Sulfonic Acid Chloride Research Articles

Exploring deep eutectic solvents of methane sulfonic acid and choline chloride: Formation, properties, and metal solvent effectiveness

Methane sulfonic acid (MSA), a hydrogen bond donor (HBD), was combined with choline chloride (HBA) at varying molar ratios (1:1, 1:2 and 2:1) to explore the formation of deep eutectic solvents (DES). The resulting blends, at 1:1 and 2:1 ratio, remained liquid at ambient temperature. Among these combinations, the DES formed with a 1:1 molar ratio (MSA-ChCl) exhibited the highest decomposition temperature (166 °C) followed by MSA-ChCl (1:2) and MSA-ChCl (2:1). Alongside, the glass transition temperature of the DES also remained relatively unaffected by the molar ratio of its components. Notably, both density and viscosity were observed to be temperature dependent. To elucidate hydrogen bonding interactions between choline chloride and MSA, Fourier Transform Infrared (FTIR) and Nuclear Magnetic Resonance (NMR) spectroscopy were employed. The broadening and shifting of IR peaks illustrate the formation of intermolecular bonding between MSA and ChCl. Density Functional Theory (DFT) calculations were conducted to optimise molecular structures, analyse HOMO-LUMO levels, estimate electronegativity and ionization potential, and generate electrostatic potential surfaces of the DES. As per calculated Molecular Electrostatic Potential (MEP) by DFT of pure MSA and ChCl, SO of MSA has most electron deficient region and it has potential to interact with electron positive OH part of ChCl, which is also demonstrated by IR spectra. MSA-ChCl (2:1) displayed the most negative electron density and proved to be the most effective metal solvent among the DES formulations tested. Exceptional solubility of lithium in MSA-ChCl (2:1) was observed, exceeding 105 mg/L. Moreover, zinc, copper, cobalt, and iron also demonstrated good solubility in MSA-ChCl (2:1), ranging from 105 to 104 mg/L.

Organic Ionic Liquid Grafted Nano‐CeO2: A Highly Efficient Photocatalyst for Hydroxylation of Benzene and Reduction of Cr (VI)

AbstractAn ionic liquid, namely imidazolium sulfonic acid chloride (ISAC) has been electrostatically grafted over cerium oxide nanoparticles to produce a nanocomposite, nano‐CeO2‐IL. The as‐prepared composite was characterized by various analytical techniques such as XRD, FT‐IR, SEM, TEM, XPS, BET, UV‐DRS, PL, and TGA to confirm the grafting of ISAC over CeO2 NPs. The photocatalytic process is regarded as the method of choice for the elimination of air pollutants because of its great efficiency and relatively benign working conditions. According to UV‐DRS spectra, its optical gap is 2.07 eV, which is appropriate for the visible light spectrum. The composite was investigated as a visible‐light‐driven photocatalyst for hydroxylation of benzene to phenol and heavy metal Cr (VI) reduction. Moreover, the scavenger experiments confirmed the detection of ⋅OH radicals which played a crucial role in the photocatalytic experiments. Within 60 minutes, 98.5 % of benzene was converted to phenol with 82.7 % selectivity in addition to 93.63 % Cr (VI) reduction within 30 mins. The photocatalytic reduction of Cr(VI) to Cr(III) follows a first‐order model with a rate constant of 0.027 min−1. The remarkably high photocatalytic performance of the catalyst may be ascribed to the synergistic interaction between the nano‐CeO2 catalyst and ionic liquid.

Synthesis and performance of temperature- and acid-resistant ternary-copolymer thickener

An amphoteric polyacrylamide thickener was synthesized using 2-acrylamido-2-methylpropane sulfonic acid (AMPS), acrylamide (AM), and dimethyl diallyl ammonium chloride (DMDAAC). According to the experimental results, the best polymerization conditions were as follows: temperature of 45 °C, AMPS:AM:DMDAAC mass ratio of 1:3:1, and monomer, initiator, guide agent, crosslinking agent, and urea concentrations of 27%, 0.6%, 0.15%, 0.3%, and 1%, respectively. The apparent viscosity, measured at room temperature with a six-speed rotational viscometer, was 135 and 45 mPa s in the absence and presence of 20% HCl, respectively. The temperature resistance of the thickener solution was evaluated using an AR2000ex rheometer; at 120 °C and a shear rate of 170 s−1, its apparent viscosity was 99.7 mPa s. Moreover, the chemical composition and morphology of the synthesized thickener were investigated via Fourier-transform infrared spectroscopy and scanning electron microscopy, respectively.

