Benzyl Chloride Research Articles

Accelerator and zinc-free prevulcanized latex based on natural rubber-bearing benzyl chloride groups

Accelerator and zinc-free prevulcanized latex based on natural rubber-bearing benzyl chloride groups

Incorporation of phenolic skeleton into imidazolium ionic polymers as recyclable catalysts for efficient fixation of CO2 into cyclic carbonates

Developing a greener and efficient catalysts towards the direct fixation of atmospheric CO2 and then being used to synthesize high-value chemicals is of great interest, but challenging. To achieve this aim, rational design of the catalyst is very important. Herein, three imidazolium-based ionic polymers (IPs), named as IP 1–IP 3, are straightforwardly synthesized through a simple one-pot quaternization method by employing benzyl chloride linkers and tri-imidazole monomers (L1 and L2). These IPs are fully characterized using FTIR spectroscopy, 13C MAS NMR, XRD, elemental analysis, SEM with elemental mapping, HRTEM, TGA, XPS spectroscopy, nitrogen adsorption–desorption, and CO2/NH3-TPD methods. The newly synthesized IP 1 catalyst with phenolic hydroxyl shows an excellent catalytic activity toward CO2 cycloaddition with 97.1 % yield of cyclic carbonate under mild conditions (80 °C, 0.1 MPa CO2, solvent-free, 4.5 h). Moreover, the IP 1 catalyst is highly robust and can be reused at least for 7 consecutive runs. Mechanistic studies indicate that the synergic effect of hydrogen bonding and halogen anion in the IP 1 catalyst afford the ability to activate the substrate and ease the reaction kinetics, which results in an enhanced catalytic efficiency toward CO2 fixation. This work provides an efficient new method for the design and synthesis of multifunctional heterogeneous catalysts for the CO2 cycloaddition reaction.

Beyond n-dopants for organic semiconductors: use of bibenzo[d]imidazoles in UV-promoted dehalogenation reactions of organic halides.

2,2'-Bis(4-dimethylaminophenyl)- and 2,2'-dicyclohexyl-1,1',3,3'-tetramethyl-2,2',3,3'-tetrahydro-2,2'-bibenzo[d]imidazole ((N-DMBI)2 and (Cyc-DMBI)2) are quite strong reductants with effective potentials of ca. -2 V vs ferrocenium/ferrocene, yet are relatively stable to air due to the coupling of redox and bond-breaking processes. Here, we examine their use in accomplishing electron transfer-induced bond-cleavage reactions, specifically dehalogenations. The dimers reduce halides that have reduction potentials less cathodic than ca. -2 V vs ferrocenium/ferrocene, especially under UV photoexcitation (using a 365 nm LED). In the case of benzyl halides, the products are bibenzyl derivatives, whereas aryl halides are reduced to the corresponding arenes. The potentials of the halides that can be reduced in this way, quantum-chemical calculations, and steady-state and transient absorption spectroscopy suggest that UV irradiation accelerates the reactions via cleavage of the dimers to the corresponding radical monomers.

Polyolefin‐Based Anion Exchange Membranes with Superior Performance and Long‐Term Durability for Green Hydrogen Production

AbstractIn this work, a commercially available styrene‐butadiene block copolymer is functionalized with vinyl benzyl chloride (VBC) via solution free‐radical polymerization to obtain g‐VBC‐x graft copolymers. The molar content of VBC, also named functionalization degree (FD) or x, of g‐VBC‐x is varied in the range 10–27 mol%, simply by varying the concentration of VBC monomer in the feed or the reaction time. The g‐VBC‐x copolymers are used to prepare films by solution casting that are converted into anionic exchange membranes (AEMs) by heterogeneous quaternization reaction with trimethylamine (TMA). The membranes are extensively characterized to assess their thermal, mechanical, and ex‐situ electrochemical properties. The best performing AEMs having an FD of 20% and 27% are tested in an AEM single‐cell electrolyzer. Both of them are found to retain their original conductivity after more than 40 and 100 days, respectively. In particular, the membrane with the higher FD is characterized by the best in‐situ performance both in terms of ionic conductivity and cell potential.

