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This study evaluated the inhibitory effect and mitigation strategy of dodecyl dimethyl benzyl ammonium chloride (DDBAC) suppression on anaerobic digestion. With the 12 h-suppression, only 16.64% of anaerobes were alive, and acetotrophic methanogens were significantly inhibited. As for batch test, DDBAC suppression significantly prolonged the start-up of systems and decreased the biogas production. In cellulose semi-continuous digestion process, the DDBAC suppression induced volatile fatty acids accumulation and pH decrease. However, the biochar amended reactor effectively mitigated the DDBAC suppression and achieved 370.5 mL/d·g-chemical-oxygen-demand biogas production. Moreover, 17.8% more protein in extracellular polymeric substances was secreted as the bio-barrier to defense the DDBAC suppression. Furthermore, microbial analysis showed that biochar addition selectively enriched directed interspecies electron transfer (DIET) participant bacteria (Anaerolineaceae and Syntrophomonas) and methanogens (Methanosaeta and Methanobacterium). Meanwhile, the potential metabolic pathway analysis showed that the abundance of amino acids and energy metabolism were increased 28% and 8%, respectively. The abundance of encoding enzyme related to hydrogenotrophic and acetotrophic methanogenesis enriched 1.88 times and 1.48 times, respectively. These results showed the performance and mechanisms involved in DIET establishment with ethanol stimulation biochar addition. [Display omitted] • The DDBAC suppressed acetotrophic methanogenesis and inhibited Methanosaeta. • Average biogas production of 370.5 mL/d·gCOD was achieved with biochar amended. • Anaerobes secreted 17.8% more protein in EPS to defense the DDBAC suppression. • Biochar promoted the growth of Anaerolineaceae , Syntrophomonas and Methanosaeta. • The genes related to energy metabolism were potentially activated by biochar. [ABSTRACT FROM AUTHOR]

• Density functional theoretical calculations were used to predict the complex structures of benzyl radical and chloride as well thermodynamic properties for electroreduction reaction of benzyl chloride on silver cathodes. • Surface-enhanced Raman feature of chemisorbed intermediates has a very strong Raman band from the wagging vibration of benzyl radical adsorbed on silver cathodes. • The high electrocatalytic activity of silver cathode arises from the synergetic effect of the thermodynamics and kinetics of the first electron transfer reaction. The reductive cleavage of carbon-halogen bonds is one of the classical model systems of concerted versus non-concerted bond breaking electron transfer in molecular electrochemistry, but most studies did not consider the influence of adsorption of reaction intermediates on this phenomenon. We performed density functional theory (DFT) calculations to understand the electrochemical reduction of benzyl chloride at silver electrodes through predicting the surface adsorption effect of the reactant and of follow-up intermediates and analyzing the energetics of the overall dissociative electron transfer. The ensuing DFT calculations of surface-enhanced Raman spectroscopic (SERS) signals provided some key information for characterizing different surface species at different potentials at the molecular level. The most intense and broad spectral peak observed near 800 cm−1 in the electrochemical SERS was thus assigned to the CH 2 wagging vibration closely associated with the co-adsorption of benzyl radical and chlorine. After the dissociation of the C-Cl benzyl chloride bond, the chloride anion adsorbs at the three-fold hollow site on silver electrodes, as indicated by a low vibrational frequency and a weak Raman signal. Conversely, the formed benzyl radical intermediate is found to adsorb at the top site with the characteristic vibrational frequency and strong Raman intensity. DFT calculations further confirmed that the kinetic effect underlying the electrocatalytic activity of silver electrodes is closely associated with the intrinsic energy barrier and the dissociative adsorption state of benzyl radical and chlorine on silver electrodes. Finally, we discuss the fundamental meaning of the kinetic rate constant of the first-step dissociative electron transfer for benzyl chloride on silver electrodes based on the different electron transfer models, indicating the synergistic roles of thermodynamics and kinetics. [ABSTRACT FROM AUTHOR]

