Benzyl Chloride Research Articles

Novel porous carbon electrode derived from hypercross-linked polymer of poly(divinylbenzene-co-vinyl benzyl chloride) for supercapacitor applications

In the present study, pores enriched high surface area of carbon electrode obtained from hypercross-linked polymer of poly(divinylbenzene-co-vinylbenzyl chloride) [P(DVB:VBC)] for supercapacitor application. First, hypercross-linking reaction was carried out in [P(DVB:VBC)] via. simple Friedel-Crafts alkylation method (HCP) followed by pyrolysis at 800 °C (HCP-800). The surface morphology of the synthesized HCP and HCP-800 materials was characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM) technique. HCP-800 showed a remarkable surface area of 1027 m2 g−1 with the abundance of micropores. In addition, the oxidation state of the porous carbon was assessed by x-ray photo electron spectroscopy (XPS). In a three-electrode and symmetric two-electrode configurations, electrodes exhibited a supreme specific capacitance of 272 and 145 F g−1 in aqueous electrolyte, respectively. Specific energy of 39.47 Wh kg−1 at specific power of 699.96 W kg−1 is yielded from the symmetric supercapacitor device (SSCD). Furthermore, SSCD retains more than 94% of its residual capacitance after 5000 GCD cycles at a current density of 5 A g−1 suggests a good cyclic stability.

Preparation, characterization and catalytic study of a nano-inorganic composite of CuO/NiO for the regioselective synthesis of 1,4-disubstituted-1,2,3-triazoles in water

In this research, a nano-inorganic composite of CuO/NiO is prepared by co-precipitation method as an efficient recyclable nanocatalyst for the regioselective synthesis of 1,4-disubstituted-1,2,3-triazoles in water. The catalyst was characterized by several techniques such as the field emission scanning electron microscopy (FESEM), energy dispersive spectroscopy (EDS), x-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), x-ray fluorescence, inductively coupled plasma atomic emission spectroscopy (ICP-OES), and brunauer-emmett-teller (BET) surface area analysis. The regioselective synthesis of 1,4-disubstituted-1,2,3-triazoles was carried out from reaction of various benzyl halides or alkyl halides with phenyl acetylene and sodium azide in water under reflux condition in high yields. The CuO/NiO nanocatalyst can be simply recovered and reused 6 runs without a significant slight in activity.

Synthesis and Antimicrobial, Antiproliferative Evaluation of Novel Quinolone and Conazole Analogues via Conventional and Microwave Techniques

Abstract1,2,4‐Triazole‐3‐one (3), acquired from cinnamaldehyde was converted to the corresponding carbox(thio)amides via several steps (6 a–c). Their reaction with sodium hydroxide gave the 1,2,4‐triazole derivatives (7 a–c). Compound 3 treatment with 2‐bromo‐1‐(4‐chlorophenyl) ethanone or 2‐chloro‐1‐(2,4‐dichlorophenyl)ethanone afforded the compounds 8 a,b and by reducing these compounds reduction products were obtained (9 a,b). The synthesis of (10 a–e) was carried out by the reaction compounds 9 a,b with different benzyl chlorides. Then oxadiazole derivative (12) was obtained by ring closure from hydrazide compound 5. Subsequently compounds 3, 7 a–c, and 12 were treated with various amines in the presence of formaldehyde to yield Mannich bases (11 a–e, 14 a–e, 13 a,b). Microwave‐assisted and conventional techniques were utilized for the syntheses. The structures of newly synthesized compounds were illuminated by spectroscopic methods. Their antimicrobial (MIC method), and anticancer activities (Abay's method) were examined. Results showed that most of the compounds exhibited good antimicrobial activities. Especially compounds 14 a–e which is a mannich base showed very good antitubercular activity against Mycobacterium smegmatis compared with Streptomycin standard drug. Also compounds 8 a and 9 b have been found to have strong antiproliferative effects on the HeLa cervical cancer cells and also these compounds did not have a cytotoxic effects on a normal cells.

