Acidolysis process, initiation

The scope of the living cationic polymerizations and synthetic applications of these functionalized monomers will be treated in the next chapter on polymer synthesis (see Chapter 5, Section III.B). One should note that the feasibility of living processes for these polar monomers further attests to the formation of controlled and stabilized growing species. Conventional nonliving polymerizations, esters, ethers, and other nucleophiles are known to function as chain transfer agents and sometimes as terminators. In addition, the absence of other acid-catalyzed side reactions of the polar substituents, often sensitive to hydrolysis, acidolysis, etc., demonstrates that these polymerization systems are free from free protons that could arise either from incomplete initiation (via addition of protonic acids to monomer) or from chain transfer reactions (/3-proton elimination from the growing end). 

A related process consists initially in the reaction between diethyl methylphosphonate carbanion and a nitrile, RCN, to give the species 318, and the alkylation (R = Me, CH2CH=CH2, CH2Ph) of the latter. Work-up of the product under basic conditions leads to the enamines 319. Work-up with acid conditions affords the (2-oxoalkyl)phosphonic diesters 320 the latter were also obtained through acidolysis (3 m H2SO4) of the enamines 319. A wide choice of alkylating species is possible alkyl halides, disulphides RSSR (R = Me or Ph), sulphenyl chlorides RSCl (R = Me or Ph), PhSeBr, MeS02SMe and PhSOoCl have all been used ". ... 

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