Benzyl Chloride Research Articles

Iron-Catalyzed Cross-Electrophile Coupling

AbstractMetal-catalyzed cross-coupling reactions have transformed molecular synthesis. Although metal-catalyzed reactions have been used for cross-electrophile coupling reactions, they remain challenging due to homodimer formation. Recently, our group developed an iron-catalyzed cross-electrophile coupling of benzyl halides and disulfides to produce thioethers without the use of an exogenous reductant or photoredox conditions, and with undetectable levels of elimination. This Synpacts article highlights both our design strategy to obviate detrimental homodimer formation and the generality of the method.1 Introduction2 Conceptualization and Development3 Mechanistic Studies and Hypothesis4 Conclusion and Future Directions

Catalytic Reductive Homocoupling of Benzyl Chlorides Enabled by Zirconocene and Photoredox Catalysis

Catalytic Reductive Homocoupling of Benzyl Chlorides Enabled by Zirconocene and Photoredox Catalysis

Synthesis, Antimicrobial and Antioxidant Activity of Some New Pyrazolines Containing Azo Linkages.

Pyrazolines and azo-pyrazolines are influential groups of heterocyclic compounds with two nitrogen atoms inside the five-membered ring. They play an important role in a wide range of biological processes, such as antifungal, antioxidant, antimalarial and other antimicrobial activities. The main objective of this study is to synthesize some new heterocyclic compounds with antioxidant and antimicrobial activity Methods: One-pot three components and traditional synthesis of new azo-pyrazoline compounds were achieved in this work. The preparation process has been started by diazotizing 4-(6-methylbenzothiazol-2-yl) benzamine and its coupling reaction with 4-hydroxy acetophenone producing azo-acetophenone, followed by benzylation with benzyl chloride to form the starting material, azo-benzyloxy acetophenone. A series of substituted benzaldehydes were reacted with the latter compound via one pot and classical methods, forming new chalcones containing azo linkages and benzyloxy moieties, which were then converted into new target azo-pyrazoline derivatives. The structures of the synthesized compounds were confirmed by spectroscopic techniques using FT-IR, 1H-NMR, 13C-NMR, and 13C- DEPT- 135 spectra. Finally, the synthesized compounds were screened for their antioxidant and antimicrobial activities against Staphylococcus aureus and Escherichia coli. Overall, the one-pot three-component synthesis of pyrazoline compounds generally provides advantages in terms of efficiency, simplicity, and time-consumption compared to classical synthesis methods. Hence, the study advocates the one-pot method because it eliminates the tedious process of making chalcones, which takes time, materials, and unnecessary effort. Therefore, this is the most convenient and effective approach to green chemistry.

Repurposing First-Row Transition Metal Carbon Dioxide Reduction Electrocatalysts for Electrochemical Carboxylation of Benzyl Chloride

Repurposing First-Row Transition Metal Carbon Dioxide Reduction Electrocatalysts for Electrochemical Carboxylation of Benzyl Chloride

Synthesis of Substituted 1-Benzyl-2H-1,2,3-Triazoles by a Click Reaction Using Calcium Carbide as an Acetylene Source

AbstractAn effective strategy for constructing substituted 1-benzyl-1H-1,2,3-triazoles was developed through click reactions of benzylic halides with sodium azide and calcium carbide as sources of nitrogen and acetylene, respectively. The advantages of this method are an easily handled inexpensive source of acetylene, a wide range of substrates, satisfactory yields, and simple workup procedures, which could promote the use of calcium carbide as a sustainable acetylene source in modern industrial chemistry.

