α,ω-Bis(3,6-dimethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-1-yl)alkanes and products of their cyclization, pyrimidinophanes: intra- and intermolecular interaction in crystals and in solutions

Abstract

Reaction of α,ω-bis(3,6-dimethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-1-yl)alkanes with paraformaldehyde leads to pyrimidinophanes, which contain four 3,6-dimethyluracil fragments, connected to each other by the methylene chains. A comparative study of intra- and intermolecular interactions of “open” and macrocyclic uracil derivatives in the crystal state and in solution was performed. According to the NMR spectroscopy data, there is no self-association of “open” and macrocyclic compounds in chloroform solutions, whereas the X-ray data revealed the intermolecular π-π contacts between the 3,6-dimethyluracil fragments in the crystals of these compounds. Conclusions on the presence of intramolecular interactions in chloroform solutions of α,ω-bis(3,6-dimethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-1-yl)alkanes and pyrimidinophanes were made based on the UV spectra, which were interpreted in terms of hypo- and hyperchromic effects relatively to the model uracil derivative. These conclusions correlate with the X-ray data: there are no intramolecular π-π contacts between the 3,6-dimethyluracil fragments both in the crystals and in solutions of “open” compounds, positions of these fragments relatively to each other in the molecules of pyrimidinophanes are defined by the lengths of the polymethylene bridges. The intramolecular stacking effect between the opposite uracil rings is observed for the macrocycles with trimethylene and hexamethylene chains, whereas there is no such interactions in pyrimidinophanes with tetramethylene chains.