P-toluenesulfonyl Hydrazide Research Articles

Development of a simple and safe route to C-3 arylated 1H-pyrazoles

A simple transition-metal-free and highly chemoselective strategy for the preparation of C-3 arylated 1H-pyrazoles with enaminones and p-toluenesulfonyl hydrazide (TsNHNH2) has been developed. The current environmental benign protocols showed that, TsNHNH2 could be served as the safe and easy-to-handle hydrazide for the preparation of C-3 arylated 1H-pyrazoles instead of the explosive and genotoxic hydrazine hydrate under mild conditions, with broad substrate scope and excellent functional group tolerance. More importantly, a gram-scale synthesis of a synthetic equivalent of key intermediate to immuno-oncology agonist BMS-986299 was demonstrated successfully through a simple crystallization or extraction process for the scalable production.

Regioselective Thiolation of Indole to Construct 3-Arylthioindoles

Abstract: A practical and novel approach for the regioselective synthesis of 3-arylthioindole derivatives has been accomplished using a combination of indole substrates with p-toluene sulfonyl hydrazide. This methodology employs NIS as the oxidant and PPh3 as the reductant to give the desired 3-arylthioindoles in good to excellent yields. This method offers several advantages, including simplicity, operational ease, and broad substrate scope. objective: To develop a highly efficient protocol for the access of diverse arylthioindoles

Unveiling the antimicrobial potency and binding interaction between sulfonamide substituted Schiff’s bases and BSA protein: An integrated experimental and theoretical approach

Sulfonamide derived Schiff’s bases encompass significant properties such as antifungal, anti-inflammatory, anticancer, antibacterial, antiproliferative, and antioxidant and hold a central position in therapeutics and diagnostics. Hence, it is essential to comprehend their interconnection with carrier proteins such as Bovine serum albumin (BSA). Herein, two different sulfonamide derived Schiff’s base derivatives,N'-(2,5-Dimethoxybenzylidene)-4-methylbenzenesulfonohydrazide SB-1 and N'-(3-Bromo-4-methoxybenzylidene)-4-methylbenzenesulfonohydrazide SB-2 were synthesized by reacting respectivealdehydes with p-toluenesulfonyl hydrazide as the amine counterpart in absolute ethanol and structurally characterized by FT-IR,1H and13C NMR, elemental analyses, thermogravimetric analysis (TGA), mass spectrometry and single-crystal X-ray crystallography. The binding interactions between BSA andSB-1 and SB-2were made by employing UV–vis. absorption and fluorescence spectroscopy. Information about the binding constant was obtained from the absorbance enhancement and fluorescence quenching of BSA in the presence ofSB-1 and SB-2respectively. However, the binding efficiency ofSB-1was found to be superior to that of BSA in comparison toSB-2. The antibacterial potential ofSB-1 and SB-2 wastested on E. coliandS. aureus using thewell diffusion method.In silicoADME properties forSB-1 and SB-2were checked to assess their stability. The binding mechanisms to the specific enzymes associated with the BSA interaction and the antibacterial capabilities of theSB-1 and SB-2were further supported by molecular docking calculations. The detailed studies provide comprehensive data to support the utility of prepared Schiff’s bases as potential biomarkers in therapeutics.

Azide-free cyclization reaction access to 4-aryl-NH-1,2,3-triazoles: P-toluenesulfonyl hydrazide and sulfamic acid as nitrogen sources.

An iodine-mediated cyclization has been developed to 4-aryl-NH-1,2,3-triazoles, with p-toluenesulfonyl hydrazide and sulfamic acid used as nitrogen sources. Sulfamic acid plays a crucial role in this reaction by both acting as a substrate and providing an acidic environment. This reaction offers a metal- and azide-free strategy to access NH-1,2,3-triazoles.

Accessing Bioactive Hydrazones by the Hydrohydrazination of Terminal Alkynes Catalyzed by Gold(I) Acyclic Aminooxy Carbene Complexes and Their Gold(I) Arylthiolato and Gold(III) Tribromo Derivatives: A Combined Experimental and Computational Study.