Synthesis and Polymerization of Poly Acryl Imide and One of Their Derivatives Then Curing the Product with Alkyl Halide

The present work involved four steps: First step include reaction of acrylamide ,N-?-Methylen-bis(acryl amide) and N-tert Butyl acryl amide with poly acryloyl chloride in the presence of triethyl amine (Et3N) as catalyst, the second step include homopolymerization of all products of the first step by using benzoyl peroxide(BPO) as initiator in (80-90)Co in the presence of Nitrogen gas(N2). In the third step the poly acrylimide which prepare in second step was convert into potassium salt by using alcoholic potassium hydroxide solution. Fourth step include Alkylation of the prepared polymeric salts in third step by react it with different alkyl halides(benzyl chloride, allylbromide , methyl iodide) by using DMF as solvent for(10-12) hours. Structure Confirmation of all prepared polymers were proved using FT-IR, 1H-NMR and C13-NMR spectroscopy for some polymers. Other physical properties including softening and melting points of the polymers were also measured.

Novel Eco‐Friendly Electrode: Copper Nanoparticle‐Doped MWCNTs for Green Electro‐Organic Synthesis of 1,2,3‐Triazoles With ChCl/Urea as a Solvent and Cocatalyst

ABSTRACTMeticulous electrode design is pivotal in advancing greener and more sustainable electro‐organic synthesis practices. In this research, our team designed and synthesized a copper‐doped electrode on multiwalled carbon nanotubes (MWCNTs) and characterized it using Fourier transform infrared spectroscopy (FT‐IR), scanning electron microscopy (SEM), energy‐dispersive X‐ray spectroscopy (EDS), thermogravimetric analysis (TGA), Brunauer–Emmett–Teller (BET) analysis, X‐ray diffraction (XRD) analysis, X‐ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV) analysis. Subsequently, this electrode was utilized as a catalyst at the electrode surface, serving as a cathode in electro‐oxidation reactions in the presence of phenylacetylene, sodium azide (NaN3), and benzyl halide for the production of 1,2,3‐triazole derivatives under ambient temperature, within a 30‐min reaction time, and at atmospheric pressure, achieving an efficiency level ranging from good to excellent, specifically between 88% and 96%. The synthesized 1,2,3‐triazole derivatives were identified using proton nuclear magnetic resonance (1H NMR) spectroscopy, CHN elemental analysis, and melting point. In this paper, choline chloride/urea deep eutectic solvents (DES) serve multiple roles in the reaction mechanism. They function as solvents and co‐catalysts, generate weak bases, and provide numerous advantages in green chemistry. These advantages include low toxicity, reduced environmental risks, improved atom economy, and non‐volatility, making them safer alternatives to traditional organic solvents.

Designing of a proficient macro porous metallo-polymer of iron with anion functionality: A sustainable approach for arsenic remediation from water

In this study, a novel porous metallo-polymeric network named poly(Ferric trimethacrylate-co-4-Vinyl benzyl chloride), incorporating an iron moiety, was developed for arsenic remediation from water. The synthesis of crosslinked q(pFeVBC) was carried out via suspension polymerization and functionalizing it with hexamethylenetetramine, resulting in a porous three-dimensional structure. Characterization using FTIR, FESEM, XPS, XRD, and BET-SA analysis confirmed its properties. Various monomer ratios were tested to optimize q(pFeVBC) for arsenic removal. The q(pFeVBC) exhibited significant adsorption capacities (qe max exp) of 8.33 mg g−1 for As(V) and 7.9 mg g−1 for As (III), owe to its unique architecture (integrated iron moiety and anion functionality) and porous texture (SA: 112 m2 g−1, pore size: 1.27–2.07 µm), which is close to the capacity calculated by Langmuir model (qe max theo) 8.719 mg g−1 for As (V) and 8.463 mg g−1 for As (III). The PSO kinetic model showed excellent fitting for both arsenic forms. Thermodynamic studies indicated a spontaneous and endothermic adsorption process. Additionally, a 4:10:1 ANN model accurately predicted adsorption behavior.

Zinc Phthalocyanine Core-First Star Polymers Through Nitroxide Mediated Polymerization and Nitroxide Exchange Reaction.

