A study was made of the addition reaction, initiated by peroxides, of diethyl malonate, dimethyl succinate and ethyl monochloroacetate to the polyhaloolefins — to hexafluoropropylene, trichloroethylene and tetrachloroethylene.
The reaction proceeds by an anomalous direction: the α-carbon atom of the alcohol portion of the ester molecule takes part either exclusively or predominantly in the formation of the new carbon — carbon bond of the adducts.
The reaction of esters with trichloro- and tetrachloroethylene is accompanied by the elimination of hydrogen chloride and leads to the respective formation of either the 1-(dichlorovinyl) or 1-(trichlorovinyl) derivatives of alkyl esters of carboxylic acids.
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Nikishin, G.I., Ogibin, Y.N. & Lebedev, V.N. Unusual direction of the radical reaction of esters with ethylenic compounds. Russ Chem Bull 20, 980–985 (1971). https://doi.org/10.1007/BF00862208
- Alkyl Ester