84553-20-8

Upstream product

• 766-83-6 m-chlorophenylacetylene 
• 64-19-7 acetic acid 
• 99-02-5 3'-Chloroacetophenone 
• 79-43-6 dichloro-acetic acid 
• 1128-76-3 3-chloro-benzoic acid ethyl ester 
• 75175-79-0 1-(3-chlorophenyl)-3-dimethylamino-prop-2-en-1-one 
• 535-80-8 3-chlorobenzoate 
• 21667-62-9 3-chlorobenzoylacetonitrile 
• 100246-30-8 α-(3-Chlorobenzoyl)acetamide 

Downstream Products

• 27683-61-0 1-(m-chlorophenyl)-2,2-dichloroethanol 
• 1588766-75-9 (R)-2,2-dichloro-1-(3-chlorophenyl)ethanol 
• 1588766-81-7 (S)-2,2-dichloro-1-(3-chlorophenyl)ethanol 
• 82082-49-3 N-benzyl-(3-chloro)benzamide 
• 13208-27-0 1-benzyl-3-(3-chlorophenyl)urea 
• 50625-49-5 m-Chlorobenzoyl azide 
• 27993-83-5 2-(3-chlorophenyl)quinoxaline 
• 73805-21-7 trans-β-chloro-m-chlorostyrene oxide 

Relevant academic research and scientific papers

Method for preparing alpha,alpha-dichloroketone under solvent-free condition

The invention provides a method for synthesizing an alpha,alpha-dichloroketone compound by taking methyl ketone and sulfonyl chloride as raw materials. The method comprises the following steps: heating a reaction mixture of methyl ketone and sulfonyl chloride to 80 DEG C under a dry air condition, stirring for 4-8 hours, after the reaction is finished, removing sulfonyl chloride from the obtained mixture, and carrying out silica gel column chromatography separation by taking ethyl acetate-hexane as an eluent to obtain the alpha,alpha-dichloroketone compound. The synthesis method provided by the invention has the advantages of extremely high chemical reactivity and selectivity, simple and easily available raw materials, low price, simple operation, no need of any catalyst and solvent, reduction of the synthesis cost and the pollution of organic solvents to the environment, greenness, economy and the like.

Solvent-free preparation of α,α-dichloroketones with sulfuryl chloride

An efficient and facile method is reported for the synthesis of a series of α,α-dichloroketones. The direct dichlorination of methyl ketones and 1,3-dicarbonyls using an excess amount of sulfuryl chloride affords the corresponding gem-dichloro compounds in moderate to excellent yields. Moreover, the protocol features high yields, broad substrate scope, and simple reaction conditions without using any catalysts and solvents.

Electrochemical synthesis of α,α-dihaloacetophenones from terminal alkyne derivatives

By virtue of electrochemistry, a series of α,α-dihaloacetophenones were easily obtained with good to excellent yields. This electrochemical procedure was taken in a divided cell with constant current in aqueous media. The reaction can be carried out smoothly at room temperature under metal and oxidant free condition, which provides an eco-friendly synthesis for the α,α-dihaloacetophenone derivatives.

Electrochemical Oxidative Oxydihalogenation of Alkynes for the Synthesis of α,α-Dihaloketones

An electrochemical oxydihalogenation of alkynes has been developed for the first time. Using this sustainable protocol, a variety of α,α-dihaloketones can be prepared with readily available CHCl3, CH2Cl2, ClCH2CH2Cl, and CH2Br2 as the halogen source under electrochemical conditions at room temperature.

Switchable Synthesis of α,α-Dihalomethyl and α,α,α-Trihalomethyl Ketones by Metal-Free Decomposition of Enaminone C=C Double Bond

The novel free radical-based cleavage of the enaminone C=C double bond is realized by using N-halosuccinimides (NXS) in the presence of benzoyl peroxide (BPO) with mild heating, enabling the tunable synthesis of α,α-dihalomethyl ketones and α,α,α-trihalomethyl ketones under different reaction conditions. The formation of these divergent products involving featured C=C double bond cleavage requires no any metal reagent, and represents one more practical example on the synthesis of poly halogenated methyl ketones via the functionalization of carbon?carbon bond. (Figure presented.).