Core-shell assembly of ZrO2 nanoparticles with ionic liquid: a novel and highly efficient heterogeneous catalysts for Biginelli and esterification reactions.

Imidazolium sulfonic acid chloride grafted ZrO2 nanoparticles (ZrO2-IL) were synthesized through facile post-treatment of the nanoparticles with the imidazolium-sulfonic acid chloride ionic liquid. The immobilization of the ionic liquid over the ZrO2 nanoparticles was evident from the XRD, SEM, TEM, Raman, BET, and XPS analysis. The results obtained from the XRD analysis clearly show that the catalyst has an orthorhombic structure and from the BET analysis it is evident that the surface is mesoporous with uniform pore sizes and pore distribution. Further evidence of immobilization of ionic liquid over the ZrO2 NPs was obtained from the SEM, TEM, XPS, and Raman analysis. Under mild conditions, the synthesized heterostructure was used in the acid-catalyzed esterification of different acids. The ZrO2-IL catalyst converts 99% of the acid to ester with a 98.9% yield in 1h. The material was also shown to be highly efficient as catalyst for the Biginelli reaction under solvent-free conditions, with the catalyst for dihydropyrimidin-2(1H)-one (DHPMs) in 1h with 99.2% conversion and 99% yield. The synergy between the ionic liquid catalyst and the substrates increased the catalytic efficiency and resulted in high-yield product conversion. The mechanism of both transformation reactions was investigated, as well as the synergy between ionic liquid and ZrO2 nanoparticles for better catalytic efficiency was established.

Phase engineering in graphitic carbon nitride with imidazolium sulfonic acid chloride ionic liquid functionalization for photocatalytic side-chain oxidation of toluene

Herein, the phase and photocatalytic property of graphitic carbon nitride (g-C3N4) are modulated with the functionalization of ionic liquid (IL) by post-treatment of g-C3N4 with imidazolium sulfonic acid chloride. The structure, morphology and optoelectronic properties of synthesized catalyst were thoroughly investigated. The functionalization of Ionic liquid has induced polycrystallinity to the amorphous g-C3N4. The g-C3N4 –IL is highly efficient towards photocatalytic side-chain oxidation of toluene using H2O2with toluene conversion of 58% with 97% benzaldehyde selectivity in acetonitrile and toluene conversion of 49% and 96% benzaldehyde selectivity in organic solvent-free conditions. The synergy between g-C3N4 and the IL elevates the visible light absorption and lower photoluminescence intensity. The g-C3N4-IL catalyst efficiently halts over-oxidation to get high selectivity for the desired product. In addition, graphene oxide and reduced graphene oxide were also functionalized with IL to examine their photocatalytic efficiency and considerable efficiencies were observed. The g-C3N4-IL is highly stable and recyclable.

Isoquinolinium-N-sulfonic acid thiocyanate/H2O2 as efficient reagent for thiocyanation of N-bearing (hetero)aromatic compounds

In the present study, isoquinoline sulfonic acid thiocyanate (isoquinoline-SO3H)SCN and isoquinoline sulfonic acid chloride (isoquinoline-SO3H)Cl as a novel and heterogeneous catalyst were designed and synthesized by a simple and inexpensive procedure. The prepared heterogeneous catalyst was characterized by FT-IR, 1H NMR, and 13C NMR techniques. Then, the catalytic activity of (isoquinoline-SO3H)SCN and (isoquinoline-SO3H)Cl were successfully investigated for the synthesis of aryl and heteroaryl thiocyanates derivatives through a one-pot reaction. Moreover, the use of (isoquinoline-SO3H)SCN provides a quite simple and more convenient procedure, due to it has both acidic group and thiocyanation agent in reaction. The present procedure offers advantages such as the usage of a commercially available materials, cheap and chemically stabile reagents, short reaction time, excellent yield, ease of separation by simple filtration, and simple reaction work-up.

