1126-46-1

Basic information

• Product Name: METHYL 4-CHLOROBENZOATE
• Synonyms: 4-Chlorobenzoic acid methyl;Methyl 4-chlorobenzoate,97%;METHYL 4-CHLOROBENZO;Chlorophenyl Methyl;4-(Methoxycarbonyl)chlorobenzene;Benzoic acid, p-chloro-, Methyl ester (6CI,7CI,8CI);NSC 8366;Methyl 4-chlorobenzoate 99%
• CAS NO: 1126-46-1
• Molecular Formula: C₈H₇ClO₂
• Molecular Weight: 170.59
• EINECS: 214-420-9
• Product Categories: blocks;Carboxes;Aromatic Esters;Benzoic acid;Acids & Esters;Chlorine Compounds;C8 to C9;Carbonyl Compounds;Esters
• Mol File: 1126-46-1.mol
• Article Data: 348

Chemical Properties

• Melting Point: 42-44 °C(lit.)
• Boiling Point: 136-137°C 10mm
• Flash Point: 224 °F
• Appearance: colourless to white crystals
• Density: 1,382 g/cm3
• Vapor Pressure: 0.12mmHg at 25°C
• Refractive Index: 1.5800 (estimate)
• Storage Temp.: 0-10°C
• Solubility: Chloroform (Slightly), Methanol (Slightly)
• Merck: 14,2125
• BRN: 1564310
• CAS DataBase Reference: METHYL 4-CHLOROBENZOATE(CAS DataBase Reference)
• NIST Chemistry Reference: METHYL 4-CHLOROBENZOATE(1126-46-1)
• EPA Substance Registry System: METHYL 4-CHLOROBENZOATE(1126-46-1)

Safety Data

• Statements: 36/37/38
• Safety Statements: 24/25
• WGK Germany: 3
• TSCA: Yes
• HazardClass: IRRITANT
• Hazardous Substances Data: 1126-46-1(Hazardous Substances Data)

Usage

Chemical Properties

COLOURLESS TO WHITE CRYSTALS

Uses

Methyl 4-chlorobenzoate was used in quantitative determination of chlorophenoxyisobutyrate (CPIB) and salicylic acid, the metabolites of clofibrate and aspirin, by GC-MS method.

Synthesis Reference(s)

Synthesis, p. 790, 1981 DOI: 10.1055/s-1981-29595

General Description

Methyl 4-chlorobenzoate undergoes room temperature Pd-mediated hydrodehalogenation with KF and polymethylhydrosiloxane (PMHS) to yield methyl benzoate. It undergoes Suzuki-Miyaura coupling reaction with phenylboronic acid in the presence of bis-carbene palladium complex catalyst to yield methyl-(4-phenyl)-benzoate.

InChI:InChI=1/C8H7ClO2/c1-11-8(10)6-2-4-7(9)5-3-6/h2-5H,1H3

Upstream product

• 67-56-1 methanol 
• 74-11-3 para-chlorobenzoic acid 
• 39561-82-5 4-chlorophenacyl acetate 
• 874-59-9 4-chlorobenzoyl bromide 
• 40137-41-5 p-Chloracetophenonhydrazon 
• 13014-48-7 4-chlorobenzoyl cyanide 
• 104-88-1 4-chlorobenzaldehyde 
• 18362-49-7 1,3-bis(4-chlorophenyl)propane-1,3-dione 
• 106-39-8 bromochlorobenzene 
• 201230-82-2 carbon monoxide 
• 106-46-7 para-dichlorobenzene 
• 17287-03-5 trimethylsulphonium hydroxide 
• 74261-45-3 1-(4-chlorophenyl)-2-nitro-1-propanone 
• 18107-18-1 diazomethyl-trimethyl-silane 