• The new SBA-15-P,P-PdCl 2 complex has been easily prepared by a simple procedure from readily available reagents. • Heterogeneous Pd-catalyzed cyclocarbonylation of benzyl chlorides and salicylic aldehydes is first reported. • The reaction generates a wide variety of coumarin derivatives in mostly good to excellent yields. • This heterogenized palladium catalyst can be recycled up to eight times without any significant loss of activity. • Our catalytic system provides an economic and eco-friendly route to coumarin derivatives. A novel and practical route to coumarin derivatives has been developed via the heterogeneous Pd-catalyzed carbonylative reaction and subsequent intramolecular condensation process starting from commercially easily available benzyl chlorides and salicylic aldehydes. Reactions were performed in the existence of 2 mol% of an SBA-15-immobilized bidentate phosphine palladium complex [SBA-15-P,P-PdCl 2 ] in dioxane at 110 °C with Et 3 N as base under 10 bar of CO to afford a wide range of coumarin derivatives mostly with good to high yields. Importantly, this new heterogenized palladium complex was easy to recover via filtration of the reaction mixture, and was recyclable up to 8 times without apparent drop in its catalytic performance. [Display omitted] [ABSTRACT FROM AUTHOR]

Interactions between coal matrix and organics are vital for adsorption [1] , surfactant adsorption on lignite [2-5] , and solid–liquid separation of coal slurry [6-10]. Herein, for studying the interaction between hydrophobic surface (coal surface) and small molecules (organics), we measured interactions between organics [nitro and phenyl, pyridine, phenyl, alkyl chain (hexyl) or cycloalkyl (hexyl)] and the coal matrix (liptinite or inertinite) using atomic force microscopy. The strength of interaction followed the order: nitro and phenyl > pyridine > phenyl > alkyl chain (hexyl) > cycloalkyl (hexyl), and liptinite > inertinite. The liptinite has a greater hydrophobicity than inertinite, the greater the attraction force. The lignite surface and coal slurry were modified in an aqueous solution using five surfactants (dodecyl trimethyl ammonium chloride, DTAC; hexadecyl trimethyl ammonium chloride, CTAC; octadecyl trimethyl ammonium chloride, STAC; hexadecyl dimethyl benzyl ammonium chloride, HDBAC; and cetyl pyridine chloride, CPC). Subsequently, the moisture adsorption on treated lignite coal surface and the sedimentation of the treated tails was compared to characterize hydrophobic modifications which showed the order of CTAC > HDBAC > DTAC > CPC > STAC. Thus, the interaction between coal surface and organics needs to consider two rules: 1) The desolvation or the hydrophobic property of the coal surface; 2) The VDW force of the organics. The nature of the difference between rules No. 1 and 2 is that with the size of hydrophobic molecules increased to a surface, the H-bond structure between water molecules in the around would change a lot, which formats great hydrophobic property or desolvation. Interaction between organic reagents and coal reveals the mechanism of restraining moisture reabsorption of lignite and solid–liquid separation of coal slurry by organics. [ABSTRACT FROM AUTHOR]

[Display omitted] • First report on oxidative Prins cyclization using FeCl 3. • Catalyst is readily available at low cost. • Mild reaction conditions. • Alternate source of aldehyde. An efficient synthesis of 2-aryl-4-chloro-tetrahydropyrans has been accomplished from benzyl chlorides and homoallylic alcohols using FeCl 3 as a promoter through a sequential oxidation/Prins cyclization in high yields. This is the first report on the use of benzyl chlorides as surrogates for aldehydes in the Prins cyclization. [ABSTRACT FROM AUTHOR]

• A new series of N-substituted [1,2,4]triazolo[4,3-a]pyrazine derivatives were synthesized. • All synthesized compounds were evaluated for their antioxidant, anticonvulsant and neurotoxicity effect. • Compounds 2a, 2b and 2e were found to be superior to sodium valproate and methaqualone. • The docking results were aligned with experimental findings. • Pharmacokinetics analysis of compounds shown as promising lead-like characters. Two new series of N -substituted [1,2,4]triazolo[4,3-a]pyrazine derivatives, 2a-e and 3a-e were synthesized by coupling substituted acid chlorides/benzyl chlorides with 3-(trifluoromethyl)-5,6,7,8-tetrahydro-[1,2,4]triazolo[4,3-a]pyrazine and investigated for antioxidant, anticonvulsant effect and neurotoxicity. The in vitro antioxidant activity was assessed using the DPPH and hydroxyl radical scavenging assays. The anticonvulsant potential of the synthesised molecules was assessed using MES and PTZ tests, and their neurotoxicity was evaluated using a rotorod test in mice. Compounds 2a, 2b, 2e, and 3d were identified to have a good anti-seizure action while causing minimal neurotoxicity. The most effective anticonvulsants were compounds 2a, 2b, and 2e, with median effective dosages of 0.38, 0.36, and 0.25 mg/kg, respectively. A computational analysis was also conducted, which included drug-likeness and docking studies, as well as prediction of pharmacokinetic parameters. Docking studies of potent compounds in the binding pocket of the 4-aminobutyrate aminotransferase protein (PDB ID: 1OHV) reveal strong binding interactions and high docking scores. From these findings, the potent compounds 2a, 2b, and 2e might be a promising lead in the quest for safer and more effective anticonvulsants with neuroprotective properties. [Display omitted] [ABSTRACT FROM AUTHOR]

