99-02-5

Usage

Uses

Used in Pharmaceutical Industry:
3'-Chloroacetophenone is used as a key raw material for the synthesis of carbamazepine, an anticonvulsant drug used in the treatment of epilepsy. Its role in the synthesis process is crucial for producing an effective medication that helps manage seizure disorders.
Used in Fine Chemicals and Pesticides:
3'-Chloroacetophenone also serves as an intermediate in the production of various fine chemicals and pesticides. Its chemical properties make it a valuable component in the development of these products, contributing to their efficacy and performance in their respective applications.

Synthesis Reference(s)

The Journal of Organic Chemistry, 60, p. 2361, 1995 DOI: 10.1021/jo00113a013

Upstream product

• 620-16-6 3-chloroethylbenzene 
• 1712-71-6 3-chloro-α-methylstyrene 
• 2892-29-7 3-chloro-4-hydroxy-acetophenone 
• 120121-01-9 1-(m-Chlorophenyl)ethanol 
• 15946-37-9 sodium 3-chlorobenzenesulfinate 
• 75-05-8 acetonitrile 
• 2888-06-4 3-chlorophenylsulfonyl chloride 
• 78-94-4 methyl vinyl ketone 
• 126-99-8 chloroprene 
• 1866-38-2 m-Chlorocinnamic acid 
• 2550-26-7 4-Phenyl-2-butanone 
• 63503-60-6 3-chlorophenylboronic acid 
• 456-39-3 3-chlorobenzenediazonium tetrafluoroborate 
• 431-03-8 dimethylglyoxal 

Downstream Products

• 107027-40-7 2-(3-Chloro-phenyl)-8-methyl-quinoline-4-carboxylic acid 
• 75175-79-0 1-(3-chlorophenyl)-3-dimethylamino-prop-2-en-1-one 
• 56915-80-1 1-[3-(4-methylpiperazin-1-yl)phenyl]ethanone 
• 235789-20-5 (Z)-4-(3-Chloro-phenyl)-2-hydroxy-4-oxo-but-2-enoic acid methyl ester 
• 3391-10-4 (S)-1-(4-Chlorophenyl)ethanol 
• 120121-01-9 (R)-1-(3-chlorophenyl)-ethanol 
• 13422-80-5 3-(3-chlorophenyl)-3-oxopropanoic acid 
• 913829-94-4 (E)-N-(1-(3-chlorophenyl)ethylidene)benzenamine 
• 43045-12-1 1-(3-chlorophenyl)-2-thiocyanatoethan-1-one 
• 57961-48-5 ethyl 4-(3-chlorophenyl)-2,4-dioxobutanoate 
• 30011-90-6 2-(3'-chlorophenyl)-2-butene 
• 120121-01-9 1-(m-Chlorophenyl)ethanol 

Relevant academic research and scientific papers

Selective Activation of Unstrained C(O)-C Bond in Ketone Suzuki-Miyaura Coupling Reaction Enabled by Hydride-Transfer Strategy

A Rh(I)-catalyzed ketone Suzuki-Miyaura coupling reaction of benzylacetone with arylboronic acid is developed. Selective C(O)-C bond activation, which employs aminopyridine as a temporary directing group and ethyl vinyl ketone as a hydride acceptor, occurs on the alkyl chain containing a β-position hydrogen. A series of acetophenone products were obtained in yields up to 75%.

V2O5@TiO2 Catalyzed Green and Selective Oxidation of Alcohols, Alkylbenzenes and Styrenes to Carbonyls

The versatile application of different functional groups such as alcohols (1° and 2°), alkyl arenes, and (aryl)olefins to construct carbon-oxygen bond via oxidation is an area of intense research. Here, we report a reusable heterogeneous V2O5@TiO2 catalyzed selective oxidation of various functionalities utilizing different mild and eco-compatible oxidants under greener reaction conditions. The method was successfully applied for the alcohol oxidation, oxidative scission of styrenes, and benzylic C?H oxidation to their corresponding aldehydes and ketones. The utilization of mild and eco-friendly oxidizing reagents such as K2S2O8, H2O2 (30 % aq.), TBHP (70 % aq.), broad substrate scope, gram-scale synthesis, and catalyst recyclability are notable features of the developed protocol.

Ruthenium(II) Complexes Bearing Schiff Base Ligands for Efficient Acceptorless Dehydrogenation of Secondary Alcohols?

Four ruthenium(II) complexes 1—4 [RN=CH-(2,4-(tBu)2C6H2O)]RuH(PPh3)2(CO) (R = C6H5, 1; R = 4-MeC6H4, 2; R = 4-ClC6H4, 3; R = 4-BrC6H4, 4) bearing Schiff base ligands were prepared by treating RuHClCO(PPh3)3 with RN=CH-(2,4-(tBu)2C6H2OH (L1—L4) in the presence of triethylamine. Their structures were fully characterized by elemental analysis, IR, NMR spectroscopy and X-ray crystallography. These Ru(II) complexes exhibit high catalytic performance and good functional-group compatibility in the acceptorless dehydrogenation of secondary alcohols, affording the corresponding ketones in 82%—94% yields.

o-Quinone methide with overcrowded olefin component as a dehydridation catalyst under aerobic photoirradiation conditions

Ano-quinone methide (o-QM) featuring an overcrowded olefinic framework is introduced, which exhibits dehydridation activity owing to its enhanced zwitterionic character, particularly through photoexcitation. The characteristics of thiso-QM enable the operation of dehydridative catalysis in the oxidation of benzylic secondary alcohols under aerobic photoirradiation conditions. An experimental analysis and density functional theory calculations provide mechanistic insights; the ground-state zwitterionic intermediate abstracts a hydride and proton simultaneously, and the active oxygen species facilitate catalyst regeneration.