Hydrohydrazination of terminal alkynes with hydrazides yielding hydrazones 5-14 were successfully catalyzed by a series of gold(I) acyclic aminooxy carbene complexes of the type [{(4-R2-2,6-t-Bu2-C6H2O)(N(R1)2)}methylidene]AuCl, where R2 = H, R1 = Me (1b); R2 = H, R1 = Cy (2b); R2 = t-Bu, R1 = Me (3b); R2 = t-Bu, R1 = Cy (4b). The mass spectrometric evidence corroborated the existence of the catalytically active solvent-coordinated [(AAOC)Au(CH3CN)]SbF6 (1-4)A species and the acetylene-bound [(AAOC)Au(HC≡CPhMe)]SbF6 (3B) species of the proposed catalysis cycle. The hydrohydrazination reaction was successfully employed in synthesizing several bioactive hydrazone compounds (15-18) with anticonvulsant properties using a representative precatalyst (2b). The DFT studies favored the 4-ethynyltoluene (HC≡CPhMe) coordination pathway over the p-toluenesulfonyl hydrazide (NH2NHSO2C6H4CH3) coordination pathway, and that proceeded by a crucial intermolecular hydrazide-assisted proton transfer step. The gold(I) complexes (1-4)b were synthesized from the {[(4-R2-2,6-t-Bu2-C6H2O)(N(R1)2)]CH}+OTf- (1-4)a by treatment with (Me2S)AuCl in the presence of NaH as a base. The reactivity studies of (1-4)b yielded the gold(III) [{(4-R2-2,6-t-Bu2-C6H2O)(N(R1)2)}methylidene]AuBr3 (1-4)c complexes upon reaction with molecular bromine and the gold(I) perfluorophenylthiolato derivatives, [{(4-R2-2,6-t-Bu2-C6H2O)(N(R1)2)}methylidene]AuSC6F5 (1-4)d, upon treatment with C6F5SH.

Low-Density Particleboards Modified with Blowing Agents—Characteristic and Properties

Although lightweight particleboards have been commercially available for years, they still have a number of disadvantages, including difficulty to process, brittleness, low impact strength, and other mechanical resistance. The aim of the paper was to determine the possibility of producing particleboards of reduced density (dedicated for furniture industry) as a result of using blowing agents from the group of hydrazides, dicarboxamides, or tetrazoles, which were modifiers of the adhesive resin used for bonding the particles of the core layer of three-layer particleboards. The concept presents the possibility of producing low-density particleboards in a standard technological process by modifying the adhesive resin, which has not been practiced by others until now. Analysis of the results of testing the particleboards properties with various types of modifiers (blowing agents), glue content (high 10%/12% and low 8%/10%), differing in glue dosing method, and different particle sizes allowed concluding that the most satisfactory effect was found in particleboards made of the variant modified with p-toluenesulfonyl hydrazide. This variant was characterised by the highest mechanical properties (bending strength, modulus elasticity, and internal bond strength) with high dimensional stability. The presented technology proposal can be applied in the industry.

Synthesis, NMR spectral, docking and antimicrobial studies of some 12-aryl-9,9-dimethyl-8,9,10,12-tetrahydrobenzo[a]xanthen-11-one tosylhydrazones

A new series of 12-aryl-9,9-dimethyl-8,9,10,12-tetrahydrobenzo[a]xanthen-11-one tosylhydrazones (7-12) have been synthesized from the corresponding 12-aryl-9,9-dimethyl-8,9,10,12-tetrahydrobenzo[a]-xanthen-11-one (1-6) and p-toluenesulfonyl hydrazide by condensation reaction. The structure of the synthesized compounds 7-12 were confirmed by their spectral analysis such as FT-IR, 1H NMR, 13C NMR, HOMOCOSY, HSQC and HMBC. Docking study was conducted to predict the significant interactions of the six compounds with the protein 1JIJ for its antibacterial activity. The docking results provided that the compounds 9 and 12 possess high inhibition constant as well as high binding energy. The synthesized compounds were screened for their in vitro antibacterial and antifungal activity and the observed activity is found to be moderate compared to the standard drugs.

Base-Promoted Stereoselective Hydrogenation of Ynamides with Sulfonyl Hydrazide to Give Z-Enamides

A base-mediated semihydrogenation of ynamides using p-toluenesulfonyl hydrazide as an inexpensive and easy-to-handle hydrogen donor is reported. This transition-metal-free protocol avoids overhydrogenation and reduction of other functional groups, generating the thermodynamically unfavorable Z-enamides exclusively.