Light‐induced FeCl3‐catalyzed selective benzyl C−H chlorination with trifluoromethanesulfonyl chloride

AbstractHere we report a light‐induced FeCl3‐catalyzed approach for benzyl C−H chlorination with remarkable regioselectivity, which enables alkylbenzenes to be converted into versatile benzyl chlorides under mild conditions using trifluoromethanesulfonyl chloride (TfCl) as the chlorine source. DFT calculations show that the dynamics preference of benzylic α−C−H chlorination is more pronounced by employing TfCl.

The predictive machine learning model of a hydrated inverse vulcanized copolymer for effective mercury sequestration from wastewater

Inverse vulcanized polysulfides (IVP) are promising sulfur-enriched copolymers with unconventional properties irresistible for diverse applications like Hg2+ remediation. Nevertheless, due to their inherent hydrophobic nature, these copolymers still offer low Hg2+ uptake capacity. Herein, we reported the synthesis of IVP by reacting molten sulfur with 4-vinyl benzyl chloride, followed by their functionalization using N-methyl D-glucamine (NMDG) to increase the hydration of the developed IVP. The chemical composition and structure of the functionalized IVP were proposed based on FTIR and XPS analysis. The functionalized IVP demonstrated a high mercury adsorption capacity of 608 mg/g (compared to <26 mg/g for common IVP) because of rich sulfur and hydrophilic regions. NMDG functionalized IVP removed 100 % Hg2+ from a low feed concentration (10–50 mg/l). A predictive machine learning model was also developed to predict the amount of mercury removed (%) using GPR, ANN, Decision Tree, and SVM algorithms. Hyperparameter and loss function optimization was also carried out to reduce the prediction error. The optimized GPR algorithm demonstrated high R2 (0.99 (training) and 0.98 (unseen)) and low RMSE (2.74 (training) and 2.53 (unseen)) values indicating its goodness in predicting the amount of mercury removed. The produced functionalized IVP can be regenerated and reused with constant Hg2+ uptake capacity. Sulfur is the waste of the petrochemical industry and is abundantly available, making the functionalized IVP a sustainable and cheap adsorbent that can be produced for high-volume Hg2+ remediation. Environmental implicationThis research effectively addresses the removal of the global top-priority neurotoxic pollutant mercury, which is toxic even at low concentrations. We attempted to remove the Hg2+ utilizing an inexpensive adsorbent developed by NMDG functionalized copolymer of molten sulfur and VBC. A predictive machine learning model was also formulated to predict the amount of mercury removal from wastewater with only a 0.05 % error which shows the goodness of the developed model. This work is critical in utilizing this low-cost adsorbent and demonstrates its potential for large-scale industrial application.

Corrosion Inhibition of Benzyl Quinoline Chloride Derivative-Based Formulation for Acidizing Process

Summary Due to the severe and rapid corrosion of metallic equipment by strong acids at high temperatures, a high concentration of acidizing corrosion inhibitors (ACIs) is required during acidizing processes. There is always a need to develop more effective and environmentally friendly ACIs than current products. In this work, a highly effective ACI obtained from a novel main component and its synergistic effect with paraformaldehyde (PFA) and potassium iodide (KI) is presented. The ACI was prepared from the crude product of benzyl quinolinium chloride derivative (BQD) synthesized from benzyl chloride and quinoline in a simple way. The new ACI formulation, named “synergistic indolizine derivative mixture” (SIDM), which consists of BQD, PFA, and KI, showed superior corrosion inhibition effectiveness (IE) and temperature stability compared with commercially available ACI. More importantly, the SIDM formulation eliminates the need for commonly used highly toxic synergists (e.g., propargyl alcohol and As2O3). In a 20 wt% hydrochloric acid (HCl) solution, the addition of 0.5 wt% SIDM mitigates the corrosion rate of N80 steel down to less than 0.00564 lbm·ft−2 at 194°F, while the corrosion rate at 320 °F is 0.0546 lbm·ft−2·when 4.0 wt% SIDM is added.