• Palladium-catalyzed aminocarbonylative cyclization of benzyl chlorides with 2-nitroaryl alkynes. • A facile and efficient method for the assembly of indole skeletons. • Employing nitroarenes as the nitrogen source. • With Mo(CO) 6 as both the CO surrogate and the reductant. • A variety of indole derivatives were prepared in moderate to high yields. A palladium-catalyzed aminocarbonylative cyclization of benzyl chlorides with 2-nitroaryl alkynes has been developed for the rapid construction of indole skeletons. The reaction utilized nitroarenes as the nitrogen source, Mo(CO) 6 as both the CO surrogate and the reductant to furnish various indole derivatives in moderate to high yields. [Display omitted] [ABSTRACT FROM AUTHOR]

[Display omitted] • Double hydrophilic, block and random, PVBTMAC-based polyelectrolyte copolymers were utilized for complexation with insulin. • PVBTMAC-based copolymers formed single chains and aggregates in aqueous media. • Well-defined spherical complexes are formed. • Characteristics of the copolymer/insulin complexes depend on (−)INS/(+)pol charge ratio. • Copolymer/insulin complexes manifested a good stability into a simulated biological environment (FBS). We report on the synthesis and preparation of four double hydrophilic polyelectrolytes and their complexation with insulin (INS). Specifically, two cationic-neutral poly[oligo(ethylene glycol) methacrylate]-b-poly[(vinyl benzyl trimethylammonium chloride)] (POEGMA-b-PVBTMAC) and two poly[oligo(ethylene glycol) methacrylate-co-vinyl benzyl trimethylammonium chloride] (P(OEGMA-co-VBTMAC)) copolymers are successfully synthesized by reversible-addition fragmentation chain transfer (RAFT) polymerization with different compositions. Based on light scattering techniques (DLS, ELS), the POEGMA 81 -b-PVBTMAC 19 , POEGMA 46 -b-PVBTMAC 54 P(OEGMA 90 -co-VBTMAC 10), P(OEGMA 75 -co-VBTMAC 25) (subscripts denote wt.% composition of the components) copolymers are present as single chains and aggregates in aqueous media. A significant aggregation tendency of bare copolymers into well-defined spherical-shape particles is also noticed in cryogenic transmission electron microscopy measurements (Cryo-TEM) measurements. The synthesized copolymers were utilized as nanocarriers for insulin (INS) encapsulation. Nanocarriers were formed via electrostatic co-assembly, and the effects of copolymer structure on the properties of the formed hybrid copolymer-INS nanostructures are studied. Physicochemical results on the copolymer/INS complexes corroborated the efficient complexation of INS with copolymers. The determined characteristics and the morphology of the copolymer/INS complexes were found to depend on (−)INS/(+)polymer charge ratio. The copolymer/INS complexes retain the initial spherical shape of neat copolymer aggregates after the electrostatic complexation with INS, according to Cryo-TEM measurements, also uncovering the presence of aggregates and threadlike structures. FBS interactions between bare copolymers and copolymer/INS complexes manifested a good stability of the hybrid copolymer/INS assemblies into a simulated biological environment. Moreover, attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy shows physical interactions between INS and the respective polyelectrolytes. Fluorescence spectroscopy (FS) measurements indicated no significant changes on the conformation of complexed INS. [ABSTRACT FROM AUTHOR]