Merging N-Hydroxyphthalimide into Metal-Organic Frameworks for Highly Efficient and Environmentally Benign Aerobic Oxidation

Two highly efficient metal-organic framework catalysts TJU-68-NHPI and TJU-68-NDHPI have been successfully synthesized through solvothermal reactions of which the frameworks are merged with N-hydroxyphthalimide (NHPI) units, resulting in the decoration of pore surfaces with highly active nitroxyl catalytic sites. When t-butyl nitrite (TBN) is used as co-catalyst, the as-synthesized MOFs are demonstrated to be highly efficient and recyclable catalysts for a novel three-phase heterogeneous oxidation of activated C?H bond of primary and secondary alcohols, and benzyl compounds under mild conditions. Based on the high efficiency and selectivity, an environmentally benign system with good sustainability, mild conditions, simple work-up procedure has been established for practical oxidation of a wide range of substrates.

Preparation of trinuclear ruthenium clusters based on piconol ligands and their application in Oppenauer-type oxidation of secondary alcohols

Treatment of Ru3(CO)12 with one equivalent of 2-indolyl-6-pyridinyl-alcohol ligands 2-(C8H6N)-6-(CR1R2OH)C5H3N (R1 = R2 = Me (L1H); R1 = R2 = C2H5 (L2H); R1, R2 = ?(CH2)4- (L3H);& R1, R2 = ?(CH2)5- (L4H)) in refluxing THF afforded the corresponding trinuclear ruthenium clusters L(μ2-H)Ru3(CO)9 (1a–1d), respectively. All the novel Ru complexes were well characterized by NMR, elemental analyses and IR spectra. Structures of complexes 1a, 1c, and 1d were further determined by X-ray crystallographic studies. Complexes 1a–1d were applied to catalytic Oppenauer-type oxidation of secondary alcohols with acetone as oxidant, and complex 1a was found to be the most efficient catalyst.

Ru(iii) -based polyoxometalate tetramers as highly efficient heterogeneous catalysts for alcohol oxidation reactions at room temperature

A novel ruthenium-containing polyoxometalate-based organic-inorganic hybrid, K4Na9H7.4[(AsW9O33)4(WO2)4{Ru3.2(C3H3N2)2}]·42H2O (1), was successfully synthesized by a one-step hydrothermal method under acidic conditions, which applied a self-assembly strategy between inorganic polyoxometalate based on trivacant [B-α-AsW9O33]9?{AsW9} fragments and an organic ligand, imidazole (C3H4N2). Compound1was further characterized by single-crystal X-ray diffraction, PXRD, IR spectroscopy, UV-Vis spectroscopy, ESI-MS, elemental analysis and TGA. Single-crystal X-ray diffraction data reveal that the polyanion consists of four trivacant Keggin-type polyanion {AsW9} building blocks bridged by four {WO6} units, leading to a crown-shaped tetrameric structure [(AsW9O33)4(WO2)4{Ru3.2(C3H3N2)2}]20.4?. The ESI-MS result reveals that the polyanion unit has excellent structural integrity in water. Moreover, the catalysis study of1was also further investigated, and the experimental results indicate heterogeneous catalyst1presents high efficiency (yield = 98%), excellent selectivity (>99%), and good recyclability for the oxidation of 1-(4-chlorophenyl)ethanol to 4′-chloroacetophenone with commercially available 70% aqueoustert-butyl hydroperoxide {TBHP (aq.)} as the oxidant at room temperature.

Iron-catalyzed domino decarboxylation-oxidation of α,β-unsaturated carboxylic acids enabled aldehyde C-H methylation

A practical and general iron-catalyzed domino decarboxylation-oxidation of α,β-unsaturated carboxylic acids enabling aldehyde C-H methylation for the synthesis of methyl ketones has been developed. This mild, operationally simple method uses ambient air as the sole oxidant and tolerates sensitive functional groups for the late-stage functionalization of complex natural-product-derived and polyfunctionalized molecules.

Organotellurium-catalyzed oxidative deoximation reactions using visible-light as the precise driving energy

Irradiated by visible light, the recyclable (PhTe)2-catalyzed oxidative deoximation reaction could occur under mild conditions. In comparison with the thermo reaction, the method employed reduced catalyst loading (1 mol% vs. 2.5 mol%), but afforded elevated product yields with expanded substrate scope. This work demonstrated that for the organotellurium-catalyzed reactions, visible light might be an even more precise driving energy than heating because it could break the Te–Te bond accurately to generate the active free radical catalytic intermediates without damaging the fragile substituents (e.g., heterocycles) of substrates. The use of O2 instead of explosive H2O2 as oxidant affords safer reaction conditions from the large-scale application viewpoint.

Photoinduced Acetylation of Anilines under Aqueous and Catalyst-Free Conditions

A green and efficient visible-light induced functionalization of anilines under mild conditions has been reported. Utilizing nontoxic, cost-effective, and water-soluble diacetyl as photosensitizer and acetylating reagent, and water as the solvent, a variety of anilines were converted into the corresponding aryl ketones, iodides, and bromides. With advantages of environmentally friendly conditions, simple operation, broad substrate scope, and functional group tolerance, this reaction represents a valuable method in organic synthesis.