In-Place Conversion of Strained Bicyclic Compounds to Stable Polymers.

A simple synthesis of new electronegatively substituted bicyclobutane monomers has been worked out. It involves a 22 cycloaddition of trielectronegatively substituted ethylenes with dimethylaminoethylenes, followed by conversion to the quaternary ammonium salt and cross-ring elimination effected by base. A new copolymer synthesis involving the copolymerization of trielectronegatively substituted ethylenes with electron-rich vinyl monomers has been established under free radical polymerization conditions. A second new copolymer synthesis, involving the copolymerization of trielectronegatively substituted ethylenes with monoelectronegatively substituted bicyclobutane monomers has been devised. The synthesis of an intermediate for a new type of monomer, the 2-oxabicyclobutanes, has been accomplished. It involves chlorination of 2-cyanooxacyclobutanes, followed by dehydrohalogenation to give the bicyclic compound.