Nitroxide-mediated polymerization (NMP) and nitroxide exchange reaction (NER) are very efficient methodologies that require only suitable alkoxyamine derivatives and create different polymeric architectures in a controlled manner. Herein, the synthesis of star polymers containing TEMPO-substituted symmetric zinc phthalocyanine (ZnPc) is presented via NMP and NER. Moreover, linear polymer formation is conducted in a single arm on TEMPO-substituted asymmetric ZnPc to elucidate the properties of star polymers. All linear and star polymers are characterized by FT-IR, UV-vis, fluorescence, GPC, NMR, and EPR techniques. The results show that the proposed reactions are capable of forming controlled star-shaped polymers. The increasing arm number (from a single to four arms) results in variable dispersity values (Đ) (1.2-3) due to different arm lengths, especially in NMP. However, this difficulty has been overcome via NER, and star polymers have been successfully synthesized with relatively low molecular weight (30 K > 10 K) and low dispersity (1.2-1.9). The results clearly indicate that while styrene and 4-vinyl benzyl chloride monomers are introduced to the structure equally, star polymers with phthalocyanine can be synthesized in a controlled manner, and their quarternized derivatives have the potential to be effective as photoactive agents in photodynamic therapy.

Direct Benzylic C-H Etherification Enabled by Base-Promoted Halogen Transfer.

We disclose a benzylic C-H oxidative coupling reaction with alcohols that proceeds through a synergistic deprotonation, halogenation and substitution sequence. The combination of tert-butoxide bases with 2-halothiophene halogen oxidants enables the first general protocol for generating and using benzyl halides through a deprotonative pathway. In contrast to existing radical-based methods for C-H functionalization, this process is guided by C-H acidity trends. This gives rise to new synthetic capabilities, including the ability to functionalize diverse methyl(hetero)arenes, tolerance of oxidizable and nucleophilic functional groups, precision site-selectivity for polyalkylarenes and use of a double C-H etherification process to controllably oxidize methylarenes to benzaldehydes.

Improved efficiency of continuous conversion of alcohols to chlorides in flow microreactors with DESs/HCl via predictive fluid model

The efficient and safe synthesis of chlorides is attractive in pharmaceutical chemicals yet presents challenges. Herein, a novel route has been developed for the conversion of alcohols into the corresponding alkyl chlorides in continuous flow microreactor. Meanwhile, the system utilizes deep eutectic solvents (DESs) hydrochloride solutions (DESs/HCl) as both solvents and catalysts for this reaction. The results suggest that the premixed mode continuous flow microreactor using DESs/HCl can significantly improve the harsh reaction conditions in the synthesis reaction of chlorides. Furthermore, tuning the HCl concentration under 383 K and 30 min conditions significantly increased the yields of n-Butanol chloride and Benzyl chloride to 86 % and 98 %, respectively. This work shows the great application potential of the continuous flow microreactor combined with DESs/HCl to convert alcohols into corresponding alkyl chlorides or aryl chlorides. Besides, the fluid model and HCl absorption kinetics were established based on the calculated diffusion coefficients (DR), Damköhler number (Da), Bodenstein number (Bo), residence time (τ), and experimental results. The flow model of the mixture of DESs/HCl and alcohols in the microreactor was a plug flow, which is beneficial for improving the efficiency of this reaction.

Corrole–chelated phosphorus complex: enabling dual C–H chlorination and H₂O₂ generation

Corroles, despite their highly tunable and excellent photophysical and electrochemical properties, have rarely been explored as mainstream photocatalytic photosensitizers. Our study introduces a novel application of the highly oxidizing penta–CF3 substituted phosphorus corrole, P–(CF3)5, which has shown remarkable efficacy in the chlorination of phenol and related natural compounds (the beta 2, 3, 8, 17, 18-substituted isomer: 2,3,8,17,18–pentatrifluoromethyl–(5,10,15–tris(pentafluorophenyl) corrole phosphorus (V) difluoride). Here, we report the first case of the simultaneous photocatalytic chlorination of phenol or toluene and H2O2 formation, with the latter achieving a notable rate of > 7 mM/g/h under ambient conditions. Notably, the oxidation of toluene predominantly yields benzaldehyde over benzyl chloride. The H2O2 formation can be finely tuned by adjusting the water/acetonitrile ratio and acid concentration. Comprehensive experimental and theoretical (DFT) investigations were conducted to elucidate the underlying mechanisms of both chlorination and oxidation. This dual–function catalytic process not only enhances reaction efficiency but also underscores the potential of corrole–based catalysts in advancing sustainable and green chemical methodologies.