(Invited) Tuning Triblock Co-Polymer Silver Interactions on the Nanoscale to Enhance Transport in Electrodes for Electrochemical Devices Based on Anion Exchange Membranes

Anion exchange membranes (AEMs) have recently attracted interest for applications in fuel cells, electrolyzers, redox flow batteries, reverse electrodialysis, and water purification. In contrast to proton exchange membranes (PEMs), AEMs operate in base instead of acid and facilitate the transport of anionic species. In fuel cells and electrolyzers, this allows for more facile kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) respectively. Therefore, AEM-based devices provide the opportunity to utilize non-precious metal catalysts to achieve similar performance to Pt-based catalysts and a substantially reduced cost. The electrodes of these devices are comprised of a heterogeneous mixture of conductive carbon support, catalyst particles, and ionomer, which form a triple-phase boundary where the electrochemical reactions take place. The ionomer is an alkaline polymer electrolyte similar to the AEM which transports OH- and water to/from the catalyst surface and promotes reactant transport.The electrode layers in PEM-based fuel cells were developed empirically, and it was not until recently that research efforts were dedicated to investigating the heterogeneous microstructure and triple-phase boundary that form. Currently, the catalyst layer as it exists in an operating device is not well understood due to its complex nature; however, model interfaces between ionomers and catalyst particles have been used to provide valuable insight on ionomer-catalyst interfacial interactions. It is known from studies with Nafion® that restructuring of the polymer morphology can occur when it exists as an ionomer thin film at a catalyst interface. The behavior of the thin film ionomer changes compared to its bulk characteristics, which ultimately affects electrode kinetics by altering the nature of its microstructure, leading to shifts in morphology, water uptake properties, and ionic and water transport networks.Initial work was driven by the overarching hypothesis that the polymer-catalyst interfacial interactions could be modified by changing the ionomer chemistry. This was investigated by studying interactions between silver nanoparticles and anion exchange ionomers functionalized with two different quaternary ammonium cations, using our previously reported block copolymer backbone polychloromethylstyrene-b-polycyclooctene-b-polychloromethylstyrene (PCMS-b-PCOE-b-PCMS) functionalized with either trimethylammonium (TMA) or methylpiperidinium (MPRD) quaternary ammonium cations. Our early findings indicated there were interactions between silver nanoparticles and C=C groups in the polycyclooctene midblock of the polymer backbone. This motivated the development of a modified anion exchange polymer by hydrogenating the PCOE midblock in PCMS-b-PCOE-b-PCMS to synthesize a polyethylene (PE) midblock. Hydrogenation was achieved through a reaction with p-toluenesulfonyl hydrazide. The improved characteristics of the PE-based membrane have prompted studies investigating the comparison of saturated and unsaturated ionomers.A uniquely tunable polymer system was developed which has enabled further investigations of ionomer thin films on silver substrates. The thin film geometry allows for the use of grazing incidence small angle x-ray scattering (GISAXS) and atomic force microscopy (AFM) to study the interfacial morphology as a function of ionomer chemistry. Restructuring of the polymer morphology compared to its bulk properties has been confirmed, and our initial findings on the contribution of different cationic moieties will be discussed in the results of this report.

New one-pot synthesis of anti-tuberculosis compounds inspired on isoniazid.

A library of thirty N-substituted tosyl N'-acryl-hydrazones was prepared with p-toluenesulfonyl hydrazide, methyl propiolate and different aldehydes in a one-pot synthesis via an aza-Michael reaction. The scope of the reaction was studied, including aliphatic, isoprenylic, aromatic and carbocyclic aldehydes. The prepared collection was tested against Mycobacterium tuberculosis H37Rv. Nine analogs of the collection showed Minimum Inhibitory Concentration ≤10μM, of which the most active members (MIC of 1.25μM) were exclusively E isomers. In order to validate the mechanism of action of the most active acrylates, we tested their activity on a M.tuberculosis InhA over-expressing strain obtaining MIC that consistently doubled those obtained on the wild type strain. Additionally, the binding mode of those analogs on M.tuberculosis InhA was investigated by docking simulations. The results displayed a hydrogen bond interaction between the sulfonamide and Ile194 and the carbonyl of the methyl ester with Tyr 158 (both critical residues in the interaction with the fatty acyl chain substrate), where the main differences on the binding mode relays on the hydrophobicity of the nitrogen substituent. Additionally, chemoinformatic analysis was performed to evaluate in silico possible cytotoxicity risk and ADME-Tox profile. Based on their simple preparation and interesting antimycobacterial activity profile, the newly prepared aza-acrylates are promising candidates for antitubercular drug development.