Improvement of product selectivity is a major concern of the day. Presence of a coreactant can alter the rate as well as product selectivity of many key reactions like Friedel-Crafts benzylation. Single pot benzylation of o-xylene with benzyl chloride and benzyl alcohol was studied over transition metal exchanged pillared clay catalysts. Complete conversion of benzyl alcohol occured within one hour with 100% monoalkylated product selectivity. The reaction of o-xylene with benzyl alcohol was found to proceed fast in presence of benzyl chloride in single pot, than when present alone as the benzylating species. This enhancement occurs at the expense of no reaction of benzyl chloride, which when present alone reacts faster than benzyl alcohol. Existence of a second transition metal exchanged between the pillars increased the rate of the reaction. A detailed investigation of the reaction variables suggested preferential adsorption of benzyl alcohol to catalyst active sites as the reason. [ABSTRACT FROM AUTHOR]

A one-pot method for the functionalization of polyvinylbenzyl chloride with a tris-(benzyltriazolylmethyl)amine (TBTA) ligand via the copper-catalyzed azide-alkyne cycloaddition reaction (CuAAC) is reported, where the ligand is constructed simultaneously with its attachment to the polymer backbone. A hydrophobic TBTA polymer as well as co-polymers containing TBTA ligands were also prepared to demonstrate the possibility of tailoring the properties of the polymers. The polymers were characterized with FT-IR and NMR spectroscopy, elemental analysis, contact angle measurement, differential scanning calorimetry and thermal gravimetric analysis. The metal coordinating properties of films prepared from the polymers was also demonstrated using X-ray photoelectron spectroscopy and their structures inspected by scanning electron microscopy. [ABSTRACT FROM AUTHOR]

The article discusses the study which focuses on the preparation of N-benzylpiperazine. Tackled is monobenzylation of biologically active compounds as well as the conversion of anhydrous piperazine. Noted is the synthesis of 1-aralkyl-4-benzylpiperazine hydrochlorides along with benzyl chloride solution.

The activating effects of the benzyl and allyl groups on SN2 reactivity are well-known. 6-Chloromethyl-6-methylfulvene, also a primary, allylic halide, reacts 30 times faster with KI/acetone than does benzyl chloride at room temperature. The latter result, as well as new experimental observations, suggests that the fulvenyl group is a particularly activating allylic group in SN2 reactions. Computational work on identity SN2 reactions, e.g., chloride- displacing chloride- and ammonia displacing ammonia, shows that negatively charged SN2 transition states (tss) are activated by allylic groups according to the Galabov-Allen-Wu electrostatic model but with the fulvenyl group especially effective at helping to delocalize negative charge due to some cyclopentadienide character in the transition state (ts). In contrast, the triafulvenyl group is deactivating. However, the positively charged SN2 transition states of the ammonia reactions are dramatically stabilized by the triafulvenyl group, which directly conjugates with a reaction center having SN1 character in the ts. Experiments and calculations on the acidities of a variety of allylic alcohols and carboxylic acids support the special nature of the fulvenyl group in stabilizing nearby negative charge and highlight the ability of fulvene species to dramatically alter the energetics of processes even in the absence of direct conjugation. [ABSTRACT FROM AUTHOR]

In this study, a beaded polymer with quaternary amine functions was prepared in two steps, starting from poly (vinyl benzyl chloride-ethylene glycol dimethacrylate) (PVBC) based beads, according to the synthetic protocol; modification of ethyl piperazine with PVBC (EP-PS), and quaternization of ethylpiperazine modified beads with chloroacetic acid (QEP-PS). The QEP-PS resin was used for the removal of reactive red 120 as an acidic dye and malachite green chloride as a basic dye. Dye extraction experiments were carried out simply by contacting wetted sorbent samples with aqueous dye solutions at room temperature. Capacities were determined by colorimetric analysis of the residual dye contents. The resin showed that reasonable high dye sorption capacity (0.34-0.41 g per gram of dry resin) was achieved. The adsorption conditions (initial dye concentration and pH) were varied to evaluate the mechanism of adsorption of both basic dyes and acidic dyes on the prepared resin. This material is also able to remove both the anionic dye and cationic dyes completely even from highly diluted aqueous dye solutions. [ABSTRACT FROM PUBLISHER]