Ni-Catalyzed Arylbenzylation of Alkenylarenes: Kinetic Studies Reveal Autocatalysis by ZnX2 *.

We report a Ni-catalyzed regioselective arylbenzylation of alkenylarenes with benzyl halides and arylzinc reagents. The reaction furnishes differently substituted 1,1,3-triarylpropyl structures that are reminiscent of the cores of oligoresveratrol natural products. The reaction is also compatible for the coupling of internal alkenes, secondary benzyl halides and variously substituted arylzinc reagents. Kinetic studies reveal that the reaction proceeds with a rate-limiting single-electron-transfer process and is autocatalyzed by in-situ-generated ZnX2 . The reaction rate is amplified by a factor of three through autocatalysis upon addition of ZnX2 .

Ni‐Catalyzed Arylbenzylation of Alkenylarenes: Kinetic Studies Reveal Autocatalysis by ZnX2**

AbstractWe report a Ni‐catalyzed regioselective arylbenzylation of alkenylarenes with benzyl halides and arylzinc reagents. The reaction furnishes differently substituted 1,1,3‐triarylpropyl structures that are reminiscent of the cores of oligoresveratrol natural products. The reaction is also compatible for the coupling of internal alkenes, secondary benzyl halides and variously substituted arylzinc reagents. Kinetic studies reveal that the reaction proceeds with a rate‐limiting single‐electron‐transfer process and is autocatalyzed by in‐situ‐generated ZnX2. The reaction rate is amplified by a factor of three through autocatalysis upon addition of ZnX2.

Palladium-catalyzed carbonylative synthesis of 3-arylquinolin-2(1H)-ones from benzyl chlorides and o-nitrobenzaldehydes

• A general and straightforward palladium-catalyzed aminocarbonylation procedure of benzyl chlorides have been developed. • o- nitrobenzaldehydes have been used as stable nitrogen sources for the synthesis of 3-arylquinolin-2(1 H )-ones. • Mo(CO) 6 has been used both as CO precursor and reductant. A palladium-catalyzed carbonylative cyclization of benzyl chlorides with o- nitrobenzaldehydes has been developed for the synthesis of 3-arylquinolin-2(1 H )-ones. Mo(CO) 6 played a dual role as both a CO surrogate and a reductant in this carbonylative transformation.

KINETICS OF QUATERNIZATION BETWEEN N, N-DIMETHYLANILINE AND BENZYL CHLORIDE IN POLAR SOLVENTS-A REVISIT TO MENSHUTKIN REACTION

This work reports an extension of Menshutkin reaction and involves the studies on kinetics of quaternization reaction between N,N-Dimethylaniline and benzyl chloride in acetone and in other various solvents at 300 K. The progress of the reaction was followed by measuring the conductance of the product formed at regular intervals of time. The effect of [benzyl chloride] and [N,N-Dimethylaniline] on reaction rate was studied under pseudo-first order condition and the rate showed first order dependence on both [benzyl chloride] and [N,N-Dimethylaniline]. The effect of dielectric constant of the medium on reaction rate was studied by employing various solvents such as methyl ethyl ketone, isopropyl alcohol, ethyl alcohol, methyl alcohol and acetonitrile and the rate is found to increase with increase in dielectric constant of the medium. The linear plot with a negative slope on plotting log k2 against 1/D where D is the dielectric constant of the medium indicates the existence of a highly charged or a polar transition state during the progress of the reaction. The quaternization reaction was also carried out at different temperatures so as to compute the various thermodynamic parameters like activation energy, enthalpy of activation, entropy of activation and Gibb’s free energy change. The higher value of activation energy is attributed for a slower reaction which is sterically controlled rather than thermodynamically controlled. The negative value of entropy of activation (ΔS*) indicates some sort of surrendering of disorder in the transition state on its formation which proves that it is highly ordered with sufficient charge separation and polar in character. The product after purification was analysed by melting point and infra-red spectral analysis and is proved to be N-Benzyl-N,N-dimethylphenylmethanaminium chloride. A plausible mechanism in accordance with the obtained experimental results is reported.