Downstream Products

• 14719-83-6 methyl 3-nitro-4-chlorobenzoate 
• 1613-88-3 4-chloro-N-hydroxybenzamide 
• 152423-67-1 1-(4-Chloro-phenyl)-2,2,2-tris-methylsulfanyl-ethanone 
• 628-29-5 n-butyl methyl sulfide 
• 6156-25-8 tetrathioorthocarbonic acid tetramethyl ester 
• 171897-88-4 p-chlorophenyl di(methylthio)methyl ketone 
• 720-75-2 methyl 4-phenylbenzoate 
• 79-20-9 acetic acid methyl ester 
• 712-95-8 tert-butyl 4-chlorobenzoate 
• 25069-30-1 4-(diphenylamino)benzoic acid methyl ester 
• 99-75-2 4-methyl-benzoic acid methyl ester 
• 321-37-9 4'-chloro-2,2,2-trifluoroacetophenone 
• 107947-17-1 methyl 3-bromo-4-chlorobenzoate 
• 1129-35-7 4-cyanobenzoic acid methyl ester 

Relevant articles and documents

Synthesis and antiviral activity of novel thioether derivatives containing 1,3,4-oxadiazole/thiadiazole and emodin moieties

A series of novel thioether derivatives containing 1,3,4-oxadiazole/thiadiazole and emodin moieties were designed and synthesized. The structures of the target compounds were confirmed by 1H NMR, 13C NMR, Infrared, and elemental analysis. The results of bioactivity analysis showed that most of the target compounds exhibited moderate to good antiviral activity against tobacco mosaic virus at a concentration of 500 mg/L. Especially, among the title compounds, Y2, Y8, and Y10 possessed appreciable curative activity in vivo, with inhibition rates of 50.51, 52.08, and 54.62%, respectively, which were similar to that of Ningnanmycin (53.40%).

N-Doped Sub-3 nm Co Nanoparticles as Highly Efficient and Durable Aerobic Oxidative Coupling Catalysts

A nano-coating associated with sulfuric acid leaching protocol was developed to prepare N-doped sub-3 nm Co-based nanoparticle catalyst (Co?N/C) using melamine–formaldehyde resin as the N-containing precursor, active carbon as the support, and Co(NO3)2 as the Co-containing precursor. By thermal treatment under nitrogen atmosphere at 800 °C and leached with sulfuric acid solution, a stable and highly dispersive Co?N coordination structure was uniformly dispersed on the formed Co?N/C catalyst with a Co loading of 0.47 wt % and Co nanoparticle size of 2.55 nm. The Co?N/C catalyst was characterized with XRD, XPS, Raman, SEM, TEM, ICP, and elemental analysis. The Co?N/C catalyst showed extremely high catalytic efficiency with a TON of 257 for the aerobic oxidative coupling of aldehydes with methanol to directly synthesize methyl esters with molecular oxygen as the final oxidant. The Co?N/C catalyst also showed broad substrate range and stable recyclability. After recycling for 7 times, no obvious deactivation was detected. It was confirmed that the sub-3 nm Co?N coordination structure formed between metallic Co nanoparticles and pyridinic nitrogen doping into graphitic layers functions as the active site to activate molecular oxygen for the β-H elimination from generated hemiacetal intermediates to produce methyl esters. The nano-coating associated with acid leaching protocol provides a novel strategy to prepare highly efficient non-precious metal-based catalysts.

Modified extra-large mesoporous silica supported Au-Ni as a highly efficient catalyst for oxidative coupling of aldehydes with methanol

Herein, we report for the first time that a La-Mg composite oxide modified extra-large mesoporous FDU-12 supported Au-Ni bimetallic catalyst exhibits excellent performance for oxidative coupling of aldehydes (including benzyl and aliphatic aldehydes) with methanol to directly produce methyl esters.

Design, synthesis, in silico molecular docking and biological evaluation of novel oxadiazole based thiazolidine-2,4-diones bis-heterocycles as PPAR-γ agonists

A library of novel 1,3,4-oxadiazole and 2-4-thiazolidinedione based bis-heterocycles 7 (a-r) has been synthesized which exhibited significant PPAR-?3 transactivation and blood glucose lowering effect comparable with the standard drugs Pioglitazone and Rosiglitazone. Compounds 7m and 7r did not cause body weight gain and were found to be free from hepatotoxic and cardiotoxic side effects. Compounds 7m and 7r increased PPAR-?3 gene expression by 2.10 and 2.00 folds, respectively in comparison to the standard drugs Pioglitazone (1.5 fold) and Rosiglitazone (1.0 fold). Therefore the compounds 7m and 7r may be considered as potential candidates for development of new antidiabetic agents.