Groups of chloromethyl were randomly grafted to Janus composite particles and quaternization was carried out on the particles. The Janus material of titania–quaternary ammoniated poly(vinylbenzyl chloride–divinylbenzene) (TiO2–QApoly(VBC–DVB)) was investigated in detail. Results revealed that the anisotropic Janus material containing quaternary ammonium groups was synthesized successfully. The Janus material could be used as the phase transfer catalyst. The catalytic activity of the Janus material was confirmed by the esterification reaction of benzyl chloride and sodium acetate. In the presence of 0.5 wt.% (relative to benzyl chloride) of TiO2–QApoly(VBC–DVB), the esterification yield of benzyl acetate reached 87.6% when the molar ratio of sodium acetate anhydrous to benzyl chloride was 1.2. The catalyst exhibited a high activity and had no obvious loss of activity when recycled three times. Moreover, the Janus material was easily recovered by centrifugation and washed with ethanol and water. [ABSTRACT FROM AUTHOR]

Hydrolysis reactions of benzyl chlorides and benzenesulfonyl chlorides were theoretically investigated with the density functional theory method, where the water molecules are explicitly considered. For the hydrolysis of benzyl chlorides (para-ZC6H4CH2Cl), the number of water molecules ( n) slightly influences the transition-state (TS) structure. However, the para-substituent (Z) of the phenyl group significantly changes the reaction process from the stepwise (SN1) to the concerted (SN2) pathway when it changes from the typical electron-donating group (EDG) to the typical electron-withdrawing one (EWG). The EDG stabilizes the carbocation (MeOC6H4CH2+), which in turn makes the SN1 mechanism more favorable and vice versa. For the hydrolysis of benzenesulfonyl chlorides (para-ZC6H4SO2Cl), both the Z group and n influence the TS structure. For the combination of the large n value ( n > 9) and EDG, the SN2 mechanism was preferred. Conversely, for the combination of the small n value and EWG, the SN3 one was more favorable. © 2014 Wiley Periodicals, Inc. [ABSTRACT FROM AUTHOR]

Cavitational reactors are a noveland promising form of multiphasereactors, based on the principle of the release of a large magnitudeof energy due to the violent collapse of the cavities, which can beeffectively applied for intensification of chemical synthesis. Inthe present work, 4-benzyloxy-3-methoxybenzaldehyde has been synthesizedby selective O-alkylation of vanillin with benzyl chloride using tetrabutylammoniumbromide-based phase transfer catalysis in the presence of ultrasonicirradiations. The reactions were performed in a 150 cm3capacity glass reactor equipped with reflux condenser, and ultrasonicirradiations were introduced using an ultrasonic horn operating ata frequency of 20 kHz with a power rating of 120 W. The effects ofdifferent operating parameters such as quantum of aqueous phase, temperature,catalyst loading, ultrasonic power dissipation, and molar ratio ofreactants have been investigated with an aim of maximizing the extentof synthesis of 4-benzyloxy-3-methoxybenzaldehyde. Kinetic studieshave also been performed, and the activation energy for the reactionhas been established. The work has clearly established a superiorprocess for synthesis based on the use of ultrasonic irradiationswith higher yields as compared to the conventional approach. [ABSTRACT FROM AUTHOR]

The ability to reversibly control protein structure and function with light would offer high spatiotemporal resolution for investigating biological processes. To confer photoresponsiveness on general proteins, we genetically incorporated a set of photoswitchable click amino acids (PSCaas), which contain both a reversible photoswitch and an additional click functional group for further modifications. Orthogonal tRNA-synthetases were evolved to genetically encode PSCaas bearing azobenzene with an alkene, keto, or benzyl chloride group in E. coli and in mammalian cells. After incorporation into calmodulin, the benzyl chloride PSCaa spontaneously generated a covalent protein bridge by reacting with a nearby cysteine residue through proximity-enabled bioreactivity. The resultant azobenzene bridge isomerized in response to light, thereby changing the conformation of calmodulin. These genetically encodable PSCaas will prove valuable for engineering photoswitchable bridges into proteins for reversible optogenetic regulation. [ABSTRACT FROM AUTHOR]

Polymer/clay nanocomposites have been extensively studied to enhance the properties of polymer by incorporation of small amount of clay, usually modified with organic cations, preferably containing long alkyl chains, which are exchanged with the inorganic cations in the clay gallery. In this work clay was modified with two different oligomeric surfactant viz: poly(styrene-co-vinylimidazole) and poly(styrene-co-4-vinyl pyridine) quarternized with benzyl chloride. The oligomeric modified clay contains 50% clay and 50% oilgomeric surfactant. The oilgomeric modified MMT clay having thermal stability higher than the processing temperature of PBT was used to prepare nanocomposites of PBT by melt blending. The resulting nanocomposites were evaluated for mechanical and rheological properties. A considerable increase in tensile strength up to 50% is observed for 2 phr incorporation of oligomeric modified clay. Rheological behavior exhibits more solid-like behavior and increased melt viscosity of the obtained nanocomposites. [ABSTRACT FROM AUTHOR]

