3167-62-2

Upstream product

• 866-23-9 diethyl (trichloromethyl)phosphonate 
• 122-78-1 phenylacetaldehyde 
• 123-11-5 4-methoxy-benzaldehyde 
• 120-92-3 cyclopentanone 
• 64-17-5 ethanol 
• 762-04-9 phosphonic acid diethyl ester 
• 110-91-8 morpholine 
• 84336-27-6 diethoxyphosphoryldichloroacetaldehyde 
• 109-72-8 n-butyllithium 
• 19928-97-3 (dichloromethylene)bisphosphonic acid, tetraethyl ester 

Downstream Products

• 3167-63-3 diethyl chloromethylphosphonate 
• 1119-82-0 dichloro-1,1 octene-1 
• 123098-31-7 (trimethoxy-2,4,6 phenyl)-2 dichloro-1,1 ethylene 
• 41448-64-0 1-(2,2-dichlorovinyl)-4-methoxybenzene 
• 123119-65-3 phosphate de diethyle et de paramethoxyphenyl-1 dichloro-2,2 ethyle 
• 477727-71-2 1-[2-chloroethenyl]-4-methoxybenzene 
• 123098-29-3 p-methoxyphenyl-2 epoxy-1,2 ethanephosphonate 
• 768-60-5 4-methoxyphenylacetylen 
• 18684-79-2 Z-1-(2-chloroethenyl)phenyl methyl ether 
• 18684-94-1 1-[(E)-2-chlorovinyl]-4-methoxybenzene 
• 122-66-7 diphenyl hydrazine 
• 6798-58-9 p-dimethylamino phenyl-2 dichloro-1,1 ethylene 
• 52890-09-2 1,1-Dichlor-4-phenyl-1-penten 
• 33491-04-2 1-(chloroethynyl)-4-methylbenzene 

Relevant academic research and scientific papers

Some Transformations of Mono-and Dichloro(diethoxyphosphoryl)acetaldehydes

Addition of ethanol and diethyl phosphonate to the carbonyl group of 2,2-dichloro-2-(diethoxyphosphoryl)-acetaldehyde has been studied, and the corresponding α-chloro ether, acetal, and phosphorylated metrifonate have been obtained. α,α-Dichloro-α-phospho

PREPARATION ELECTROCHIMIQUE DES CHLOROMETHYL ET DICHLOROMETHYL-PHOSPHONATES DE DIETHYLE

Diethylchloromethyl and dichloromethyl-phosphonates are easily prepared by electrochemical reduction of diethyltrichloromethylphosphonate in alcoholic acetate solutions at a graphite electrode under galvanostatic conditions.

Synthesis of dichloromethylphosphonates

Efficient synthesis of O,O-dialkyl, O-alkyl-N,N-dialkylamido and N,N,N',N'-tetraalkyldiamido dichloromethylphosphonates via treatment of O,O-dialkyl, O-alkyl-N,N-dialkylamido, and N,N,N',N'-tetraalkyldiamido trichloromethylphosphonates with diethyl phosph

Intramolecular Nucleophilic Reactions of Dialkyl 1,1-Dichloro-2-hydroxyethylphosphonates

Methods are developed for preparing dialkyl (1,1-dichloro-2-hydroxyethyl)phosphonates. Under the action of sodium hydride these esters enter into intramolecular nucleophilic reactions via two routes yielding α-ketophosphonates and phosphates.

Carbanions phosphonate prepares par voie electrochimique: formation et reactivite vis-a-vis d'un aldehyde

Reactivity towards p-methoxybenzaldehyde (ArCHO) of electrochemically generated phosphonate carbanions has been investigated.Electrolyses were carried out at a mercury cathode in DMF and two routes to the desired carbanion have been compared: (i) Deprotonation of phosphonates of general formula (EtO)2P(O)CHYW (Y = W = Cl; Y = H, W = Cl; Y = Cl, W = CO2Et; Y = H, W = CO2Et; Y = CH3, W = CO2Et; Y = Cl, W = CH3), by the bases resulting from the electroreduction of azobenzene; addition of the carbanion formed onto the carbonyl group takes place and leads to the adduct (EtO)2P(O)CYW(Ar)O-. (ii) Two-electron reduction of halophosphonates (EtO)2P(O)CXYW (X = Cl, Y and W as above; X = Br, W = CO2Et, Y = Cl, Br, or CH3); when no H atom is present on the carbon bearing the phosphonate group (Y and W no = H), the same evolution leading to the above adduct is observed, on the contrary, when Y = H, the electrogenerated carbanion deprotonates the substrate and the resulting carbanion (EtO)2P(O)CXW reacts with the aldehyde; giving the adduct (EtO)2P(O)CXW(Ar)O-.Evolution of the intermediate adduct depends on the substituents Y (or X) and W: when W = CO2Et, whatever the nature of Y (or X), diethyl phosphate is eliminated with formation of the ethylenic ArCH=CWY (or X) (Wittig-Horner reaction); the same evolution is observed when Y = W = Cl.When W = Cl and Y = H or CH3, the final product is the phosphonate epoxyde resulting from chloride elimination (Darzens reaction).Chemo- and stereoselectivity depend only on the nature of Y and W but are independent of the mode of generation of the carbanion.Yields are limited by side-protonation reactions, which are related to the basicity of the phosphonate carbanions.Analysis of the results permits selection of the optimal electrolysis conditions for purposes of synthesis.Key words: electrosynthesis, electrogenerated bases, phosphonates, Wittig-Horner.

The electrochemical Wittig-Horner reaction; evidence of a stepwise cleavage of a four-membered ring Wittig intermediate

Electro-reduction of diethyl(trichloromethyl)phosphonate in the presence of aldehydes or ketones relpaces the oxygen atom of the carbonyl group by a dichloromethylene group.The yield of 1,1-dichloroethene product decreases subtantially if the carbonyl com