Novel Schiff bases derived from N-aryl maleimide derivatives as an effective antimicrobial agent: Theoretical and experimental approach

A set of new Schiff bases of N-aryl 3- and 4-substituted maleimides has been prepared via condensation of N-aryl 3- and 4- substituted maleimides with p-toluene sulfonyl hydrazide in acidic medium at room temperature. The structures of synthesized compounds were characterized by IR, 1H NMR, 13C NMR, MS spectral data, and further confirmed by single-crystal x-ray crystallography for 5c. The computational study was carried out using Gaussian 09 software by using the B3LYP/6-311+G(d,p) basis set. Single-crystal study results showed much closeness with computational study results. These novel compounds were screened for their antimicrobial activity against two pathogenic bacteria such as Escherichia coli (ATCC 8739) and Staphylococcus aureus (ATCC25923) and two pathogenic fungi such as Aspergillus niger (MCIM10231) and Candida albicans (MTCC6275). The investigation of antimicrobial screening data showed that the most of tested compounds are moderate to good microbial inhibitors.

Modifications of addition poly(5-vinyl-2-norbornene) and gas-transport properties of the obtained polymers

Herein four modified polymers were prepared from readily available addition poly(5-vinyl-2-norbornene) (PVNB) and their gas-transport properties were studied in detail. Hydrogenation, epoxidation, cyclopropanation and thiol-en reactions were chosen for the modifications of PVNB. Hydrogenation of PVNB was performed using p-toluenesulfonyl hydrazide. Epoxidation of PVNB was realized employing m-chloroperoxybenzoic acid. Cyclopropanation of PVNB was carried out using diazomethane in the presence of a Pd-catalyst. For thiol-en reaction, thioacetic acid was applied as the source of a thiol and AIBN as an initiator. All listed modifications were performed in high yields (≥80%) without the destruction of polymer main chains. The degree of functionalizations was up to 99%. The influence of these modifications on the properties of the resulting polymers was evaluated. Cyclopropanation and hydrogenation of PVNB led to an enhancement of gas permeability with minimal decrease in selectivity, while epoxidation or thioacetylation gave a substantial increase in CO2/N2 selectivity with decrease in permeability. The modified polymers with polar side-groups exhibited attractive selectivities for CO2/N2, CO2/CH4 and H2/N2 gas separations.

“ESIPT-AIE” based sequential fluorescence ‘on-off’ marker for endogenous detection of hypochlorite and cobalt (II)

Discrimination of a specific metal ion and ROS (Reactive Oxygen Species) among a library of ionic species in a water medium is one of the daunting tasks and it has been a hot-bed in the aspect of analytical chemistry. In the same objective, we have designed a tailor-fit molecule which serves as a sequential detector for ROS (−OCl) and a transition metal ion (Co2+). The novel receptor R has been derived from a simple condensation reaction between 2,5-thiophenedicarboxaldehyde and p-toluenesulfonyl hydrazide. The receptor is efficient for hypochlorite detection among all anions and other reactive oxygen species via ‘turn-on’ emission in 20% water (HEPES buffer, pH = 8) + DMSO medium without any interference through oxidative chemodosimetric mechanism. And the resultant emissive solution is extremely efficient for Co2+ among all cations via both change in colour and ‘turn-off’ emission. The obtained results are well supported by theoretical calculations. Limit of detection for hypochlorite and Co2+ are found to be 0.53 nM and 0.97 µM, respectively. The receptor showed real-time working efficiency in a bleach solution and chocolate extract. The receptor is proven to be biocompatible and is applied for endogenous fluorescence cell imaging of hypochlorite and Co2+.

Effect of p-toluenesulfonyl hydrazide on copper corrosion in hydrochloric acid solution

The adsorption effect of a new inhibitor “p-toluenesulfonylhydrazide (p-TSH)” on copper corrosion in 0.5 M HCl solution was studied by weight loss, electrochemical methods, morphological characterization and quantum chemical calculations. Electrochemical impedance spectroscopy and potentiodynamic polarization produced the same results, indicating that p-TSH reduces the corrosion rate of copper as its concentration increases in acidic solutions, provided that the adsorption mechanism of the inhibitor obeyed the Langmuir isotherm. The results of scanning electron microscopy suggested the possible adsorption of p-TSH molecules on the Cu(111) surface. In addition, quantum chemical simulations were used to explain the p-TSH inhibition performance for the copper.