The reaction of 1,4-benzodioxane-2-carbonyl chloride with 5-(4-aminophenyl)-1,3,4-oxa- and -thiadiazole-2-thiols afforded new biheterocyclic compounds which were converted into the corresponding S-benzyl derivatives by treatment with benzyl chloride. 5-(4-Aroylaminophenyl)-1,3,4-oxa(thia)diazole-2-thiols reacted with 2-bromomethyl-1,4-benzodioxane to give compounds in which the 1,4-benzodioxane nucleus and fivemembered heterocycle are linked through a CHS bridge. [ABSTRACT FROM AUTHOR]

A novel plasma graft-polymerization approach is adopted to prepare hydroxide exchange membranes (HEMs) using cardo polyetherketone powders (PEK-C) and vinylbenzyl chloride. The benzylic chloromethyl groups can be successfully introduced into the PEK-C polymer matrix via plasma graft-polymerization. This approach enables a well preservation in the structure of functional groups and formation of a highly cross-linked structure in the membrane, leading to an improvement on the stability and performance of HEMs. The chemical stabilities, including alkaline and oxidative stability, are evaluated under severe conditions by measuring hydroxide conductivity and weight changes during aging. The obtained PGP-NOH membrane retains 86% of the initial hydroxide conductivity in 6 mol L−1 KOH solution at 60 °C for 120 h, and 94% of the initial weight in 3 wt% H2O2 solution at 60 °C for 262 h. The PGP-NOH membrane also possesses excellent thermal stability (safely used below 120 °C), alcohol resistance (ethanol permeability of 6.6 × 10–11 m2 s–1 and diffusion coefficient of 3.7 × 10–13 m2 s–1), and an acceptable hydroxide conductivity (8.3 mS cm–1 at 20 °C in deionized water), suggesting a good candidate of PGP-NOH membrane for HEMFC applications. [ABSTRACT FROM AUTHOR]

Abstract: A new material based on crosslinked poly(vinylbenzyl chloride) (PVBC) with a macromolecular crosslinker is synthesized and employed as the membrane for anion exchange membrane fuel cells (AEMFCs). PVBC is used as the hydroxide conducting polymers, while poly(vinyl acetal) (PVAc) containing dimethylamino groups plays the role as macromolecular crosslinker and the supporting matrix simultaneously. Fourier transform infrared (FT-IR) absorption spectra and X-ray photoelectron (XPS) spectra prove successful crosslinking between PVBC and PVAc. The crosslinked membrane shows hydroxide conductivity larger than 0.01 S cm−1 at room temperature, and the swelling by water at elevated temperature is suppressed. The H2/O2 AEMFC using the crosslinked membrane shows a peak power density (P max) of 124.7 mW cm−2 at 40 °C, and the decrease of the open circuit voltage (OCV) of the fuel cell is negligible under continuous OCV conditions for 120 h. All the results indicate that the crosslinking with a macromolecular crosslinker may be a promising strategy to fabricate anion exchange membrane for the application in the AEMFCs. [Copyright &y& Elsevier]

Highlights: [•] Pd NPs have been electrodeposited on nitrogen doped GC. [•] XPS reveals the formation of several types of nitrogen based defects on GC. [•] Pd NPs grown on nitrogen doped GC are smaller than those grown on GC. [•] Pd NPs on nitrogen doped GC are more active than Pd NPs on pristine GC. [•] Pd NPs loaded on nitrogen doped GC are even more active than bulk Pd toward R X reduction. [ABSTRACT FROM AUTHOR]