Boosting Photoredox Catalysis Using a Two-Dimensional Electride as a Persistent Electron Donor.

Electrides, which have excess anionic electrons, are solid-state sources of solvated electrons that can be used as powerful reducing agents for organic syntheses. However, the abrupt decomposition of electrides in organic solvents makes controlling the transfer inefficient, thereby limiting the utilization of their superior electron-donating ability. Here, we demonstrate the efficient reductive transformation strategy which combines the stable two-dimensional [Gd2C]2+·2e- electride electron donor and cyclometalated Pt(II) complex photocatalysts. Strongly localized anionic electrons at the interlayer space in the [Gd2C]2+·2e- electride are released via moderate alcoholysis in 2,2,2-trifluoroethanol, enabling persistent electron donation. The Pt(II) complexes are adsorbed onto the surface of the [Gd2C]2+·2e- electride and rapidly capture the released electrons at a rate of 107 s-1 upon photoexcitation. The one-electron-reduced Pt complex is electrochemically stable enough to deliver the electron to substrates in the bulk, which completes the photoredox cycle. The key benefit of this system is the suppression of undesirable charge recombination because back electron transfer is prohibited due to the irreversible disruption of the electride after the electron transfer. These desirable properties collectively serve as the photoredox catalysis principle for the reductive generation of the benzyl radical from benzyl halide, which is the key intermediate for dehalogenated or homocoupled products.

Nickel-Catalyzed Multicomponent Coupling: Synthesis of α-Chiral Ketones by Reductive Hydrocarbonylation of Alkenes.

A nickel-catalyzed, multicomponent regio- and enantioselective coupling via sequential hydroformylation and carbonylation from readily available starting materials has been developed. This modular multicomponent hydrofunctionalization strategy enables the straightforward reductive hydrocarbonylation of a broad range of unactivated alkenes to produce a wide variety of unsymmetrical dialkyl ketones bearing a functionalized α-stereocenter, including enantioenriched chiral α-aryl ketones and α-amino ketones. It uses chiral bisoxazoline as a ligand, silane as a reductant, chloroformate as a safe CO source, and a racemic secondary benzyl chloride or an N-hydroxyphthalimide (NHP) ester of a protected α-amino acid as the alkylation reagent. The benign nature of this process renders this method suitable for late-stage functionalization of complex molecules.

Nickel Nanoparticles Immobilized over Mesoporous SBA-15 for Efficient Carbonylative Coupling Reactions Utilizing CO2: A Spotlight.

Ecofriendly routes for the synthesis of carbamates and carbonylative coupling products such as benzyl formate derivatives are very demanding for both academia and industries. Foreseeing a sustainable green future, we systematically analyzed the synthesis history of both these chemicals, mentioning their pros and cons. As a step towards green chemistry, here we have optimized the reaction conditions for the synthesis of various benzyl formates from corresponding benzyl halides and carbamates from substituted anilines and alkyl halides catalyzed by Ni(0) nanoparticles (NPs) immobilized over amine-functionalized ordered mesoporous SBA-15 material in the presence of CO2 as C1 source. This spotlight on applications is aimed to provide a clear outlook to date regarding the gradual progress in the synthesis of both these aforementioned chemicals and finally addresses further efforts for overcoming the current challenges.

External Catalyst‐Free Oxidation of Benzyl Halides to Benzoic Acids Using NaOH/TBHP in Water

AbstractAn efficient and metal‐free methodology for the oxidation of benzyl halides to benzoic acids using an inexpensive and green oxidant (TBHP) in aqueous basic medium has been developed. This protocol offers an excellent way to avoid adding catalysts and involves the use of an in‐situ generated halide ion as catalyst. It is also the first report on the oxidation of benzyl iodides to benzoic acids. A series of carboxylic acids were prepared from benzyl halides in high yields under mild reaction conditions by this method which does not require chromatographic purification. Gram scale reactions for the synthesis of the carboxylic acids in good yields have been successfully carried out using benzyl chloride, bromide and iodide. As an industrial application, the synthesis of a key monomer used for the synthesis of polyethylene terephthalate (PET), i. e., terephthalic acid (PTA), has also been accomplished in good yields.

