Anionic oligomerization of acrylamide by alkali metal methoxides

The anionic oligomerization of acrylamide by methanolic alkali metal methoxides was studied in methanol and in aprotic solvents. Oligomer yield increased with increasing initiator concentration, the dielectric constant of the solvent, the electropositivity of the alkali metal and with decrease in methanol concentration. Initiation occurred by addition of methoxide to the double bond. Simultaneous monitoring of the reactants and products showed that β-methoxypropionamide, first formed in up to 70% yield, undergoes a base-catalysed reversible reaction generating acrylamide which participates in propagation. Acid hydrolysis of the oligomers showed that propagation had proceeded through 1.2-addition (30-50%) leading to an acrylamide structure. and 1.4-addition (50-70%) leading to a β-alanine structure in the polymers.