A Highly Efficient, Catalyst-Free Synthesis of S-Alkyl/aryl Dithiocarbamate Derivatives under Green Conditions and Evaluation of their Biological Activity

An efficient, feasible, transition metal catalyst-free and environmental friendly approach for the synthesis of dithiocarbamate in an ethanol-water solvent combination at room temperature has been established. Alkyl/aryl halide, carbon disulfide and secondary amine were condensed in one pot to produce a range of dithiocarbamate derivatives. Based on the results, the yields were higher when aliphatic amine reacted with benzyl halides as compared to alkyl halides. This method has the advantage of using no hazardous solvents. Other benefits of this method include producing compounds with a good yield by a catalyst-free reaction employing a simple, affordable and useful method. When tested against specific pathogens, selected dithiocarbamate derivatives showed strong antibacterial activity but weak antifungal activity.

Alkali-resistant poly (vinyl benzyl chloride) based anion exchange membranes with outstanding flexibility and high hydroxide ion conductivity

Preparing AEMs with robust mechanical properties, high ionic conductivity and excellent chemical stability is challenging. Here, cross-linked/aggregated AEMs are prepared by incorporating hydrophilic Jeffamine cross-linkers and hydrophobic side chains into the rigid quaternized poly (vinyl benzyl chloride). Jeffamine's flexibility ensures high elongation at break of the cross-linked/aggregated membranes (125.0–199.8%). The hydrophobic side chain limits excessive water absorption and facilitates self-aggregation of hydrophilic and hydrophobic domains, enhancing tensile strength (5.08–7.40 Mpa in wet state) and improving ionic conductivity of the AEMs (73.8–110.4 mS cm−1 at 80 °C). Alkali-resistant PVB, restricted dimensionality, and ordered micro-phase separation morphology contribute to outstanding chemical stability of the AEMs. Degradation of both backbones and cations is <20% after treatment in 1 M NaOH solution at 80 °C for 30 days. Based on the membrane, a peak power density of 354.4 mW cm−2 at 60 °C is yielded.

Novel Thiazolactone Derivatives: Synthesis and Quantum Chemical Study

In this research, 15 novel derivatives of the thiazolactone skeleton were synthesized using the Erlenmeyer–Plöchl reaction procedure. Glycine, alanine and leucine amino acids were used to make dithiocarbamate precursor by reacting amino acids with carbon disulfide and benzyl chloride. Obtained benzyl dithiocarbamate underwent thiazolactone formation in the presence of acetic anhydride and then condensed with arylglyoxals as condensing carbonyl group source. Products were characterized using their spectroscopic IR, 1H NMR, and 13C NMR data. In continuation, computational chemistry methods were used to get some information about the products such as structural characteristics, charge distribution, 1H NMR and UV-visible spectra. Results showed that the calculated chemical shifts are in good agreement with experimentally recorded ones. The B3LYP density functional method in conjunction with the 6-311++G(d,p) basis set was used for all calculations.

Effective Activation of Strong C−Cl Bonds for Highly Selective Photosynthesis of Bibenzyl via Homo‐Coupling

AbstractCarbon‐carbon (C−C) coupling of organic halides has been successfully achieved in homogeneous catalysis, while the limitation, e.g., the dependence on rare noble metals, complexity of the metal‐ligand catalylst and the poor catalyst stability and recyclability, needs to be tackled for a green process. The past few years have witnessed heterogeneous photocatalysis as a green and novel method for organic synthesis processes. However, the study on C−C coupling of chloride substrates is rare due to the extremely high bond energy of C−Cl bond (327 kJ mol−1). Here, we report a robust heterogeneous photocatalyst (Cu/ZnO) to drive the homo‐coupling of benzyl chloride with high efficiency, which achieves an unprecedented high selectivity of bibenzyl (93 %) and yield rate of 92 % at room temperature. Moreover, this photocatalytic process has been validated for C−C coupling of 10 benzylic chlorides all with high yields. In addition, the excellent stability has been observed for 8 cycles of reactions. With detailed characterization and DFT calculation, the high selectivity is attributed to the enhanced adsorption of reactants, stabilization of intermediates (benzyl radicals) for the selective coupling by the Cu loading and the moderate oxidation ability of the ZnO support, besides the promoted charge separation and transfer by Cu species.