Visible-light-promoted oxidative halogenation of alkynes

In nature, halogenation promotes the biological activity of secondary metabolites, especially geminal dihalogenation. Related natural molecules have been studied for decades. In recent years, their diversified vital activities have been explored for treating various diseases, which call for efficient and divergent synthetic strategies to facilitate drug discovery. Here we report a catalyst-free oxidative halogenation achieved under ambient conditions (halide ion, air, water, visible light, room temperature, and normal pressure). Constitutionally, electron transfer between the oxygen and halide ion is shuttled via simple conjugated molecules, in which phenylacetylene works as both reactant and catalyst. Synthetically, it provides a highly compatible late-stage transformation strategy to build up dihaloacetophenones (DHAPs).

Mild Homologation of Esters through Continuous Flow Chloroacetate Claisen Reactions

The selective chloromethylenation of functionalized esters using chloroacetic acid (CA) and LiHMDS (HMDS=hexamethyldisilazide) in a continuous-flow setup is reported. This Claisen homologation is for the first time extended to bis-chloromethylenation using dichloroacetic acid (DCA), thus giving access to under-explored α,α′-bis-chloroketones. The use of flow conditions enables efficient generation and reaction of the unstable chloroacetate dianion intermediates, leading to unprecedented mild and scalable reaction conditions at an economical reagent stoichiometry (?10 °C, 1 min, 1.0–2.4 equiv dianion). The clean reaction profiles allow subsequent use of the unpurified crude products, which is demonstrated in the synthesis of various heterocycles of broad interest. Furthermore, we report a novel, catalyst-free substitution of the obtained monochloro ketone products with (hetero)aryl zinc enolates to give valuable 1,4-diketones.

Dichloroacetophenones targeting at pyruvate dehydrogenase kinase 1 with improved selectivity and antiproliferative activity: Synthesis and structure-activity relationships

Dichloroacetophenone is a pyruvate dehydrogenase kinase 1 (PDK1) inhibitor with suboptimal kinase selectivity. Herein, we report the synthesis and biological evaluation of a series of novel dichloroacetophenones. Structure-activity relationship analyses (SARs) enabled us to identify three potent compounds, namely 54, 55, and 64, which inhibited PDK1 function, activated pyruvate dehydrogenase complex, and reduced the proliferation of NCI-H1975 cells. Mitochondrial bioenergetics assay suggested that 54, 55, and 64 enhanced the oxidative phosphorylation in cancer cells, which might contribute to the observed anti-proliferation effects. Collectively, these results suggested that 54, 55, and 64 could be promising compounds for the development of potent PDK1 inhibitors.

Pathways in the Degradation of Geminal Diazides

The degradation of geminal diazides is described. We show that diazido acetates are converted into tetrazoles through the treatment with bases. The reaction of dichloro ketones with azide anions provides acyl azides, through in situ formation of diazido ketones. We present experimental and theoretical evidence that both fragmentations may involve the generation of acyl cyanide intermediates. The controlled degradation of terminal alkynes into amides (by loss of one carbon) or ureas (by loss of two carbons) is also shown.

Method for removal of methanamide by dichlorination

A method for removal of methanamide by dichlorination is disclosed, according to the method, a finished product is obtained by removal of methanamide by dichlorination by one-step-reaction of various beta-carbonyl amide derivatives as raw materials, 2,2,6,6-Tetramethylpiperidinooxy (TEMPO) and an alkali as additives and N-chlorosuccinimide as a reagent in a reaction solvent, and then concentration and purification. According to the method, synthesis of an alpha-dichloroacetophenone derivative can be realized for the first time by a method of removal of methanamide by fracturation of carbon-carbon single bond. The method is novel and unique, has certain universality, is mild in reaction conditions, low in requirement of production equipment, and simple in technology, has the advantages of high efficiency, simple operation, high safety, economy and environmentally-friendliness; high-quality diverse alpha-dichloroacetophenone derivative products can be prepared by the method, and the products prepared by the method are important drug synthesis intermediates and material intermediates, can be widely used in the synthesis of heterocycles, unsaturated acids, acetylene alcohols and other compounds and cyclopropanation, and have wide market prospects.