A water-soluble colorimetric and fluorescent probe for rapidly sensing of ClO− in organisms

A simple colorimetric and fluorescent probe bearing coumarin and p-toluenesulfonyl hydrazide moieties was developed, which was capable of displaying excellent selectivity for hypochlorite. The distinct absorption spectral shift (49 nm) was induced by ClO−-triggered oxidative hydrolysis of CN double bonds in aqueous solution, which was accompanied by the optical variation from yellow to colorless. Besides, this probe solution underwent a dramatic intensification (162-fold) of the fluorescence signaling at 444 nm via the addition of ClO− (3 equiv.) within a short time. More importantly, the results achieved by fluorescence spectra revealed an excellent linear relation of probe 1 for ClO− with excellent sensitivity (9.1 nM). Further, the good recoveries and cellular experiments verified the prospective functions of this probe in real water environment and SW 480 cells.

Effect of Temperature, Time and Diimide/Rubber Ratio on the Hydrogenation of Liquid Natural Rubber by Response Surface Methodology

Hydrogenated liquid natural rubber (HLNR) was synthesized from liquid natural rubber (LNR) by thermolysis of p-toluenesulfonyl hydrazide (TSH). The HLNR structure was characterized by Fourier-transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopies. Thermogravimetric analysis (TGA) showed that the HLNR had higher decomposition temperature compared to LNR. A response surface methodology (RSM) based on a central composite rotatable design (CCRD) with five-level-three-factors was used to optimize the main important reaction parameters, such as the TSH:LNR weight ratio (1–3), reaction temperature (110–150 °C), and reaction time (1–8 h). A quadratic model was developed using this multivariate statistical analysis. Optimum conditions for the non-catalytic hydrogenation of LNR using TSH were obtained; an LNR hydrogenation percentage of 83.47% at a TSH:LNR weight ratio of 1.41, a reaction temperature of 118.11 °C, and a reaction time of 3.84 h were predicted. The R2 value of 0.9949 indicates that the model provides data that are well matched with those from the experiment.

I2/CuCl2-promoted one-pot three-component synthesis of aliphatic or aromatic substituted 1,2,3-thiadiazoles.

An efficient I2/CuCl2-promoted one-pot three-component strategy for the construction of 1,2,3-thiadiazoles from aliphatic- or aromatic-substituted methyl ketones, p-toluenesulfonyl hydrazide, and potassium thiocyanate has been developed. Simple and commercially available starting materials, a broad substrate scope, and excellent functional group tolerability make this strategy practical for applications. Furthermore, 1,2,3-thiadiazole synthesis was realized by using potassium thiocyanate as an odorless sulfur source.

Synthesis of Mixed-Ligand Nitrileand Carbonyl–Isocyanide Complexes of Platinum(II) and Their Reaction with P-Toluenesulfonyl Hydrazide

Mixed-ligand nitrile- and carbonyl-isocyanide complexes of platinum(II) trans-[PtCl2(NCEt)CNXyl] and trans-[PtCl2(CO)CNXyl] (Xyl = 2,6-Me2C6H3) have been prepared for the first time. The compounds have been characterized by mass spectrometry, IR and NMR spectroscopy. Reactivity of the prepared complexes towards N-nucleophiles has been studied using the reaction with p-toluenesulfonyl hydrazide as the example.

Glacial Acetic Acid-Assisted One-Pot Synthesis of Diverse Octahydroacridin-4-Methylbenzenesulfonamides via Tandem Cascade Reactions

We have synthesized a new series of 1,8-dioxo-octahydroacridin-4-methylbenzenesulfonamide scaffolds via the one-pot multicomponent condensation reactions of diverse aryl aldehydes and p-toluenesulfonyl hydrazide with dimedone or 1,3-cyclohexanedione in glacial acetic acid as an efficient and cheaper reaction medium. The progress of the reaction was monitored by thin layer chromatography and the recrystallized products were analyzed by FT-IR, 1H, 13C NMR and mass spectral techniques.

Synthesis, Characterization and Antimicrobial Activity of Two Novel Sulfonamide Schiff Base Compounds

Reactions of 2-hydroxy-3-methoxybenzaldehyde with p-toluenesulfonyl hydrazide and 4-nitrosulfonyl hydrazide under classical heating led to the corresponding sulfonamide Schiff bases 1 and 2. Both synthesized compounds were characterized by their spectroscopic data and elemental analysis. The antimicrobial activity of 1 and 2 against Gram-positive bacteria Staphylococcus epidermidis and Staphylococcus saprophyticus and Gram-negative bacteria Proteus mirabilis has been investigated by disc diffusion and minimum inhibitory concentration (MIC) methods. The disc diffusion method was also used to study antifungal activity of compounds against Aspergillus fumigates, Aspergillus clavatus, and Aspergillus flavus. Vancomycin and sulfamethoxazole/trimethoprim were used as standard drugs for bacteria and miconazole was used as antifungal standard.