Effective Activation of Strong C-Cl Bonds for Highly Selective Photosynthesis of Bibenzyl via Homo-Coupling.

Carbon-carbon (C-C) coupling of organic halides has been successfully achieved in homogeneous catalysis, while the limitation, e.g., the dependence on rare noble metals, complexity of the metal-ligand catalylst and the poor catalyst stability and recyclability, needs to be tackled for a green process. The past few years have witnessed heterogeneous photocatalysis as a green and novel method for organic synthesis processes. However, the study on C-C coupling of chloride substrates is rare due to the extremely high bond energy of C-Cl bond (327 kJ mol-1 ). Here, we report a robust heterogeneous photocatalyst (Cu/ZnO) to drive the homo-coupling of benzyl chloride with high efficiency, which achieves an unprecedented high selectivity of bibenzyl (93 %) and yield rate of 92 % at room temperature. Moreover, this photocatalytic process has been validated for C-C coupling of 10 benzylic chlorides all with high yields. In addition, the excellent stability has been observed for 8 cycles of reactions. With detailed characterization and DFT calculation, the high selectivity is attributed to the enhanced adsorption of reactants, stabilization of intermediates (benzyl radicals) for the selective coupling by the Cu loading and the moderate oxidation ability of the ZnO support, besides the promoted charge separation and transfer by Cu species.

Bridging organic, molecular, macromolecular, supramolecular and biological sciences to create functions via fluorine chemistry and fluorinated reagents

After a brief introduction highlighting the challenges of fluorine chemistry and the latest developments in the field, this Perspective will discuss how a combination of fluorine and fluorous chemistry together with fluorinated reagents helped to bridge between organic, molecular, macromolecular, supramolecular and biological sciences to create functions in the laboratory of the corresponding author. The reactivity of fluoride as a leaving group is best illustrated by SNAr reactions when it helped to demonstrate single electron transfer-mediated side reactions and through molecular design replaced activated aryl fluorides with aryl chlorides in the synthesis of poly(etherketone)s. Subsequently it was demonstrated how Ni(II) sigma complexes provided an orthogonal approach to the Suzuki-type cross-coupling of arylfluorides, other halides and all aryl C–O based electrophiles. Fluorinated reagents facilitated cylotrimetrization vs cyclotetramerization of bis(methoxy)benzyl chloride and alcohol and the synthesis of the simplest molecular liquid crystals. Triflic acid, methyl triflate facilitated the most tolerant living polymerizations including of cyclic siloxanes, functional vinyl ethers and oxazolines to generate self-organizable dendronized polymers while fluorine, trifluoromethyl and trifluoromethoxy groups facilitated disassembly and reassembly of liquid crystal polyethers and poly(p-phenylenes). Fluorinated stereocenters accessed the first heterochiral recognition in side-chain liquid crystal poly(vinyl ether)s and their model compounds. Alkali metal triflates mediated self-organization of supramolecular nonfluorinated and fluorinated self-assembling minidendrons, dendrons, dendrimers and self-organizable dendronized polymers. The role of fluorinated alkyl groups and of alkali metal triflates in the self-assembly, disassembly and isomorphic replacement analysis, of supramolecular helical columns, of the assembly of helical cogwheel coat and of spherical supramolecular dendrimers forming Frank-Kasper periodic and quasiperiodic arrays was highlighted. A brief discussion of fluorinated amino acids, peptides and peptoids and their potential role in the self-assembly and functions resulted from dendritic dipeptides followed by a discussion of semifluorinated amphiphilic Janus dendrimers as models of biological membranes, including for cell fusion and fission, concludes this Perspective.