Facile Coupling of Aldehydes with Alcohols: An Evolved Tishchenko Process for the Preparation of Unsymmetrical Esters

A facile coupling process between aldehydes and alcohols to afford unsymmetrical esters is presented herein. This transformation is complementary to the Tishchenko reaction and provides access to unsymmetrical esters under very mild conditions. Various aldehydes and alcohols are suitable in this reaction, and the addition of a sacrificial trifluoromethyl ketone allows the process to take place in a highly selective manner. A plausible mechanism based on details obtained by monitoring the reaction progress and deuterium-labeling studies has been proposed.

Activating cobalt nanoparticles via the Mott-Schottky effect in nitrogen-rich carbon shells for base-free aerobic oxidation of alcohols to esters

Heterogeneous catalysts of inexpensive and reusable transition-metal are attractive alternatives to homogeneous catalysts; the relatively low activity of transition-metal nanoparticles has become the main hurdle for their practical applications. Here, the de novo design of a Mott-Schotfky-type heterogeneous catalyst is reported to boost the activity of a transition-metal nanocatalyst through electron transfer at the metal/nitrogen-doped carbon interface. The Mott-Schottky catalyst of nitrogen-rich carbon-coated cobalt nanoparticles (Co@NC) was prepared through direct polycondensation of simple organic molecules and inorganic metal salts in the presence of g-C3N4 powder. The Co@NC with controllable nitrogen content and thus tunable Fermi energy and catalytic activity exhibited a high turnover frequency (TOF)value (8.12 mol methyl benzoate mol-1 Co h-1) for the direct, base-free, aerobic oxidation of benzyl alcohols to methyl benzoate; this TOF is 30-fold higher than those of the state-of-the-art transitionmetal-based nanocatalysts reported in the literature. The presented efficient Mott-Schottky catalyst can trigger the synthesis of a series of alkyl esters and even diesters in high yields.

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Controlled immobilization of Keggin-type heteropoly acids on the surface of silica encapsulated γ-Fe2O3 nanoparticles and investigation of catalytic activity in the oxidative esterification of arylaldehydes with methanol

Preparation, leaching and solid acidity measurements of H 3PW12O40, H3PMo12O 40 and H4SiW12O40 supported on silica-encapsulated γ-Fe2O3 nanoparticles were performed. The impregnating solvent and calcination temperature were optimized using various techniques. Catalytic activity of samples was examined by carrying out oxidative esterification of benzaldehyde with methanol under the same conditions. The acidity of the catalysts that was determined by NH 3-temperature-programmed desorption technique and chemisorption of pyridine. The best catalyst was characterized by Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy and laser particle size analyzer. Finally, a mild, simple and clean procedure was presented for the one-pot oxidative esterification of arylaldehydes with methanol using magnetically recoverable nanocatalyst and hydrogen peroxide as a green oxidant.

Cobalt single atoms anchored on nitrogen-doped porous carbon as an efficient catalyst for oxidation of silanes

The oxidation reactions of organic compounds are important transformations for the fine and bulk chemical industry. However, they usually involve the use of noble metal catalysts and suffer from toxic or environmental issues. Here, an efficient, environmentally friendly, and atomically dispersed Co catalyst (Co-N-C) was preparedviaa simple, porous MgO template and etching method using 1,10-phenanthroline as C and N sources, and CoCl2·6H2O as the metal source. The obtained Co-N-C catalyst exhibits excellent catalytic performance for the oxidation of silanes with 97% isolated yield of organosilanol under mild conditions (room temperature, H2O as an oxidant, 1.8 h), and good stability with 95% isolated yield after nine consecutive reactions. The turnover frequency (TOF) is as high as 381 h?1, exceeding those of most non-noble metal catalysts and some noble metal catalysts. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), extended X-ray absorption fine structure (EXAFS), and wavelet transform (WT) spectroscopy corroborate the existence of atomically dispersed Co. The coordination numbers of Co affected by the pyrolysis temperature in Co-N-C-700, Co-N-C-800, and Co-N-C-900 are 4.1, 3.6, and 2.2, respectively. Owing to a higher Co-N3content, Co-N-C-800 shows more outstanding catalytic performance than Co-N-C-700 and Co-N-C-800. Moreover, density functional theory (DFT) calculations reveal that the Co-N3structure exhibits more activity compared with Co-N4and Co-N2, which is because the Co atom in Co-N3was bound with both H atom and Si atom, and it induced the longest Si-H bond.