4-Chlorobenzyl Chloride

The X-ray structure of the title compound has been determined for the first time. Its molecular structure is in good agreement with those previously determined for similar benzyl halides and the angles between the ring–Cl bonds in adjacent molecules show values in good agreement with an early Zeeman quadrupole spectroscopy study.

Studies on the Processes of Electron Capture and Clustering of Benzyl Chloride by Ion Mobility Spectrometry.

This paper presents the results of the study on the course of the benzyl chloride (BzCl) ionization process in a drift tube ion mobility spectrometer (DT IMS) in which nitrogen was used as the carrier gas. BzCl ionization follows the dissociative electron capture mechanism. The chloride ions produced in this process take part in the formation of cluster ions. Using DT IMS allows for estimation of the value of the electron attachment rate for BzCl and the equilibrium constant for the cluster ion formation. The basic experimental method used in this work was to analyze drift time spectra obtained for the introduction of the sample to the spectrometer with the drift gas. The theoretical interpretation of the results is based on the mathematical description of the ion transport. This description takes into account the phenomenon of diffusion, as well as the processes of formation and dissociation of ionic clusters occurring during the movement of ions in the drift section.

Selective C-alkylation of substituted naphthols under non-aqueous conditions

A simple and selective C-alkylation of 1- and 2-naphthols with benzylic and allylic halides was developed. In an organic solvent, like cyclopentyl methyl ether, or toluene in the presence of the ether or alcohol additives, a selective ortho-addition leading to substituted naphthalenones up to 90 % was achieved.

Reductive Radical Conjugate Addition of Alkyl Electrophiles Catalyzed by a Cobalt/Iridium Photoredox System.

Alkyl and aryl halides have been studied extensively as radical precursors; however, mild and less toxic conditions for the activation of alkyl bromides toward alkyl radicals are still desirable. Reported here is a reductive radical conjugate addition that allows for the formation of alkyl radicals via activation of alkyl bromides through cobalt/iridium catalysis. The developed conditions are emphasized in the broad substrate scope presented, including benzylic halides and halides containing free alcohols, silanes, and chlorides.

Synthesis, Characterization, Theoretical Analyses, and Investigation of Their Biological Activities of Acetovanillone-Derived Novel Benzyl Ethers

In this study, acetovanillone-derived novel benzyl ethers were synthesized as target compounds. For the synthesis of these target compounds, ketone derivatives (3a–b) were synthesized as the starting compounds. Compounds 4a–b, which are alcohol derivatives, were then synthesized from the reduction of these ketone derivatives. In the last stage of the synthesis study, benzyl ether derivatives (6a–h, 7a–h), the target compounds containing acetovanillone, were synthesized from the reaction of the alcohol derivatives (4a–b) with various benzyl halides (5a–h). The structures of the synthesized compounds were characterized by various spectroscopic methods (FT-IR, 1H NMR, 13C NMR, mass spectrometry, and elemental analysis). In vitro antileishmanial and antibacterial activity tests were then performed for all synthesized compounds. Biological activity tests showed that while only a few of the compounds had antileishmanial activity, most had antibacterial activity. In addition, the ADME parameters, pharmacokinetic properties, and drug-like nature of all compounds were theoretically investigated using the SwissADME webserver. Finally, molecular docking simulations were carried out to support in vitro investigations and evaluate the inhibition effect of the synthesized compounds on the 3IW2 (Mycobacterium tuberculosis (Mtb) Cyp125; Pdb ID: 3IW2) receptor structure. Also, possible binding sites of some compounds with high affinity to Mtb Cyp125 according to docking results were identified.