Reactions of phosphorus (iv) and orthocarboxylic acid esters with benzal and benzyl halides: pathways and catalysis

Reactions of phosphorus (iv) and orthocarboxylic acid esters with benzal and benzyl halides: pathways and catalysis

Transition Metal–Free Synthesis of Vinyl Nitriles from Aldehydes with Acetonitrile at Room Temperature

AbstractA simple and mild protocol for the direct synthesis of vinyl nitriles is described. By employing potassium trimethylsilanolate as the mild base and benzyl chloride as the efficient promoter, a series of E‐configured vinyl nitriles are selectively obtained from readily available aldehydes and acetonitrile at room temperature without the aid of a transition metal catalyst. Mechanistical investigations reveal that this transformation may go through a Knoevenagel condensation process.

Sustainable and versatile Aza-Michael additions promoted by acidic ionic liquids

Acidic ionic liquids are a subset of ionic liquids where the cation or anion possess acidic properties with huge applications in various fields. Here we describe environmentally safe and highly efficient conjugate addition of aromatic and aliphatic amines to α, β-unsaturated compounds in the presence of novel acidic ionic liquids. The acidic ionic liquid catalyst was prepared by combining benzyl chloride with 2-(dimethylamino) ethanol and SnCl2 in a simpler manner. The resulting acidic ionic liquid was characterized using SEM, EDS and FTIR spectroscopy. In the presence of ionic liquids, a wide variety of amines undergo facile conjugate addition to α, β-unsaturated compounds affording the corresponding β-amino compounds in good to excellent yields (72–97 %), shorter reaction times (1–4 h) and mild reaction conditions (60 °C). Furthermore, the study demonstrated the sustainability of the process by showcasing that the acidic ionic liquids could be reclaimed and reused for up to five cycles without compromising their catalytic effectiveness.

Tetra Butyl Ammonium Bromide Catalyzed Synthesis of Thiols and Thioethers

A simple and commercially feasible route of synthesis of thiols and thioethers was developed using a simple phase transfer catalyst, i.e., Tetra Butyl Ammonium Bromide (TBAB). Sodium hydrogen sulfide (NaSH) is used as a sulfurization agent which is easily available and cost-effective. Thiols are obtained by treating alkyl or benzyl halides with sodium hydrogen sulfide (NaSH) in the presence of a phase transfer catalyst (TBAB) at 10 to 15℃. Thioethers are obtained by benzyl thiols treated with corresponding benzyl halides in the presence of a phase transfer catalyst (TBAB) at 10 to 15℃. Synthesis of thiols and thioethers is achieved by substitution reaction of benzyl or alkyl halides with sulfide in the presence of phase transfer catalyst (TBAB) and monochlorobenzene as a solvent at 10 to 15℃. Milder reaction conditions, excellent yield, shorter reaction time and operational simplicity are the key features of this procedure.

Sodium dispersion-mediated reductive dimerization of benzylic halides for symmetrical bibenzyls: Column-free applications to natural products

We report a method for the synthesis of symmetrical bibenzyls by the reductive dimerization of benzylic halides using sodium dispersion (SD). SD, a reagent consisting of sodium particles dispersed in mineral oil, has recently attracted attention as a safer but more reactive source of sodium than sodium lump. We have found that the reductive dimerization of benzylic halides proceeds within 1 h at room temperature in tetrahydrofuran (THF) solvent using SD as a reducing agent. This method is highly sustainable for the synthesis of symmetrical bibenzyls since it uses sodium, which is abundant on earth. As the SD-derived mineral oil in the crude product can be readily removed, three natural products were synthesized on a gram scale without the need for column chromatography. The utility of this reaction was also exemplified by a decagram-scale reaction using 2-methyltetrahydrofuran, known as a green alternative solvent to THF.

