Benzene Chloride Research Articles

Nickel-Catalyzed Enantioselective Carbonyl Addition of Aryl Chlorides and Bromides to Aldehydes.

The Ni-catalyzed enantioselective addition reaction of aryl halides to aldehydes was studied with cyanobis(oxazoline) as chiral ligands and Mn as reductant. Aryl and heteroaryl bromides reacted with phenyl aldehyde at room temperature to produce dibenzyl alcohols in 16-99 % yields with 53-92 % ees. Moreover, the coupling of phenyl chloride with a variety of aryl, heteroaryl and alkyl aldehydes was demonstrated in the presence of cyanobis(oxazoline)/Ni(II) at 60 °C in generally high yields with moderate enantioselectivities.

Chemical Transformations of Benzyl Alcohol Caused by Atomic Chlorine.

Atomic chlorine present in the polluted troposphere can form potentially carcinogenic compounds as a result of a reaction with a natural product. This paper examines the stability of benzyl alcohol-a natural product commonly found in cosmetics-in interaction with atomic chlorine, which is becoming ever more present in the Earth's atmosphere as a result of its pollution. Research shows that atomic chlorine generated in the gas phase easily penetrates the liquid phase of benzyl alcohol, resulting in the formation of hydrochloric acid. The resulting HCl initiates further transformations of benzyl alcohol. Our study presents the amounts of the reaction products. The quantitative analysis was made using the GC method, and all the products were identified using the GC-MS method. The products include dichloromethyl benzene, 2-chlorobenzyl alcohol, and 3-chlorobenzyl alcohol, which are harmful, but are formed in very small amounts. The harmful substance occurring in a much higher amount is benzyl chloride-that is a product of acidification of benzyl alcohol by HCl.

Enhanced properties of a positive-charged nanofiltration membrane containing quaternarized chitosan through second interfacial polymerization for the removal of salts and pharmaceuticals.

Nanofiltration (NF) membrane technology has been widely used in the removal of salts and trace organic pollutants, such as pharmaceuticals and personal care products (PPCPs), due to its superiority. A positive-charged composite NF membrane with an active skin layer was prepared by polyethyleneimine (PEI), trimethyl benzene chloride, and quaternate chitosan (HTCC) through second interfacial polymerization on the polyethersulfone ultrafiltration membrane. The physicochemical properties of the nanocomposite membrane were investigated using surface morphology, hydrophilicity, surface charge, and molecular weight cut-off (MWCO). The influence of the concentration and reaction time of PEI and HTCC was documented. The optimized membrane had a MWCO of about 481 Da and possessed a pure water permeability of 25.37 L·m-2·h-1·MPa-1. The results also exhibited salt rejection ability as MgCl2 > CaCl2 > MgSO4 > Na2SO4 > NaCl > KCl, showing a positive charge on the fabricated membrane. In addition, the membrane had higher rejection to atenolol, carbamazepine, amlodipine, and ibuprofen at 89.46, 86.02, 90.12, and 77.21%, respectively. Moreover, the anti-fouling performance and stability of the NF membrane were also improved.

Exploring the energetics of Suzuki cross-coupling reaction: A computational study of palladium and nickel catalysts

The present study employed density-functional theory (DFT) calculations to investigate the Suzuki-Miyaura Cross-Coupling reaction using single atom catalysis (SAC) via palladium or nickel. The reaction barriers for chloride bond cleavage in phenyl chloride were found to be 34.68 kJ/mol and 24.24 kJ/mol for palladium and nickel catalysts, respectively. During the transmetalation process, the energy barrier for boronic acid release from phenyl trihydroxyboronate using SAC via palladium and SAC via nickel was calculated to be 74.17 kJ/mol and 65.22 kJ/mol, respectively. The results indicated that in the oxidative addition and transmetalation reactions, the SAC via nickel outperforms the SAC via palladium, while the SAC via palladium excels in the reductive elimination reaction. These findings suggest the effectiveness of a SAC via nickel as a substitute for SAC via palladium in the synthesis of biphenyls in the Suzuki-Miyaura cross-coupling reaction.