Heterogeneous Copper-catalyst Anchored on Chitosan Schiff Basemodified Carbon Nanotubes for Click Reaction

Abstract: A newly designed heterogeneous copper catalytic platform immobilizing copper (II) salt on chitosan Schiff base-modified carbon nanotubes was developed (Cu@CS-Py@CNT). The structure of the catalyst platform was fully characterized by spectroscopic analyses. The catalytic activity of the Cu@CS-Py@CNT was investigated in a one-pot synthesis of 1,4-disubstituted 1,2,3-triazoles by the regioselective click reaction using various benzyl halides or their surrogates, terminal alkynes, and sodium azide in an aqueous environment without using any external Cu-reducing agents.

Photoredox/HAT dual-catalyzed carboxylation of benzyl chlorides with CO2 using thiophenolate and formate as reductants

Carboxylation of benzyl chlorides with CO2 has been developed with photoredox/HAT dual-catalysis. The reaction could be conducted at room temperature with blue LED light source. Potassium formate (HCO2K) is used as a green reductant and a catalytic amount of sodium thiophenolate (PhSNa) is applied as the HAT reagent. Strongly reductive carbon dioxide radical anion (CO2‧–) is produced to promote the cleavage of C–Cl bond.

Building Porous Ni(Salen)-Based Catalysts from Waste Styrofoam via Autocatalytic Coupling Chemistry for Heterogeneous Oxidation with Molecular Oxygen.

The development of robust and industrially viable catalysts from plastic waste is of great significance, and the facile construction of high performance heterogeneous catalyst systems for phenol-quinone conversions remains a grand challenge. Herein, a feasible strategy is demonstrated to reclaim Styrofoam into hierarchically porous nickel-salen-loaded hypercrosslinked polystyrene (PS@Ni-salen) catalysts with high activities through an unusual autocatalytic coupling route. The salen is immobilized onto PS chain by Friedel-Crafts alkylation of benzyl chloride derivatives, and the generated hydrogen chloride coordinately promotes the simultaneous crosslinking and bridge formation between aromatic rings via a Scholl coupling route, leading to hierarchically porous networks. After the metallization with Ni, the resultant networks exhibit high catalytic activity for the oxidation of 2,3,6-trimethylphenol to 2,3,5-trimethyl-1,4-benzoquinone under mild conditions (303 K, 1bar of O2 ). This catalyst also demonstrates attractive recycling performance without an obvious loss of catalytic efficiency over five consecutive cycles. This methodology might provide a potential sustainable alternative to construct environmentally benign and cost-effective catalysts for specific organic transformation.

Development and Validation of a Solvent-Free Headspace GC-MS Method for the Screening of Benzyl Chloride in Pharmaceutical Products

This study presents a solvent-free headspace gas chromatography–mass spectrometry (SF-HS-GC/MS) method for robustly screening benzyl chloride, a mutagenic carcinogen, impurities in active pharmaceutical ingredients (APIs) and drug products. The SF-HS-GC/MS method simplifies analysis by eliminating solvent use, reducing matrix interference. Optimized headspace parameters include incubation temperature, time, and sample amount. Validation, aligned with Q2(R1) ICH guidelines and ICH M7 recommendations, covers selectivity, linearity, limit of detection (LOD), limit of quantification (LOQ), precision, accuracy, system suitability, and robustness. Employing a DB-5MS column (30 m × 0.25 mm, 0.25 µm) with solvent-free split injection, the method’s calibration curve (0.05–5 μg/g) exhibits a strong correlation (&gt;0.9998). The LOQ was 0.1 μg/g, with precision (%CV) consistently &lt;5% and accuracy within 95–105%. Furthermore, an investigation confirmed the absence of artefactual benzyl chloride formation in drug products under headspace conditions. The developed SF-HS-GC/MS method successfully screened benzyl chloride in cinnarizine drug substances and products.