The reaction of hydrazine hydrate with carbon disulfide and 4-methylbenzyl chloride in basic solution yielded 2,5-bis(4-methylbenzylthio)-1,3,4-thiadiazole (CHNS, compound 1) in addition to the expected S-4-methylbenzyldithiocarbazate. The molecule has approximate twofold symmetry with the C=S bond lying on the pseudo axis. The five membered ring is planar with the three S atoms mutually syn, and with pendent 4-methylbenzylthio substituents; the dihedral angle between the terminal rings is 52.21(7)°. The compound 1 crystallizes in the triclinic space group $$P\bar{1}$$ with a = 6.0139(3) Å, b = 11.8694(7) Å, c = 12.6330(7) Å, α = 72.583(5)°, β = 82.827(4)°, γ = 89.882(4)° and Z = 2. Graphical Abstract: In situ cyclization of an authenticated dithiocarbazate gave rise to a supramolecular layerered assembly of new molecules containing a 1,3,4-thiadiazole ring system having a strictly planar central core with mutually syn sulfur atoms and terminal aryl groups twisted out of this plane.[Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

Ethylene is one of the most important building blocks in industry for the production of polymers and commodity chemicals. 13C- and D-isotope-labeled ethylenes are also valuable reagents with applications ranging from polymer-structure determination, reaction-mechanism elucidation to the preparation of more complex isotopically labeled compounds. However, these isotopic derivatives are expensive, and are flammable gases, which are difficult to handle. We have developed a method for the controlled generation of ethylene and its isotopic variants including, for the first time, fully isotopically labeled ethylene, from simple alkene precursors by using Ru catalysis. Applying a two-chamber reactor allows both the synthesis of ethylene and its immediate consumption in a chemical transformation permitting reactions to be performed with only stoichiometric amounts of this two carbon olefin. This was demonstrated in the Ni-catalyzed Heck reaction with aryl triflates and benzyl chlorides, as well as Ru-mediated enyne metathesis. [ABSTRACT FROM AUTHOR]

In this work, we show our most recent results on the reductive dehalogenation of organic chlorides in acetonitrile + water media on silver electrodes, whose impressive catalytic power toward this reaction have already been extensively demonstrated and discussed. We adopt benzyl chloride as model molecule because of its wide use in previous literature. The results show that the presence of increasing amount of water to pure acetonitrile deeply and quantitatively modifies not only the peak potential (and thus the apparent reaction kinetics) but also the reaction mechanism. [ABSTRACT FROM AUTHOR]

Objective(s): Nowadays, cancer is an important public health problem in all countries. Limitations of current chemotherapy for neoplastic diseases such as severe adverse reactions and tumor resistance to the chemotherapeutic drugs have been led to a temptation for focusing on the discovery and development of new compounds with potential anticancer activity. Materials and Methods: A new series of 1,3,4-thiadiazole-derived compounds (3a-3l) were synthesized. N-(5-Mercapto-1,3,4-thiadiazol-2-yl)-2-(4-methoxyphenyl) acetamide (2) was prepared through direct amidation of 4-methoxyphenylacetic acid (2) with 5-amino-1,3,4- thiadiazole-2-thiol using EDC (N-Ethyl-N-dimethylaminopropyl carbodiimide) and HOBt (Hydroxybenzotriazole). Then, various derivatives of benzyl chloride containing electron withdrawing and electron donating moieties were reacted with compound 2 to prepare compounds 3a-3l. In vitro cytotoxicity assessment using MTT method was applied and results are presented as IC50. Results: All the synthesized compounds were characterized by 1H-NMR and IR spectroscopy. Some of the synthesized compounds were also characterized using MS spectroscopy. Related melting points were also recorded. According to the obtained data from MTT assay, all compounds (3a-3l) demonstrated a higher cytotoxic activity against MDA-MB-231 breast cancer cell line in comparison with other cell lines. Conclusion: It is notable that four synthesized compounds 3h (IC50= 11 ± 0.18 μM), 3j (IC50= 10 ± 0.39 μM), 3k (IC50= 11 ± 0.77 μM) and 3l (IC50= 8 ± 0.69 μM) exhibited higher cytotoxic activity against MDA-MB-231 cell line compared to imatinib (IC50= 20 ± 0.69 μM) as the reference drug. [ABSTRACT FROM AUTHOR]

Dialkylformamides are excellent N-sources in the amination of benzyl chlorides when catalysed by a NHC-Pd(II)-Im complex. In the presence of NaOH and the catalyst, variously substituted benzyl chlorides and five different dialkylformamides reacted smoothly to afford the corresponding N,N-dialkyl-benzylamines in good to almost quantitative yields in eco-friendly solvent water at 50 °C within 3 h. [ABSTRACT FROM AUTHOR]