The effect of indium(III) triflate in oxone-mediated oxidative methyl esterification of aldehydes

An oxidative methyl esterification of aldehydes was effectively achieved. The trivalent indium reagent, indium(III) triflate, was revealed to accelerate the reactions in many cases. Aromatic aldehydes with various substituents were subjected to this method, and each produced the corresponding methyl esters in good to excellent yields within a relatively short reaction time.

One Pot Electrooxidative Conversion of Benzyl Type Alcohols into the Corresponding Methyl Carboxylates

One-pot conversion of several benzyl type alcohols into the corresponding methyl carboxylates was carried out by indirect electrooxidation using iodide ion as the electron carrier.

NaIO4/LiBr-mediated direct conversion of benzylic alcohols and aromatic aldehydes to aromatic esters

Aromatic aldehydes or benzylic alcohols are directly converted to the corresponding aromatic esters in high yields on treatment with methanol or ethanol mediated by sodium metaperiodate (NaIO4)/LiBr in an acidic medium. Copyright Taylor & Francis Group, LLC.

Aerobic oxidative esterification of benzyl alcohols with catalytic tetrabromomethane under visible light irradiation

We report a useful method for the facile synthesis of aromatic esters from benzyl alcohols with molecular oxygen and catalytic tetrabromomethane in alcohol under visible light irradiation with a fluorescent lamp. This is the first metal-free reaction using molecular oxygen as the terminal oxidant.

Direct oxidative esterification of alcohols and hydration of nitriles catalyzed by a reusable silver nanoparticle grafted onto mesoporous polymelamine formaldehyde (AgNPs@mPMF)

A nitrogen-rich mesoporous organic polymer was synthesized as a novel support. A silver nanoparticle was synthesized and grafted onto it. The prepared catalyst (AgNPs@mPMF) was characterized by powder X-ray diffraction (XRD), scanning electron microscopy(SEM) and energy dispersive X-ray spectrometry (EDS), thermogravimetric analysis (TGA), high-resolution transmission electron microscopy (HRTEM), UV-vis diffuse reflectance spectroscopy (DRS), N2 adsorption, Raman spectroscopy and EPR study. The catalytic activity was evaluated for the oxidative esterification reaction of alcohols and hydration of nitriles. The oxidative esterification reaction was carried out for various activated alcohols giving excellent yields of the corresponding ester products. The catalyst was also efficient in the hydration of nitriles. Both reactions were optimized by varying the bases, temperatures and solvents. The catalyst can be facilely recovered and reused six times without a significant decrease in its activity and selectivity.

The synergistic role of the support surface and Au-Cu alloys in a plasmonic Au-Cu?LDH photocatalyst for the oxidative esterification of benzyl alcohol with methanol

Layered double hydroxide-supported Au-Cu alloy nanoparticles (NPs) were found to be highly efficient catalysts for the oxidative esterification of benzyl alcohol with methanol in the presence of molecular oxygen under visible-light irradiation to prepare methyl benzoate. Here, we report that alloying small amounts of copper into gold nanoparticles can increase the ability to activate oxygen molecules to O2- radicals and display greater charge heterogeneity to promote the cleavage of the C-H bond of benzyl alcohol molecules by reinforcing the coordination of the intermediate with unsaturated metal active sites due to the LSPR effect of alloy NPs, which is the rate-limiting step of the reaction. Besides the Au-Cu alloy NPs, the support also played a pivotal role in the catalytic process. The support with the presence of acid-base pairs, in which the basic sites served as the reactant molecule adsorption sites to provoke the intermediate formation and the acidic sites promoted the recovery of the support surface, showed better performances by affecting the overall reaction rate completely. Moreover, applying this photocatalyst in the cross-esterification of aromatic alcohols and aliphatic alcohols displayed excellent yields.

