16208-23-4

Upstream product

• 100-19-6 (4-nitrophenyl)ethanone 
• 79-43-6 dichloro-acetic acid 
• 619-50-1 4-nitrobenzoic acid methyl ester 
• 68760-11-2 1-(4-nitrophenyl)-3-N,N-dimethylamino-2-propen-1-one 
• 75-09-2 dichloromethane 
• 52898-51-8 N-methoxy-N-methyl-4-nitrobenzamide 
• 3156-41-0 1-nitro-4-(2-nitrovinyl)benzene 
• 937-31-5 (4-Nitrophenyl)acetylene 
• 62-23-7 4-nitro-benzoic acid 
• 99-77-4 ethyl 4-nitrobenzoate 
• 3383-43-5 (4-Nitrobenzoyl)acetonitrile 
• 90417-69-9 3-(4-nitro-phenyl)-3-oxo-propionic acid amide 
• 36458-78-3 α,α,α-trichloro-4-nitroacetophenone 
• 54075-25-1 4-nitro-α-(trichloromethyl)benzyl alcohol 

Downstream Products

• 1588766-87-3 C₈H₇Cl₂NO₃ 
• 1588766-92-0 C₈H₇Cl₂NO₃ 
• 73805-22-8 trans-β-chloro-p-nitrostyrene oxide 
• 201206-07-7 (Z)-2,2-Dichloro-1-(4-nitrophenyl)ethanone oxime 
• 35996-51-1 1-(p-nitrophenyl)-2,2-dichloroethanol 

Relevant academic research and scientific papers

Access to α,α-dihaloacetophenones through anodic C[dbnd]C bond cleavage in enaminones

We have developed a method to synthesize α,α-dihaloketones under electrochemical conditions. In this reaction, the Cl- or Br- is oxidized to Cl2 or Br2 at the anode, which undergoes two-step addition reactions with the N,N-dimethyl enaminone, and finally breaks C[dbnd]C of the N,N-dimethyl enaminone to generate α,α-dihaloketones. The electrosynthesis reaction can be conveniently carried out in an undivided electrolytic cell at room temperature. In addition, various functional groups are compatible with this green protocol which can be applied simultaneously to the gram scale without significantly lower yield.

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.

Modular and Chemoselective Strategy for Accessing (Distinct) α,α-Dihaloketones from Weinreb Amides and Dihalomethyllithiums

The selective transfer of diversely functionalized dihalomethyllithiums (LiCHBrCl, LiCHClI, LiCHBrI, LiCHCl2, LiCHBr2, LiCHFI) to Weinreb amides for preparing gem-dihaloketones in one synthetic operation is reported. The capability of these amides as acylating agents and, the wide availability of dihalomethanes as pronucleophiles, enable a straightforward route to the title compounds under full chemocontrol. No racemization phenomena were evidenced in the case of optically active materials. Additionally, tolerance to sensitive functional groups (esters, amides, halogens, olefins etc.) was uniformly noticed, thus making this conceptually intuitive strategy flexible and tunable by the operator. (Figure presented.).

Method for preparing alpha,alpha-dihalogenated acetophenone compound

The invention belongs to the technical field of organic synthesis and in particular relates to a method for preparing an alpha,alpha-dihalogenated acetophenone compound. The preparation method provided by the invention comprises the following steps: in an alcohol solvent, enabling nitroalkenes, electrophilic halogen reagents and sodium hydride to react at 55-65 DEG C under a heating condition for5-10 hours, cooling the components to the room temperature, adding a diluted acid solution, and performing continue stirring for 2-5 hours, so as to obtain a target compound, namely alpha,alpha-dihalogenated acetophenone. The method for preparing the alpha,alpha-dihalogenated acetophenone compound, which is provided by the invention, is simple and efficient, mild in condition, easy in raw materialobtaining, green and environment-friendly and simple and convenient to operate, and as a synthesis intermediate, the obtained alpha,alpha-dihalogenated acetophenone compound has the potential of being widely used in fields such as medicine chemical engineering.

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.

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.

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.

Micelle-Enabled Photoassisted Selective Oxyhalogenation of Alkynes in Water under Mild Conditions

Using micelles of FI-750-M, visible light, photocatalysts, and inexpensive halogenating reagents, such as N-bromosuccinimide and N-chlorosuccinimde, selective oxyhalogenations of alkynes were achieved in water under very mild conditions. No halogenation at the aromatic rings was detected, and control experiments revealed the radical pathway. The easily conducted protocol exhibited high reproducibility, was readily adjusted to gram scale, and allowed for recycling of reaction medium and catalyst.