14737-97-4

Upstream product

• 4519-49-7 2-Bromo-2-chloro-3-(4-chloro-phenyl)-propionic acid methyl ester 
• 104-88-1 4-chlorobenzaldehyde 
• 21204-67-1 methyl (triphenylphosphoranylidene)acetate 
• 42175-03-1 methyl (E)-3-(3-chlorophenyl)prop-2-enoate 
• 598-99-2 Methyl trichloroacetate 
• 133474-01-8 1-(4-chlorophenyl)-2,3,3-trichloro-1-oxopropene 
• 106-47-8 4-chloro-aniline 
• 1552-77-8 methyl α,α-dichloro-β-(4-chlorophenyl)propionate 

Downstream Products

• 1376212-91-7 (Z)-methyl 4-chloro-5-(4-chlorophenyl)-3-hydroxypent-4-enoate 
• 105072-49-9 (E)-2-chloro-3-(4-chlorophenyl)acrylic acid 
• 1552-71-2 (Z)-2-chloro-3-(4-chlorophenyl)acrylic acid 
• 1376213-59-0 (Z)-methyl 4-chloro-5-(4-chlorophenyl)-3-oxopent-4-enoate 
• 88286-08-2 trans-2-(4-chlorophenyl)aziridine-3-carboxylic acid amide 

Relevant academic research and scientific papers

Ru-catalyzed highly chemo- and enantioselective hydrogenation of γ-halo-γ,δ-unsaturated-β-keto esters under neutral conditions

Finely-tuned ruthenium-catalyzed highly chemoselective and enantioselective hydrogenation of γ-halo-γ,δ-unsaturated-β-keto esters at the carbonyl group was achieved under neutral reaction conditions (ee up to 97%). Both olefin and alkenyl halogen moieties, which are labile under hydrogenation conditions, remained untouched during the reaction.

A novel and convenient protocol for synthesis of a-haloacrylates

A novel and convenient protocol for synthesis of a-haloacrylates starting from phosphonium ylide and aldedyde or alcohol was described. Halodimethylsulfonium halide was used for the first time in halogenation of phosphonium ylide. Good yield as well as a

Addition of α-halocarboxylic acid esters to para-substituted benzaldehydes in the presence of pentacarbonyliron

Pentacarbonyliron promotes addition of α-halocarboxylic acid esters at the carbonyl group of benzaldehyde and its para-substituted analogs. The substituent in the benzene ring strongly affects the process.

Synthesis of α-Halocinnamate Esters via Solvolytic Rearrangement of Trichloroallyl Alcohols

Aryl trichlorovinyl ketones undergo regioselective reduction to the corresponding carbinols with sodium borohydride in alcoholic solvents and are transformed to the (Z)-α-chlorocinnamate ester derivatives via an acid-catalyzed allylic rearrangement.Micharl addition of ammonia to these ester derivatives affords cis- and/or trans-aziridine amides.The facile rearrangement allows the synthesis of d,l-phenylalanine derived from perchloroethylene and toluene.

Reactions of α,β-Unsaturated Carboxylates, Malonates and Phenylacetates with Manganese(III) Acetate in the Presence of Chloride Ions

The reaction of alkyl (E)-3-phenylpropenoates with manganese(III) acetate of Cl- ions gave alkyl (Z)-2-chloro-3-phenylpropenoates and alkyl 2,3-dichloro-3-phenylpropenoates.Ethyl (E)-2,3-diphenylpropenoate yielded ethyl 2,3-dichloro-2,3-diphenylpropanoate.Alkyl 3,3-diphenylpropenoates gave mainly alkyl 2-chloro-3,3-diphenylpropenoates.Ethyl 1-cyclohexenecarboxylate gave ethyl 1,2-dichlorocyclohexanecarboxylate.Dimethyl malonate yielded dimethyl dichloromalonate and tetramethyl 1,2-dichloro-1,1,2,2-ethanetetracarboxylate.Substituted malonates resulted in α-chloro derivatives.Methyl phenylacetates gave α-acetoxy derivatives.

Mechanism of Dehydroacetoxylation of Methyl 3-Acetoxy-3-aryl-2-halogenopropanoates

The rate of sodium methoxide-induced dehydroacetoxylation of the diesters p-RC6H4CH(OAc)CXHCO2Me (X= Br or Cl) has been studied as a function of the para-substituent.The results correspond to the para-substituent effects expected for proton abstraction from C-2, as estimated from the diastereoisomerisation of model compounds under similar conditions.This suggests that the elimination occurs via a carbanion mechanism, with C(2)-H bond-breaking rate-determining.The apparent insensitivity of the kinetic behaviour to configuration differences, together with the response of the reactions to the effect of the 3-substituent, is interpreted in terms of inductive stabilisation by the 2-halogen atom, which tends to localise the incipient negative charge at C-2, inhibiting distortion of its tetrahedral geometry.