PHOTOOXYDATION AND PHOTOOXYGENATION OF α-DIAZOKETONE IN ALCOHOL

The investigation of the mechanism of oxydative-cleavage reaction of azibenzil in alcohol to give benzoates revealed the role of oxygen (either 1O2 or 3O2) in the photolysis of α-diazoketone-

Potential tuberculostatic agents. Topliss application on benzoic acid [(5-nitro-thiophen-2-yl)-methylene]-hydrazide series.

Nitroaromatic compounds such as nifuroxazide are used in many human enteropathogenic bacteria infections without causing an increase in the plasmidial antibiotic resistance of the aerobic Gram-negative intestinal Enterobacteriaceae. For these reasons, these compounds have been synthesized using the rational approach of Topliss' decision tree. Generally, this approach allows us to obtain the most active derivative from the series in a few steps. These compounds were tested against Mycobacterium tuberculosis in vitro and the most active of the series identified. A new lead for potential tuberculostatic activity has been predicted and will be used in further QSAR studies.

Mechanistic investigation of the gold-catalyzed aerobic oxidation of aldehydes: Added insight from Hammett studies and isotopic labelling experiments

The gold-catalyzed aerobic oxidation of aldehydes proceeds through development of a partial negative charge and has a significant kinetic isotope effect (kH/kD = 2.8-2.9), which illustrates that activation of the C-H bond takes place in the rate-determining step. The Royal Society of Chemistry.

Design, synthesis, antibacterial evaluation, and computational studies of hybrid oxothiazolidin–1,2,4-triazole scaffolds

Bacterial infections are a serious threat to human health due to the development of resistance against the presently used antibiotics. The problem of growing and widespread antibiotic resistance is only getting worse with the shortage of new classes of antibiotics, creating a substantial unmet medical need in the treatment of serious bacterial infections. Therefore, in the present work, we report 18 novel hybrid thiazolidine–1,2,4-triazole derivatives as DNA gyrase inhibitors. The derivatives were synthesized by multistep organic synthesis and characterized by spectroscopic methods (1H and 13C nuclear magnetic resonance and mass spectroscopy). The derivatives were tested for DNA gyrase inhibition, and the result emphasized that the synthesized derivatives have a tendency to inhibit the function of DNA gyrase. Furthermore, the compounds were also tested for antibacterial activity against three Gram-positive (Bacillus subtilis [NCIM 2063], Bacillus cereus [NCIM 2156], Staphylococcus aureus [NCIM 2079]) and two Gram-negative (Escherichia coli [NCIM 2065], Proteus vulgaris [NCIM 2027]) bacteria. The derivatives showed a significant-to-moderate antibacterial activity with noticeable antibiofilm efficacy. Quantitative structure–activity relationship (QSAR), ADME (absorption, distribution, metabolism, elimination) calculation, molecular docking, radial distribution function, and 2D fingerprinting were also performed to elucidate fundamental structural fragments essential for their bioactivity. These studies suggest that the derivatives 10b and 10n have lead antibacterial properties with significant DNA gyrase inhibitory efficacy, and they can serve as a starting scaffold for the further development of new broad-spectrum antibacterial agents.

Microwave-assisted esterification of diverse carboxylic acids and chiral amino acids

A facile and efficient synthetic method of esters from their corresponding carboxylic acids and amino acids is described. The esterification reaction of carboxylic acids and amino acids could be greatly accelerated under microwave irradiation because the reactions described in this article took place in only 5 min with almost quantitative yields, and distinct acidity of catalytic acids was well tolerated. Unlike the racemation problem in microwave-assisted N-acylation reactions, the esters of chiral amino acids could be achieved with retention of configuration under this condition. Copyright Taylor & Francis Group, LLC.

Calcium and magnesium chlorides-catalyzed oxidative esterification of aromatic aldehydes

An interesting procedure for the oxidative esterification of aromatic aldehydes has been developed. By using catalytic amount of CaCl2 or MgCl2, various methyl benzoates were isolated in good yields with hydrogen peroxide as the terminal oxidant.