Preparation of cyclic acetals and gem-dichlorocyclopropanes based on 1,2-dichloromethylbenzol

Using 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane (sol-ketal) and 1,2-dichlomethylbenzene under the conditions of phase transfer catalysis, mono- and diesters containing cycloacetal fragments were synthesized. Also, with the help of dichloride, in the presence of benzene, mono- and diesters of allyl alcohol were obtained. Dichlorocyclopropanation of unsaturated ethers using chloroform, alkali and catamine AB catalyst made it possible to obtain compounds containing gem-dichlorocyclopropane fragments. O-alkylation of the sol-ketal with 1-[(alloxy)methyl]-2-(chloromethyl)benzene (mono-derivative of allyl alcohol) was used to synthesize an ether combining in its structure 1,3-dioxolane and gem-dichlorocyclopropane fragments simultaneously. The obtained substances were analyzed and confirmed by mass spectrometry («Chromatek-Kristall» instrument with Nist research database) and NMR spectroscopy («Bruker instrument»). It was found that among a number of compounds obtained, only 4-{[(2-{[(2,2-dichlorocyclopropyl) methoxy]methyl}-benzyl)oxy] methyl}-2,2-dimethyl-1,3-dioxolane exhibits cytological activity against the cell lines HEK293, SH-SY5Y, MCF-7 and A549.

A Preliminary Study on the Synthesis of poly(vinylbenzyl chloride) with Different Solvents

Polyvinyl benzyl chloride (PVBC) was synthesized by free radical polymerization of 4-vinylbenzyl chloride using benzoyl peroxide initiator at 60 °C. PVBC was synthesised in different solvents such as toluene, xylene, 1,4-dioxane, and tetrahydrofuran. The polymers were structurally characterized by 1H NMR and FTIR spectroscopic techniques. The thermal property of the polymer was investigated by thermogravimetric analysis (TGA) and differential thermogravimetric analysis (DTA).The number average molecular weight, weight average molecular weight and polydispersity index of PVBC synthesised in different solvents were determined and compared by gel permeation chromatography technique.

Cu(I)-Catalyzed 1,2-Alkynyl-propargylation and -benzylation of Benzyne Derivatives.

We report here a three-component, Cu(I)-catalyzed hexadehydro-Diels-Alder (HDDA) benzyne 1,2-difunctionalization reaction. This protocol allowed the introduction of two different carbon-based substituents onto the in situ-generated benzyne. These substituents were terminal monoynes or diynes partnered with propargylic, benzylic, or allylic chlorides. An example of a sequential HDDA reaction is demonstrated using the product of a 1,3-diyne and a propargylic halide, itself a newly created HDDA precursor.

Production of polyalfaolefin-based lubricants using new (poly)ionic liquid /AlCl3 catalysts as environmentally friendly alternatives to commercial AlCl3 route

Aiming to decrease corrosive AlCl3 dosage in polyalphaolefin production, two new (poly)ionic liquid /AlCl3 catalysts were synthesized from the reaction of 1-vinylimidazole with benzyl chloride (to yield IL) and subsequent polymerization of its vinyl bond by radical route, to achieve polyionic liquid (PIL). Cationic oligomerization of three α-olefin monomers, from 1-hexene to 1-decene, was accomplished using IL(or PIL)/AlCl3 catalysts with 50:50 wt.% composition to halve the usage of hazardous AlCl3. Microstructure and flow characteristic of the obtained PAO oligomers were characterized by 1HNMR, 13CNMR, GPC, viscometry, GC-Mass, and SimDis analyses and compared with those of PAOs from neat AlCl3. Results from GPC, viscometry and GC revealed that molecular weight decreases using lighter α-olefin monomers. Notably, while the PAOs from IL/AlCl3 have almost heavier fractions, the ones from PIL/AlCl3 and neat AlCl3 demonstrated similar molecular weight and KV100 amounts. The PAOs from PIL/AlCl3 and IL/AlCl3 represented a more uniform structures, with low short chain branching, beneficial to higher viscosity index (VI). This achievement featured PIL/AlCl3 as a suitable alternative to corrosive AlCl3, which besides its more environmentally friendly character, thanks to PIL presence, is capable of producing PAOs with the same KV100, however, with much higher VI values.