvent. When ethanol was used as the solvent, sulfoxides were obtained in excellent yield; the reaction almost exclusively gave the sulfone in water. Furthermore, this protocol worked well for various sulfides to the corresponding sulfoxides in ethanol or sulfones in water.

ChemInform Abstract: The Organocatalytic Enantioselective Michael Addition of Aldehydes to Vinyl Sulfones in Water.

ChemInform Abstract: The Organocatalytic Enantioselective Michael Addition of Aldehydes to Vinyl Sulfones in Water.

The Organocatalytic Enantioselective Michael Addition of Aldehydes to Vinyl Sulfones in Water

The first organocatalytic enantioselective Michael addition of aldehydes to vinyl sulfones in water was achieved using our rationally designed organocatalyst. The rigid nature of the tricycle with an inherent chiral pocket provides a well-organized chiral environment, which together with the hydrophobic pocket, enabled this elusive reaction to proceed smoothly in water.

Using second-order calibration to identify and quantify aromatic sulfonates in water by high-performance liquid chromatography in the presence of coeluting interferences

We used the Generalized Rank Annihilation Method (GRAM), a second-order calibration method, to quantify aromatic sulfonates in water with high-performance liquid chromatography (HPLC) when interferences coeluted with the analytes of interest. With GRAM, we can quantify in only two chromatographic analyses, one for a calibration sample and one for the unknown sample. The calculated concentrations were not statistically different to those obtained when the chromatographic separation of the unknown sample was modified in order to completely separate the analyte from the interferences before univariate calibration. With GRAM, the concentrations are determined much more quickly because a complete resolution is not required.

Analysis of aromatic sulfonates in water by solid-phase extraction and capillary electrophoresis

The separation of 14 different aromatic sulfonates of environmental concern by capillary (zone) electrophoresis (CZE) is presented. A new off-line solid-phase extraction (SPE) enrichment procedure, that is compatible with CE analysis, was developed, using the styrene–divinylbenzene adsorbent LiChrolut EN. The combined method of SPE and CE allows the determination of aromatic sulfonates in water samples in the low μg/l range. Separations are performed with a simple sodium borate buffer at pH 9.3. Analytes are detected by UV absorbance and fluorescence emission with a Xe-lamp excitation source, and both principles are compared. The recoveries for most of the sulfonates are >70% for the extraction from spiked tap and river water. The average method precision is <20% for replicate analyses. Very hydrophilic sulfonates cannot be extracted by this method. The detection limit of the combined method of SPE enrichment and CE analysis is approximately 0.1 μg/l for 200-ml water samples. The performance of the method was checked with the analysis of river and contaminated seepage water.