66051-39-6

Upstream product

• 7071-12-7 triethyl 2-chloro-2-phosphonoacetate 
• 5823-12-1 ethyl 2,2-dichloro-2-diethoxyphosphorylacetate 
• 123-11-5 4-methoxy-benzaldehyde 
• 791131-05-0 ethyl chloro(diphenylphosphono)acetate 

Relevant academic research and scientific papers

One-pot process in phosphonium-iodonium ylides: Nucleophilic substitution and the Wittig reaction

The nucleophilic substitution in mixed phosphonium-iodonium ylides was investigated. The iodonium group is replaced by such S-containing nucleophiles as the thiocyanate anion or thiourea, as well as by halide ions. The structure of the reaction product with the thiocyanate ion was established by X-ray diffraction. A one-pot process involving the nucleophilic substitution and the Wittig reaction was developed.

Stereoselective preparation of (E)-α-bromoacrylates from mixtures of brominated ando phosphonates

We prepared 69:31-11:89 mixtures of phosphonates 6b and 7b containing two phenoxy substituents, a CO2Et group, and 1 or 2 bromine atoms, respectively, at the interspersed methylene group. Deprotonating 64:36 mixtures of these reagents with NaH

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

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.