Quantum chemical calculation for synthesis some thiazolidin-4-one derivatives

In this study, outline the synthesis and spectroscopic characterization of novel 2-imino-thiazolidin-4-one derivatives. The synthesis process is divided into three main parts. Firstly, we prepared the starting material, 2-amino-4-(substitutedphenyl)-1,3-thiazole, by reacting thiourea with substituted acetophenone in the presence of iodine. The second part involved the synthesis of 2-chloroacetamido-4-(substitutedphenyl)-1,3-thiazole through the reaction of heterocyclic amine with chloroacetyl chloride in benzene. The third part focused on the cyclization reaction of synthesized intermediate compounds, leading to the formation of a new series of desired products, namely, 2-imino-3-[4-(substitutedphenyl)-1,3-thiazol-2-yl] thiazolidin-4-ones. The structures of the synthesized compounds were determined based on spectral data, including IR, 1HNMR, and 13CNMR. Various analytical methods were employed to explore intermolecular interactions, nonlinear optical properties, HOMO-LUMO energy gap, potential energy maps, Natural Bond Orbital (NBO) analysis, and thermodynamic parameters of diverse compounds. The assessment of weak intermolecular interactions using Noncovalent interactions (NCI) and reduced density gradient (RDG) methods revealed the presence of robust hydrogen bonds, van der Waals forces, and steric effects within the compounds. Topological parameters highlighted significant hydrogen bonding capabilities among the studied compounds. Additionally, the analysis of the HOMO-LUMO energy gap and other quantum chemical parameters unveiled the influence of protonation on polarization, chemical reactivity, and corrosion resistance. Molecular Electrostatic Potential (MEP) analysis indicated changes in electrophilicity and nucleophilicity upon the addition of protons, altering chemical reactivity. Stabilization energies of donor-acceptor interactions, assessed through Natural Bond Orbital (NBO) analysis, provided insights into charge transfer and conjugative interactions, particularly emphasizing electron delocalization within the compounds' phenyl rings.

Modification, Characterization of New Thiazolidinone and Oxazolidinone Derived from Levofloxacin and Evaluation of Anti-Oxidant

The research study included the synthesis of a new series of heterocyclic derivatives containing the antibiotic Levofloxacin. The first way provides for the reaction of Levofloxacin with thionyl chloride in benzene as a solvent to give an acid chloride derivative. A new class of acid hydrazide synthesized from Levofloxacin was studied. Schiff bases were produced via the reaction of acid hydrazide with substituted aromatic ketones in methanol. The next stage involved the response of Schiff bases with thioglycolic acid and mono chloroacetic acid in DMF to produce derivatives of the antibiotic levofloxacin that have five heterocyclic members, including the derivatives thiazolidine-4-one and oxazolidine-5-one. The FTIR, 1HNMR, and 13CNMR spectra methods were used to confirm the structures of newly synthesized compounds. Also, the antioxidant properties of the synthetic compounds were evaluated in vitro. According to this study, levofloxacin-derived compounds have higher antioxidant capacities than ascorbic acid (vitamin C), and the medication also acts as an anti-inflammatory for respiratory infections.

L-MM Auger electron emission from chlorinated organic molecules under proton impact: Angular distribution and total cross section measurement

We have measured the absolute cross section for L-MM Auger electron emission in chlorinated methanes and benzene chloride molecules in collision with keV energy protons. The measurements have been performed with four different chlorine containing organic molecules viz CCl4, CHCl3, CH2Cl2 and C6H5Cl. We have measured the angular distribution of chlorine L-MM Auger electrons at backward emission angles (90° – 150°). The angular distribution shows an isotropic character. We also studied the projectile energy dependence of the total L-MM Auger yield for proton energy ranging from 125 keV to 275 keV. Carbon K-LL Auger yield was also obtained in the same experiments.

Synthesis of Few New Carrier Polymers Derived from 2-hydrazinylbenzo[d]thiazole

2-hydrazinylbenzo[d]thiazole compound [1] is produced from reaction of 2-mercapto-benzothiazole with hydrazine hydride in ethanol. Compound [1] reacted with maleic anhydride in DMF to produce (Z)-4-(2-(benzo[d] thiazol-2yl) hydrazinyl)-4-oxobut-2-enoic acid [compound (2)]. While the treatment of compound [2] with the ammonium persulfate (NH4)2S2O8 (as the initiator) in order to produce compound [3], then compound [3] reacted with thionyl chloride in benzene to produce compound [4], finally compound [4] reaction with various drugs: cephalexin, amoxicillin, sulfamethizole, elecoxib obtained polymers [5–8]. The structure of synthesized compounds identified by spectral data: fourier transform infrared (FTIR) and proton nuclear magnetic resonance (1HNMR) spectroscopy. The polymers [5–8] have been screened for their antibacterial activities against Staphylococcus aureus (G+), Escherichia coli (G-) and compared with the drug (amoxicillin). The anticancer activity (Hep G2 (human liver cancer cell line) of some prepared polymers were also studied.