Synthesis, characterization and application of N,N,N',N'-tetramethylethylenediaminium-N-(silica-n-propyl)-N'-sulfonic acid chloride trifluoroacetate as a novel and effective catalyst for preparation of bis-coumarins

In this research, a novel material namely N,N,N',N'-tetramethylethylenediaminium-N-(silica-n-propyl)-N'-sulfonic acid chloride trifluoroacetate ([TEDSPSCT]) was synthesized, and its structure was characterized using Fourier-transform infrared spectroscopy (FT-IR), energy-dispersive X-ray (EDS), field emission scanning electron microscopy (FE-SEM), thermal gravimetric (TG), differential thermal gravimetric (DTG) and x-ray diffraction (XRD); most of the partcles were in nano-size, and a few of them were in micro-size. Afterward, [TEDSPSCT] was used as effective and recyclable catalyst for the preparation of bis-coumarins via the reaction of 4-hydroxycoumarin (2 equivalents) with arylaldehydes (1 equivalent) under solvent-free conditions; these compounds were obtained in high yields and short reaction times. Moreover, an attractive and logical mechanism based on dual-functionality of the catalyst has been described {this catalyst has both acidic group (SO3H) and weak basic group (trifluoroacetate)}.

A benevolent direction to environmental suitability: ionic liquid immobilized MoO3 nanoparticles used in the efficient visible light-driven photocatalytic degradation of antibiotics

This paper summarizes the synthesis of a novel MoO3-bonded imidazolium sulfonic acid chloride (MoO3-IL) using a facile precipitation method and its application in the degradation of two organic pollutants.

Recyclable deep eutectic solvent coupling sodium hydroxide post-treatment for boosting woody/herbaceous biomass conversion at mild condition

A novel recyclable deep eutectic solvent (DES) consisting of p-toluene sulfonic acid (p-TsOH) and choline chloride (ChCl) was developed for efficient woody poplar sawdust (PL) and herbaceous miscanthus (MC) conversion at mild condition. The extraction of leftover lignin on the surface of DES pretreated residues using NaOH solution at room temperature greatly improved the enzymatic hydrolysis efficiency. Near complete cellulose conversion of PL and MC residues were obtained with a degree of delignification and xylan removal over 90% at 100 °C within 40 min. The strong correlations between xylan (R2 = 0.95) and lignin (R2 = 0.82) removal with cellulose conversion were observed in MC as well as positive correlations (R2 > 0.77) in PL. The results demonstrated that the DES system coupling NaOH post-treatment was a promising method to achieve an economically feasible biomass conversion process, which was effective for both woody PL residues and herbaceous MC.

Fe3O4@SiO2@(CH2)3-urea-quinoline sulfonic acid chloride: A novel catalyst for the synthesis of coumarin containing 1,4 dihydropyridines

Fe3O4@SiO2@(CH2)3-urea-quinoline sulfonic acid chloride, as a novel and efficient nanomagnetic catalyst bearing urea linkers, was designed, synthesized and then fully characterized by using various techniques. To investigate the catalytic activity of the described catalyst, it was used for the synthesis of coumarin containing 1,4-dihydropyridines (DHPs), through a condensation reaction of aromatic aldehydes, 4-hydroxycoumarin, and ammonium acetate under solvent-free conditions. This procedure includes important aspects like simple procedure, simplicity of product isolation using water, decreasing the temperature of reaction, disuse of solvent, high to excellent yields, environmentally benign reaction conditions and short reaction times. Also, the presented catalyst was recycled and reused for at least five times with only a negligible decrease in its catalytic activity. The applied catalyst has both acidic and H-bond donor-acceptor sites so that it can use as a dual role catalytic system.

Ionically Tagged Magnetic Nanoparticles with Urea Linkers: Application for Preparation of 2-Aryl-quinoline-4-carboxylic Acids via an Anomeric-Based Oxidation Mechanism.

In this exploration, we reported the design and synthesis of a novel ionically tagged magnetic nanoparticles bearing urea linkers, namely, Fe3O4@SiO2@(CH2)3–urea–thiazole sulfonic acid chloride. The structure of the mentioned compound was fully characterized by using several techniques including Fourier transform infrared spectroscopy, energy-dispersive X-ray analysis, elemental mapping analysis, thermogravimetric analysis/differential thermal analysis, scanning electron microscopy, transmission electron microscopy, and vibrating sample magnetometer. In the presence of the novel reusable catalyst, applied starting materials including aryl aldehydes, pyruvic acid, and 1-naphthylamine condensed to afford the desired 2-aryl-quinoline-4-carboxylic acid derivatives via an anomeric-based oxidation pathway under solvent-free conditions.

Synthesis of Novel Chiral 18‐Sulfanyl and Sulfonyl Dehydroabietane Derivatives

AbstractFor the first time, dehydroabietic acid ethyl ester was used as initial material to produce the corresponding at the C‐18 position thioacetate, thiol, disulfide, sulfonic acid and sulfonyl chloride which open up prospects for the synthesis of other polyfunctional compounds combining a biologically active dehydroabietane fragment with various pharmacophore groups. The optimal conditions were found to directly oxidize dehydroabietanthiol to sulfochloride using chlorine dioxide as an oxidant in the presence of vanadyl acetylacetonate as a catalyst. This sulfochloride synthesized was proposed to use for obtaining a series of sulfonamides with alkyl, aryl, hetaryl and monosaccharide fragments.