Direct Benzylic C−H Etherification Enabled by Base‐Promoted Halogen Transfer

AbstractWe disclose a benzylic C−H oxidative coupling reaction with alcohols that proceeds through a synergistic deprotonation, halogenation and substitution sequence. The combination of tert‐butoxide bases with 2‐halothiophene halogen oxidants enables the first general protocol for generating and using benzyl halides through a deprotonative pathway. In contrast to existing radical‐based methods for C−H functionalization, this process is guided by C−H acidity trends. This gives rise to new synthetic capabilities, including the ability to functionalize diverse methyl(hetero)arenes, tolerance of oxidizable and nucleophilic functional groups, precision site‐selectivity for polyalkylarenes and use of a double C−H etherification process to controllably oxidize methylarenes to benzaldehydes.

Voltammetric Investigations of Low-Coordinate Manganese As an Electrocatalyst for Organic Coupling and Functionalization

Earth-abundant, first row, low coordinate transition metal complexes are considered promising candidates for the electrocatalysis of many organic reactions. The use of transition metal catalysts is no stranger to the field of synthetic organic chemistry; however, many of the existing catalysts require the use of rare and expensive metals such as platinum, palladium, ruthenium, and iridium. In this study, we seek to identify and understand the mechanism by which an Mn(I) complex may act as an electrocatalyst for simple organic coupling and C-H functionalization reactions, beginning with the radicalization of benzyl bromide and benzyl chloride as representative organic halide substrates. The careful design and evaluation of this manganese complex has the potential to offer an effective non-toxic 3d metal electrocatalyst, provided that common transition metal behaviors, such as disproportionation or carbon-metal bond formation, are avoided. Initial characterization of the complex by cyclic voltammetry (CV) demonstrates general reversibility of the catalyst, while additions of benzyl halide exhibit the execution of the electron transfer and catalytic step. Electrochemical simulations run in parallel with CV experiments provide supplementary guidance into the relationship between the substrate and catalyst. Additional studies conducted using bulk electrolysis, mass spectrometry, nuclear magnetic resonance, and density functional theory (DFT) calculation will help to further characterize the mechanism and supporting details. Elucidation of the catalytic mechanism will allow us to use this electrocatalyst in a series of synthetic organic conditions and aid in our advancement toward sustainable organometallic catalysis.

Real time precisely tracing the fluctuations of mitochondrial SO2 in cells during ferroptosis and tissues using a mitochondrial-immobilized ratiometric fluorescent probe

Mitochondrial sulfur dioxide (SO2) plays important roles in physiological and pathological activities. Unfortunately, it is lack of a reliable tool to precisely visualize the mitochondrial SO2 and elaborate its complicated functions in various cytoactivities. Here we report a mitochondrial-immobilized fluorescent probe PM-Cl consisting of coumarin and benzyl chloride modified benzothiazole, which enables selective visualization of mitochondrial SO2via chemical immobilization. The spectral results demonstrated that probe PM-Cl could respond to SO2 with high selectivity and sensitivity. Co-localization and the fluorescence of cytolysis extraction verified the excellent mitochondrial targeting and anchoring abilities. Due to the chemical immobilization, probe PM-Cl could firmly retain into mitochondria after stimulation of carbonyl cyanide m-chlorophenyl hydrazone (CCCP) and H2O2. Significantly, a series of fluorescence images are indicative of capability for detecting the fluctuations of SO2 in mitochondria during ferroptosis. Furthermore, PM-Cl also could visualize SO2 in myocardium and muscle tissues after the stimulation of CCCP. Taken together, probe PM-Cl is a very potential molecular tool for precisely detecting mitochondrial SO2 to explore its complex functions in physiological and pathological activities.