Deoxygenative Chlorination of Aldehydes and Alcohols with Dichloromethyl Methyl Ether and TiCl4

AbstractHere, we report highly efficient deoxygenative chlorination of aldehydes and alcohols with a dichloromethyl methyl ether and TiCl4 system. The method converts various aldehydes and alcohols into the desired geminal dichlorides or chlorides with good to excellent yields (up to 99 %). Combined with a subsequent Rieche formylation step using the same reagent system, this method provides an efficient approach for synthesis of aromatic dialdehydes. This strategy involves deoxy‐chlorination of the aryl aldehydes followed by a second formylation of more activated benzal chloride derivatives. Dialdehydes can be easily obtained by hydrolyzing the corresponding of dichloromethyl derivative.

Density Functional Theory Study on [Ni0(1,10-Phenanthroline)]-Catalyzed Reductive Carboxylation of Alkyl and Aryl Halides with CO2: Effect of the Lewis Acid and β-H Elimination Side Reaction in the Crucial CO2 Insertion Step.

The [Ni0(phen)] (1)-catalyzed reductive carboxylation of propyl and phenyl chloride with a CO2 molecule has been compared using the density functional theory method. The reactivity of 1 in the initial oxidative addition with the propyl and phenyl chloride and in the subsequent single electron transfer step to form the NiI intermediates, [NiI(phen)(R'-CH2)], 4, (R' = CH3-CH2-), and [NiI(phen)(C6H5)], 4', is almost the same. However, an apparent reactivity difference is interpreted in the CO2 insertion step, which involves the NiI and the NiII intermediates. In both propyl and phenyl chloride, the NiI-mediated CO2 insertion is kinetically more preferred than that mediated by the analogues NiII intermediates (3 and 3') by +5.0 and +33.4 kcal/mol, respectively. This trend in energetics clearly shows that the CO2 insertion of phenyl chloride exclusively occurs via the NiI-mediated pathway, whereas in propyl chloride, it follows both NiI- and NiII-mediated pathways. Overall, the catalytic efficacy of 1 is found to be higher in phenyl chloride (by +11.3 kcal/mol) than that in propyl chloride. Furthermore, the effect of a plausible β-H elimination side reaction in the CO2 insertion step is modeled for propyl chloride. Herein, the β-H elimination of the NiII propyl species (3) is kinetically more feasible than its CO2 insertion, while the β-H elimination of NiI propyl (4) is rather difficult compared to its CO2 insertion by +16.3 kcal/mol. This strongly supports the suitability of the NiI intermediate in the CO2 insertion step. In addition, the role of the Lewis acid (X) in the CO2 insertion step is tested by incorporating various Lewis acids (X = MgCl2, ZnCl2, AlCl3, and LiCl) in the NiII propyl (7) and NiI propyl (5) intermediates. The Lewis acids effectively facilitate the CO2 insertion step, and the effect due to MgCl2 is found to be more evident. MgCl2 enhances the CO2 insertion of 5 and 7 by 89 and 84%, respectively, and hence, the NiI-mediated CO2 insertion of propyl halide (ΔG⧧ = +1.4 kcal/mol) is now comparable with that of phenyl halide (ΔG⧧ = +0.9 kcal/mol). This suggests that in the presence of Lewis acids, the catalytic efficacy of 1 is enhanced for the reductive carboxylation of propyl halide and exhibits similar reactivity to that of phenyl halide.

Derivatization of Inseparable Ursolic and Oleanolic Acids of Fagraea fragrans Fruits to Enhance Their Anticancer Activity

Inseparable Ursolic acid and its isomeric oleanolic acid are the major compounds in Fagraea fragrans fruits. The white solid crystals , 3.1 % of these triterpenic acids are easyly isolated from alcoholic extracts of these dried fruits. They are well known in both cosmeticeutical and medicinal industries. Therefore the objective of this work is to derivative those to be the inseparable ethyl ursolate 3-ethyl ether [its isomeric ethyl oleanolate 3-ethyl ether], and to evaluate their anticancer activity against P-388 murine leukemia cells. The results are 71% of the derivatives have been successfully made from the inseparable ursolic [its isomeric oleanolic] acids by in situ reaction between those triterpenic acids with thionyl chloride and ethanol in benzene. The anticancer activity of ethyl ursolate 3-ethyl ether [its isomeric ethyl oleanolate 3-ethyl ether] against P-388 murine leukemia cells with IC50 value of 31.36 µg/mL is twofold (1.7) more potent then their mother compounds, the inseparable ursolic [its isomeric oleanolic] acids with IC50 value of 53.5 µg/mL.

