INVESTIGATIONS IN THE COMPETITION OF THE CLEAVAGE OF THE C-CL BOND OFA TELOGEN THAT EXHIBITS BOTH TRICHLOROMETHYL AND DICHLOROMETHYLENE GROUPS FOR THE REDOX TELOMERIZATION OF METHYLMETHACRYLATE AND ETHYLACRYLATE

The redox telomerizations of ethylacrylate and methylmethacrylate with the 2,2,4,4,4-pentachloromethylbutyrate catalyzed by copper salts or by RuCl2(PPh(3))(3) were investigated to obtain monodispersed telechel ic oligomers. For both monomers, the expected linear products were pro duced in low yields mainly in the presence of the ruthenium complex. T he difunctional telomers Cl-3 CCH2 CCl(CO2CH3)CH(2)CXYCl where X = CH3 (or X = H) and Y = CO2CH3 or CO2C2H5 were obtained as the major produ cts. This was explained by the cleavage of the C-Cl bond of the dichlo romethylene group, more activated by the ester group than the trichlor omethyl one. The copper salts led to better yields than the ruthenium complex. The evidence of the formation of such products was given by H -1 and C-13 NMR spectroscopy.