Le Menn, Jean Christophe published the artcileElectrochemically generated phosphonate carbanions: formation and reactivity towards aldehydes, Application of Diethyltrichloromethylphosphonate, the publication is Canadian Journal of Chemistry (1989), 67(8), 1332-43, database is CAplus.
Reactivity towards p-methoxybenzaldehyde (ArCHO) of electrochem. generated phosphonate carbanions was investigated. Electrolysis were carried out at a Hg cathode in DMF and two routes to the desired carbanion were 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)CXYZ (X = Cl, Y and W as above; X = Br, W = CO2Et, Y = Cl, Br, or CH3); when no H atoms is present on the carbon bearing the phosphonate group (Y and W ≠ 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), di-Et 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 epoxide resulting from chloride elimination (Darzens reaction). Chemo- and stereoselectivity depends 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. Anal. of the results permits selection of the optimal electrolysis conditions for purposes of synthesis.
Canadian Journal of Chemistry published new progress about 866-23-9. 866-23-9 belongs to chlorides-buliding-blocks, auxiliary class Aliphatic Chain, name is Diethyltrichloromethylphosphonate, and the molecular formula is C5H10Cl3O3P, Application of Diethyltrichloromethylphosphonate.
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