Abstract Hexahydropyrimidine and some N-alkylated derivatives have been obtained from the reaction of the corresponding trimethylenediamine or its monoprotonated salt with formaldehyde. A variety of spectroscopic evidence supports a cyclic structure for these compounds in preference to a tautomeric open-chain form. The chemical behaviour of hexahydropyrimidine is explicable in terms of a cyclic di-secondary amine structure. The ...