Regioselective Synthesis of 4,7,12,15‐Tetrasubstituted [2.2]Paracyclophanes: A Modular Route Involving Optical Resolution

AbstractA practical synthetic method for preparing bis‐(para)‐pseudo‐ortho and bis‐(para)‐pseudo‐meta type 4,7,12,15‐tetrasubstituted [2.2]paracyclophanes is reported. Regioselective double Rieche formylation was successfully applied to the corresponding dibromo[2.2]paracyclophanes under slightly modified conditions. Aldehydes reacted in an unknown direction with Rieche formylation agents, dichloromethyl methyl ether and titanium(IV) tetrachloride, leading to the formation of benzal chlorides. Formylated products were obtained after hydrolysis of these benzal chloride derivatives. Optical resolution was performed with the diastereomer method and (RP)‐4,12‐dibromo‐7,15‐diformyl[2.2]paracyclophane was successfully obtained in an enantiomerically pure form (99 % ee). Their synthetic utility is demonstrated with some exploratory transformations to access corresponding differently functionalized tetrasubstituted [2.2]paracyclophane derivatives.

Synthesis and antiviral activity of 1-(n-substituted amino acetyl)-2-(5-substituted phthalimidomethyl) benzimidazoles

Phthalic anhydride and 3-Nitro Phthalic anhydride were reacted with 2-aminomethyl benzimidazole in pyridine to give 2- (5-substituted phthalimidomethyl) bezimidazoles. These benzimidazoles were refluxed with chloroacetyl chloride in dry benzene followed by reaction with different secondary amines to give 1-(N-substituted amino acetyl)-2-(5-substituted phthalimidomethyl) benzimidazoles. Antiviral activity of these compounds was studied against Ranikhet Disease Virus (RDV) and Vaccinia Virus (VV). Some of these compounds have been found to be active against RDV.

Component composition of dissolved organic compounds of sewage water of uzen’ oilfield

The composition of extracts of volatile dissolved organic compounds of the wastewater of the Ozen oilfield was studied by chromatography-mass spectrometry (GC/MS). It has been established that the main components are hydrocarbons. It should be noted the presence in the water of benzyl chloride (benzene chloride) -1.3%, the content of which is strictly regulated in oil. A low content of organic acids (palmitic acid) is observed. It should also be noted the presence of tertiary N, N-dimethyldodecanamine (C-12) upto 2.3% and N, N-dimethyltridecanamine (C-13), which are components of corrosion inhibitors. The presence of xylene, mesitylene, 1,2,3-trimethylbenzene and 2,6-dimethylnaphthalene indicates the possible use of the demulsifier type Tretolite. A significant amount of squalene, which is a natural biomarker of oils has also been discovered.

Reactions of Benzylidene Chlorides with S-Methyl Diethylphosphinothioate

S-Methyl diethylphosphinothioate reacted with benzylidene chlorides to give the corresponding aryl(chloro)methyl methyl sulfide and diethylphosphinoyl chloride. The product structure suggests initial attack of the methylsulfanyl group on the CH carbon atom of dichloromethylarene. Arenecarbothialdehyde dithioacetals and trimers and O,O-dialkyl[aryl(methylsulfanyl)methyl]phosphonates were synthesized.

Regioselective Synthesis of 1,3,5-Trisubstituted Pyrazoles Containing an Anthranilic Acid Motif

An effective method was developed for the synthesis of 1,3,5-trisubstituted pyrazoles by using acetylenic ketones, obtained from ethyl 5-ethynylanthranilate, in reactions with substituted hydrazines and hydrazides. It was shown that the cyclization of ethyl 5-(3-aryl-3-oxopropinyl)- anthranilates with arylhydrazines proceeded regioselectively and led to the formation of 1,3,5-trisubstituted pyrazoles containing an anthranilate moiety at the position С-3. Significant deterioration of regioselectivity was observed in the reactions of ethyl 5-(3-aryl-3-oxopropinyl)anthranilates with N-methyl- and N-tert-butylhydrazines. The initial products formed in reactions of ethyl 5-[3-(4-fluorophenyl)-3-oxopropinyl]anthranilate with benzoyl and isonicotinoyl hydrazides were 5-hydroxypyrazolines, which underwent dehydration in the presence of pyridine and thionyl chloride in benzene, giving the respective 1,3,5-trisubstituted pyrazoles.