Deep eutectic solvents (DESs) as powerful and recyclable catalysts and solvents for the synthesis of 3,4-dihydropyrimidin-2(1H)-ones/thiones

Abstract Deep eutectic solvents (DESs) are successfully used as powerful and recyclable catalysts and solvents for the synthesis of 3,4-dihydropyrimidin-2(1H)-ones/thiones (DHPMs). The acidity of DESs is the main factor that determines catalytic activity. DESs, based on p-toluene sulfonic acid (PTSA) and choline chloride (ChCl), exhibits the highest catalytic activity. ChCl/2PTSA is suitable for a vast variety of aromatic aldehydes with electron-donating and electron-withdrawing groups, different β-diketonates, and urea or thiourea to obtain the corresponding DHPMs. Furthermore, DESs can be recycled easily after synthesis. The reused DESs achieve catalytic efficiency six times without significant changes. This study will provide a new green catalyst and efficient process for the synthesis of DHPMs.

Synthesis and characterization of 4,4′-bipyridinium sulfonic acid chloride as a new and efficient catalyst for the preparation of amidoalkyl phenols and bis amidoalkyl phenols

4,4′-bipyridinium sulfonic acid chloride {[SO3H-4,4′-bipyridine-SO3H]Cl2}, as a new solid acid, was synthesized and fully characterized by fourier transform infrared spectroscopy (FT-IR), X-ray diffraction analysis (XRD), scanning electron microscope (SEM), Energy-dispersive X-ray spectroscopy (EDX), thermal gravimetric analysis (TGA), 1H NMR and 13C NMR as well as mass spectra. [SO3H-4,4′-bipyridine-SO3H]Cl2 was successfully applied as a new and efficient catalyst for the preparation of amidoalkyl phenols and bis amidoalkyl phenols as a new category of compounds at 110 °C under solvent-free conditions.

Bronsted acidic ionic liquids: New transesterification agents for the compatibilization of polylactide/ethylene-co-vinyl acetate blends

Sulfonic acidic ionic liquids (ILs) based on imidazolium or triphenylphosphonium cations were synthesized and used as new transesterification agents to compatibilize partially bio-based thermoplastic blends composed of polylactide (PLA) and ethylene-co-vinyl acetate (EVA) copolymer containing 18% of VA. The influence of these Bronsted acidic ionic liquids (BAIL) as catalysts was investigated and compared with conventional catalyst such as titanium tetrabutoxide (Ti(BuO)4). In all cases, the presence of the sulfonic acidic ionic liquids resulted in an increase of the torque during the processing of the polymer blends, suggesting the transesterification reaction, which was confirmed by Fourier transform infrared spectroscopy (FTIR). Moreover, the degradation of PLA chain was minimized by the presence of ILs, whereas Ti(BuO)4 promoted a decrease of molar mass of the PLA component and a decrease of the torque. Thus, the influence of the transesterification on the final properties such as the thermal degradation as well as the thermomechanical and mechanical properties has been studied. The highest efficiency of the blend compatibilization was achieved by using only 1wt% of IL denoted triphenylphosphonium butyl sulfonic acid chloride [TPP-bSO3H.Cl]. Indeed, the SEM micrograph of this blend was more uniform with EVA particles well adhered to the PLA matrix.

Preparation and characterization of WO3 bonded imidazolium sulfonic acid chloride as a novel and green ionic liquid catalyst for the synthesis of adipic acid

The work represents the synthesis of a novel WO3 bonded IL catalyst. It is used as a heterogeneous recoverable catalyst in the oxidation of cyclohexene to adipic acid.

Application of Deep Eutectic Solvent (DES) as a Reaction Media for the Esterification of Acrylic Acid with n-Butanol

Abstract Within the framework of green chemistry, catalysts should be met different criteria such as biodegradability, recyclability, flammability, non-toxicity and low price. Acidic deep eutectic solvent (DES) have been synthesized for this purpose, by mixing para-toluene sulfonic acid and choline chloride. The catalytic activity of DES was studied in the esterification of acrylic acid with n-butanol. The usage of DES as catalyst is simple, safe and cheap. The effects of temperature, catalyst loading, n-butanol/acrylic acid molar ratio on the conversion of acrylic acid were performed. The batch reactor experiments were carried out at temperatures of 338, 348, 358 and 368 K, molar ratio of butanol to acrylic acid of 1, 2,3 and catalyst loading of 10, 15, 20 and 90 g/L. 90.2% of acrylic acid conversion was achieved at a temperature of 358 K and catalyst loading of 20 g/L. Reusability of DES was investigated. Reusability and catalytic activity makes DES efficient as catalyst.