Antimicrobial agents based on new lipophilic alkyl (N-alkyl-N,N-dioctylammoniomethyl)phosphonates

(N-Alkyl-N,N-dioctylammoniomethyl)phosphonates were obtained by alkylation of amino phosphonate potassium salt with alkyl iodides or benzyl chloride. All synthesized compounds demonstrated high antibacterial and antifungal activity against Gram-positive bacterial strains B. cereus and S. aureus and were not active against Gram-negative strains Ps. aeruginosa. Some regularity connecting the structure of the obtained compounds with their antimicrobial action has been established.

Targeting the Carbonic Anhydrase Enzyme with Synthesized Benzenesulfonamide Derivatives: Inhibiting Tumor Growth

Objectives: To assess the anticancer effects of recently developed compounds, Sa, Sb, Sc, and Sd. These compounds were designed to specifically target the carbonic anhydrase enzyme in solid tumors.&#x0D; Methods: The chemical synthesis involved the use of sulfanilamide, chloroacetyl chloride, GABA, thionyl chloride, methanol, hydrazine hydrate, potassium hydroxide, carbon disulfide, and benzyl chloride derivatives. Docking studies were conducted using the MOE software program version 2015.10, and cytotoxic activity was predicted using the MTT assay.&#x0D; Results: The newly synthesized compounds exhibited notable antineoplastic activity in both in silico and cell line investigations. Although they showed a significant difference in potency compared to cisplatin against cancer cells, they also demonstrated significant differences in toxicity towards normal cells. When compared to acetazolamide, compounds Sb displayed an IC50 = 28.41 μM, which was significantly different, and compound Sd showed a non-significant difference with an IC50 = 61.20 μM against MCF7 cells. Additionally, Sb and Sd demonstrated significant difference in toxicity, with IC50 = 279.02 μM and 194.00 μM, respectively, against MCF10a cells. These findings indicate a significant difference compared to acetazolamide for the Sb compound and suggest that the synthesized compounds hold potential for further development as antineoplastic agents. Furthermore, the results from the cell line study align with the in silico study, where both compounds Sb and Sd exhibited higher S scores compared to acetazolamide, implying a stronger binding affinity with the receptor's catalytic site. The presence of a substituted 1,2,4-triazole ring in these compounds contributed to enhanced flexibility and improved interaction with the receptor.&#x0D; Conclusion: A new synthesized compounds exhibited cytotoxicity and demonstrated inhibitory potencies against carbonic anhydrase.

Evaluation of Newly Synthesized Compounds Targeting Carbonic Anhydrase Enzyme for Antineoplastic Activity in Solid Tumors

&#x0D; &#x0D; &#x0D; Objective: This study was conducted with the aim of assessing the antineoplastic potential of recently developed compounds, namely F3, F4, and F5. These compounds were designed to target the carbonic anhydrase enzyme in solid tumors.&#x0D; Methods: The synthesis of these compounds involved the utilization of sulfanilamide, chloroacetylchloride, thiourea, benzyl chloride derivatives, and silver nitrate. Docking studies were carried out using the MOE software program version 2015.10, and the cytotoxic activity was predicted through the implementation of the MTT assay.&#x0D; Results: The compounds that were synthesized displayed noteworthy antineoplastic activity, as evidenced by both in silico simulations and cell line investigations. Notably, Compound F5 exhibited an IC50 value of 9.02 μg/ml for MCF7 cells, signifying a substantial difference when compared to the IC50 value of cisplatin. Moreover, Compounds F3 and F4 exhibited higher S scores in the docking study compared to acetazolamide, implying a more robust binding affinity to the catalytic site of the receptor. The inclusion of a substituted thiazole ring contributed to increased flexibility and enhanced receptor interaction.&#x0D; Conclusion: The synthetic compounds put forth in this study demonstrated notable antineoplastic properties. Furthermore, the complexation process notably augmented the inhibition of cancer cell growth, underscoring their potential as promising agents for combating cancer.&#x0D; &#x0D; &#x0D;