66051-36-3

Upstream product

• 623-73-4 diazoacetic acid ethyl ester 
• 98-87-3 benzylidene dichloride 
• 64-17-5 ethanol 
• 705-54-4 (Z)-α-chlorocinnamic acid 
• 1727-39-5 α-chloro β-phenyl acrylic acid 
• 3167-63-3 diethyl chloromethylphosphonate 
• 100-52-7 benzaldehyde 
• 105-58-8 Diethyl carbonate 
• 4192-77-2 ethyl cinnamate 
• 5823-12-1 ethyl 2,2-dichloro-2-diethoxyphosphorylacetate 
• 87439-84-7 ethyl 2,3-dichloro-3-phenylpropenoate 
• 515-84-4 Ethyl trichloroacetate 
• 18365-42-9 α-chloro-cinnamaldehyde 
• 698-88-4 (2,2-dichlorovinyl)benzene 

Downstream Products

• 705-54-4 (Z)-α-chlorocinnamic acid 
• 74305-85-4 (Z)-2-chloro-3-phenylpropenoic acid amide 
• 637-44-5 phenylpropyolic acid 
• 2021-28-5 ethyl dihydrocinnamate 

Relevant academic research and scientific papers

Stereoselective Halo-Succinimide Facilitated α-Halogenations of Substituted α-Trialkylsilyl-β-Substituted-α,β-Unsaturated Esters

The NXS (X = Cl, Br)-mediated halogenation of a series of (E)-α-trimethylsilyl-β-alkyl(aryl)-α,β-unsaturated esters in dimethylformamide (DMF) has furnished (Z)-β-substituted-α-halogenated-α,β-unsaturated ester products in moderate to high isolated yields (58-90%) with dr values of >20:1 coupled with the inversion of olefin stereochemistry. The reaction process was hypothesized to include an initial halonium cation intermediate, followed by regioselective ring opening with DMF. Subsequentanti-E2-type concomitant elimination allowed for the stereoselective formation of the product vinylic bromo-and chloroesters.

Pd0-Catalyzed carbonylation of 1,1-dichloro-1-alkenes, a new selective access to Z-α-chloroacrylates

A novel and fully chemo- and stereoselective three component strategy leading to Z-α-chloroacrylates by a Pd0-catalyzed reaction of CO (1 atm) with 1,1-dichloro-1-alkenes and various alcohols is disclosed. This catalytic approach compares favourably with the Wittig type strategies as α-chloroacrylates of pure Z configuration are obtained in high yield. The Royal Society of Chemistry.

A convenient method for the synthesis of (Z)-α-haloacrylates: Lewis base-catalyzed carbonyl olefination using α-halo-C,O-bis(trimethylsilyl)ketene acetals

A highly useful method for the stereoselective synthesis of (Z)-α-haloacrylates from various aldehydes that uses α-halogenated ethyl-C,O-bis(trimethylsilyl)ketene acetals in the presence of a Lewis base catalyst such as acetate salts was established. This

Chemo- and stereoselectivity of the reaction of aromatic aldehydes with triphenylphosphine and trichloroacetic acid derivatives

Aromatic aldehydes react with triphenylphosphine and ethyl trichloroacetate or trichloroacetonitrile to give the corresponding benzylidene dichlorides or α-chlorocinnamic acid derivatives. The chemo- and regioselectivity of these reactions depend on both the substituent in the aromatic ring and reaction conditions. The product configuration was determined on the basis of the coupling constants 2JCH and 3JCH in the 13C NMR spectra. Pleiades Publishing, Inc., 2006.

Highly selective reaction of α-halo-αβ-unsaturated esters with ketones or aldehydes promoted by SmI2: An efficient alternative access to Baylis-Hillman adducts

A samarium diiodide promoted addition of aromatic or aliphatic β-substituted-α-halo-α,β-unsaturated esters 1 or 3 to both ketones (in THF) and aldehydes (in acetonitrile) led to (Z)-2-(1-hydroxyalkyl)- 2,3-alkenoates 2 and 4 in good yields and very high stereoselectivity. This method constitutes an efficient and valuable alternative to the synthesis of Baylis-Hillman adducts. A mechanism is proposed to explain this transformation.

A convenient halogenation of α,β-unsaturated carbonyl compounds with OXONE and hydrohalic acid (HBr,HCl)

Mixtures of OXONE and hydrobromic acid or hydrochloric acid afford solutions of bromine or chlorine, respectively, α-Bromo- or α-chloro-α,β-unsaturated carbonyl compounds were prepared by addition of hydrobromic acid or hydrochloric acid to the mixture of

α-hypervalent iodine functionalized phosphonium and arsonium ylides and their tandem reaction as umpolung reagents

α-Hypervalent iodine functionalized phosphonium and arsonium ylides 2 can be used as umpolung ylides to react with nucleophiles to give α-heteroatom substituted ylides 4 in good yields. The nucleophilic substitution - Wittig tandem reaction of 2 can occur smoothly to provide an efficient method for the synthesis of (Z)-α-halo-α,β-unsaturated enoates or enones 6, stereoselectively.

Efficient electrosynthesis of α-chloro-α,β-unsaturated carboxylic and phosphonic esters using magnesium electrochemical activation

Various α-chloro-α,β-unsaturated carboxylic or phosphonic esters were easily and rapidly prepared under mild conditions in DMF, by electrolysing respectively triethyl dichloromethylphosphonoacetate and tetraethyl dichloromethyl-bis-phosphonate, then treat

Reaction of Benzeneseleninyl Chloride with Olefins in the Presence of a Lewis Acid. A Novel One Step Vinylic Chlorination

In the presence of aluminum chloride benzeneseleninyl chloride was found to be an exellent vinylic chlorinating reagent of olefins under mild conditions.However, such olefins as styrene, trans-stilbene, and trans-1-phenylpropene afforded dichloro adducts under similar conditions.A plausible reaction mechanism involving positive chlorine intermediate is proposed.

α-LITHIOALKYLPHOSPHONATES AS FUNCTIONAL GROUP CARRIERS. AN IN SITU ACRYLIC ESTER SYNTHESIS

Condensation of α-lithioalkylphosphonates with diethylcarbonate in the presence of LDA generates carbethoxyalkylphosphonate anions which upon treatment at room temperature with aldehydes constitutes an in situ acrylic ester synthesis.