Synthesis, characterization and evaluation of a quadripolymer with low molecular weight as a water based drilling fluid viscosity reducer at high temperature (245 °C)

AbstractTo construct an ultra‐high temperature stable drilling mud with a relatively low viscosity, a new viscosity‐reducing additive was synthesized and evaluated. This additive is a quadripolymer of acrylic acid (AA), 2‐acryl‐amido‐2‐methyl‐1‐propane sulfonic acid (AMPS), methyl acrylate (MA) and dimethyl diallyl ammonium chloride (DDAC) with low molecular weight synthesized by free radical polymerization, and its general molecular composition was confirmed by Fourier transform infrared spectroscopy. Thermal gravimetric analysis showed that the polymer has a very high temperature tolerance, i.e. it is stable up to 340 °C. Turbidity measurements with a UV−visible spectrophotometer showed that the polymer has a high salt tolerance in solution. It remained in solution at NaCl concentrations of up to 266 958 mg L−1 and at CaCl2 concentrations of up to 5000 mg L−1. The quadripolymer was found to inhibit hydration of the exchangeable ions in the clay particles and this was affirmed by a reduction in interlayer spacing. It also displayed high adsorption on calcium montmorillonite at different pH and even in the presence of NaCl, and caused the breakup of the particle network structure. This additive, when added to drilling mud prepared in both fresh and salt water, was found to reduce the mud viscosity and yield stress before and after aging for 16 h at 245 °C compared to base mud especially below 220 °C and 4.5 MPa. Importantly, this additive in mud was found to perform effectively at a relatively high pH and in a broad pH range of 7–11. © 2015 Society of Chemical Industry

Synthesis of copolymer from lactic acid-polyethylene terephthalate (LA-PET) copolymerization

Bio-plastic has been a need of the hour for the past few decades and the usage of lactic acid (LA) in the production of bio plastic opens a new window to the field. Polyethylene terephthalate (PET) thermoplastic polyester with excellent tensile and impact strength, chemical resistance, clarity, process ability, and transparency has become a bane to the society. The co polymerization increases the mechanical strength of LA. In this study, the production and optimization of the copolymer of LA –PET was done. The blend of sugarcane bagasse and corn stover was used for the production of LA by incubating with Lactobacillus sp. for 24 h. Lactobacillus sp. is a potent producer of lactic acid and crude curd was used as the source. The optimization in lignin breakdown by 10% NH4OH and 2% NaOH and acid hydrolysis by 10% H 2 SO 4 of the blend was done. The process parameters in the copolymerization LA-PET using p-toluene sulfonic acid, ethylene glycol and stannous chloride were also analyzed. The products formed were confirmed by the FTIR analysis at various transmittance peaks at 1681, 3008 and 3610 cm -1 . The process of production of the copolymer proves to be a green technology by decreasing the PET contamination of the environment and also helping in the production of bio-degradable plastics in the run. Key words : Lactic acid, copolymer, bioplastic, polyethylene terephthalate.

Influence of Dodecylbenzene Sulfonic Acid Doping on Structural, Morphological, Electrical and Optical Properties on Polypyrrole/3C-SiC Nanocomposites

Dodecylbenzene sulfonic acid (DBSA) doped nanocomposites of Polypyrrole-silicon carbide (PPy-SiC) were synthesized via insitu chemical oxidation polymerization of Pyrrole act as monomer. Dodecylbenzene sulfonic acid and Iron (III) chloride were used as a dopant and oxidization agent, respectively. The molar ratio of monomer unit to oxidization agent was 1:2.4. These nanocomposites were characterized for their structure, thermal stability, surface morphology and DC electrical conductivity by UV-Visible spectroscopy, FT-IR, XRD, TGA, SEM and four-probe method respectively. The electrical property of chemically prepared Polypyrrole and Polypyrrole/SiC in aqueous solution was found to be strongly depending on doping material, oxidant and solvent. It obeys Ohm’s Law and convincing applies for battery technology and sensor applications.