Efficient and practical approach to esters from acids/ 2-oxoacids/ 2-oxoaldehydes &/ 2-oxoesters

An efficient, mild, cost effective and practical method is presented for generation of esters (RCO2R′) from acids (RCO2H)/ 2-oxoacids (RCOCO2H)/ 2-oxoaldehydes (RCOCHO)/ 2-oxoesters (RCOCO2R″) and alcohols by using oxone as catalyst. In addition to deciphering the scope of our process, we propose a mechanism for esterification through a common intermediate IV. Reaction with 2-oxoacids and 2-oxoaldehydes proceed with initial CO-C cleavage followed by oxone mediated esterification with alcohols. In addition, reaction with 2-oxoesters proceeds through CO-CO bond cleavage and trans-esterification.

SOLVOLYSIS OF BENZOYL CYANIDES IN METHANOL-ACETONITRILE AND METHANOL-ACETONE MIXTURES.

Rate constants for solvolysis of benzoyl cyanides in methanol-acetonitrile and methanol-acetone mixtures were determined.Effects of substituent and solvent indicated that the reaction preceeds via an associative SN2 mechanism.

Multi-scale promoting effects of lead for palladium catalyzed aerobic oxidative coupling of methylacrolein with methanol

A highly efficient Pd2Pb8/alumina catalyst was prepared, which provided the highest turnover number (TON) of 302 for aerobic oxidative coupling of methylacrolein with methanol. The enhanced catalytic efficiency could be attributed to the multi-scale (micron, nano and atom scales) promoting effects of the pre-loaded Pb species. This journal is

Hexa-arm star shaped hydrazone derivatives from hexakis(4-formylphenoxy)- cyclotriphosphazene core

A series of novel hexasubstituted cyclophosphazene hydrazones [N 3P3(OC6H4pCHNNHC(O)C 6H4pX)6] (X = H, Br, Cl, F, OH, OCH 3, CH3, NO2, NH2) were prepared by a sixfold condensation reaction of [N3P3(OC 6H4pCHO)6] with para-substituted benzoic hydrazides [NH2NHC(O)C6H4pX] with excellent yields (91-98%). The structures of the compounds were confirmed by elemental analysis, FT-IR, 1H, 13C, 31P, 2D-HSQC NMR and mass spectrometry (MALDI-TOF). All the synthesized cyclophosphazene hydrazones exhibit high thermal stability. The crystal structure of a homogeneously substituted hexakis(4-formylphenoxy)-cyclotriphosphazene was determined by X-ray diffraction analysis. The compound crystallizes in the monoclinic system, space group P21/n with a = 16.558(3) , b = 10.250(2) , c = 23.429(5) , α = γ = 90.00°, β = 90.461(4)°, V = 3976.5(14) 3 and Z = 4. The R value is 0.0823 for 4290 observed reflections. The conformations of the 4-formylphenoxy-groups are different at the three phosphorus atoms.

Photochemical Sandmeyer-type Halogenation of Arenediazonium Salts

Trihalide salts were found to efficiently promote photochemical dediazotizing halogenations of diazonium salts. In contrast to classical Sandmeyer reactions, no metal catalysts are required to achieve high yields and outstanding selectivities for halogena

Antibacterial and Antiviral Activities of 1,3,4-Oxadiazole Thioether 4H-Chromen-4-one Derivatives

Various 1,3,4-oxadiazole thioether 4H-chromen-4-one derivatives were conceived. The title compounds demonstrated striking inhibitory effects againstXac,Psa, andXoo. EC50data exhibited that A8 (19.7 μg/mL) had better antibacterial activity againstXoothan myricetin, BT, and TC. Simultaneously, the mechanism of action of A8 had been verified by SEM. The results of anti-tobacco mosaic virus indicated that A9 had the bestin vivoantiviral effect compared with ningnanmycin. From the data of MST, it could be seen that A9 (0.003 ± 0.001 μmol/L) exhibited a strong binding capacity, which was far superior to ningnanmycin (2.726 ± 1.301 μmol/L). This study shows that the 1,3,4-oxadiazole thioether 4H-chromen-4-one derivatives may become agricultural drugs with great potential.