Synthesis and Characterization of a New Series of Arylidene Compounds from 2-Iminothiazolidine-4-one derivatives

The present work describes the synthesis and characterization of a new series of arylidene compounds from 2-iminothiazolidine -4-one which includes the preparation of   2-chloro-N-(4-(6-methyl benzo [d] thiazol-2-yl) phenyl) acetamide which was prepared through the reaction of 4-(6-methylbenzothiazole-2-yl) benzyl amine with chloroacetyl chloride in dry benzene to afford 2-chloro-N-(4-(6-methyl benzo [d] thiazol-2-yl)phenyl) acetamide . The later compound easily undergo cyclization reaction by potassium thiocyanate in dry acetone and results the formation of 2-imino-3-(4-(6-methylbenzo [d] thiazol-2-yl) phenyl) thiazolidin-4-one. After cyclization let react with different aromatic aldehydes to produce 5-benzylidene-2-imino-3-(4)6-methyl benzo [d]thiazol-2-yl) phenyl) thiazolidin-4-one . The FT-IR, 1H-NMR and 13C-NMR, 13C-DEPT-135, UV-Visible) spectra of the prepared compounds were confirmed the proposed structure, ultimately antimicrobial activity of the newly obtained compounds were tested against (Staphylococcus aureus ) (+ ve) , (Pseudomonas aeruginosa ) (-ve) and the results showed that most of the prepared compounds are sensitive against both types of test organisms in different activities.

S-Methyl diethylthiophosphinate in mono- and di(dechloromethylthioylation) of substituted benzylidene chlorides

The main route of a new reaction of (dichloromethyl)arenes with S-methyl diethylthiophosphinate is the attack of the thiol sulfur atom (P–SMe) on the methylene carbon atom. A new method for synthesizing dimethyl dithioacetals of arenecarbaldehydes without using highly toxic methanethiol was developed. The suggested approach involves di(dechloromethylthioylation) of the dichloromethyl group of (dichloromethyl)arenes with S-methyl diethylthiophosphinate at a reagent ratio of 1: 2.

Synthetic Studies toward Bazzanin K: Regioselective and Chemoselective Three-Component Suzuki Coupling.

The terphenyl substructure of the chiral cyclophane natural product bazzanin K was constructed. The key step involved sequential Suzuki couplings of a nonsymmetric dibromobenzene, which can be performed as a two-step process or as a one-pot three-component coupling. The key step represented a regioselective coupling of a dibromobenzene, as well as a chemoselective coupling of phenyl bromides in the presence of phenyl chlorides. Terphenyl intermediates displayed atropdiastereoisomerism, and they were converted to a single phenanthrene target by way of ring-closing metathesis.

Pd-KIT-6: synthesis of a novel three-dimensional mesoporous catalyst and studies on its enhanced catalytic applications

Synthesis of a novel three-dimensional mesoporous Pd-KIT-6 is carried out by a room temperature sol–gel method. The synthesised material is well crystalline observed from the Small angle powder X-ray diffraction. Calcination at 550 °C for 8 h retains the structure. The particle sizes are in the micron range. Si/Pd ratio of the as-synthesized material is found to be 45 against the input ratio 100. Transmission electron micrograph reveals the presence of the porous hexagonal structure. Thermogravimetric studies reveal that the KIT-6 (Korea Advanced Institute of Science and Technology number 6) undergo less weight-loss compared to Pd-KIT-6, which indicates the material is more crystalline than its metal-free counterpart due to the enhanced crystallisation rate. These results also supported by BET-surface area and Transmission electron microscopic picture. The 960 cm−1 band at Fourier transform Infrared spectroscopic analysis shows that the incorporation of Pd in the framework. These FT-IR results also supported by Raman Spectroscopic analysis. Electron spin resonance spectroscopic analysis shows that the Palladium is present in the +2 oxidation state in as-synthesized samples. Diffused reflectance Ultraviolet–Visible spectroscopic results show that Palladium is in tetrahedral coordination. Microwave irradiated Suzuki–Miyaura (SM) cross-coupling reactions studied by using the Pd-KIT-6 catalyst in detail without any organic solvent at 100 °C for 10 min. The reaction carried out in the presence of phenyl iodide, phenylboronic (PhB(OH)2), and K2CO3 produce biphenyl, with 98% yield. Change of halide to Phenyl bromide gave similar results, but Phenyl chloride gave lesser conversion (20%). It is due to the electronegativity difference between the halides. A plausible reaction mechanism is also proposed.