CROSS HYDRODIMERIZATION OF ACRYLONITRILE ETHYL ACRYLATE AND METHACRYLONITRILE BY SODIUM AMALGAM

The reaction of acrylonitrile (M1), ethyl acrylate (M2), and methacrylonitrile (M3) with Na amalgam was studied in solvent systems, DMSO-diglyme and liquid ammonia. It was found that when phenol was used as proton donor the homo hydro dimers and the cross hydro dimers of these monomers were obtained. It was thus possible to measure relative rate constants for the electron-transfer reactions Na(Hg) + M(solvent) → Na + (solvent) M-, the reaction of the radical anion with itself M1- + M1 →M1M1, and the cross reaction of the radical anion with another monomer M1 + M2 → M1M2. The following relative rate constants were measured: electron transfer (DMSO) k1k12 = 0.6,k′1lk′3 = 120, and k′2/k′3 = 200; (liquid NH3) k′1k2 = 0.7, k1k′3 = 3, and k′2/k′3 = 4.5; cross hydrodimerization (DMSO) k11k12 = 0.7, K22/k21 = 0.3, k11/K13 = 3.5, and k22k23 = 1.2; (liquid NH3) k11/k12 = 0.8 and k22d21 = 0.4. © 1969, American Chemical Society. All rights reserved.