Cyclic diamides. II. Syntheses and polymerizations of perhydro-1,5-diazocine-2,4-dione and its derivatives

One isomer, perhydro-1,5-diazocine-2,4-dione, was obtained exclusively by the double Beckmann-rearrangement reactions of cyclohexane-1,3-dione dioxime. It is suggested that the other possible isomer was decomposed by a transannular reaction. Perhydro-1,5-diazocine-2,4-dione was polymerized in the solid state in the presence of water vapor and produced polytrimethylenemalonamide. Further, this monomer was polymerized in the molten state without water. 7-Methyl- and 7,7-dimethyl-perhydro-1,5-diazocine-2,4-dione were prepared, and the latter was polymerized in molten state. Differential thermal analyses of the monomer and x-ray diffraction measurements of the polymers were carried out.