Triuracils – 1,3‐Bis[ω‐(N‐methyluracil‐1‐yl)alkyl]thymines and Their 5,5′‐Cyclic Counterparts

Abstract

AbstractA series of acyclic compounds with two 3,6‐dimethyluracil or 3‐methyluracil units attached to a a thymine or isocyanurate fragment by polymethylene or xylylene spacers are investigated. Ring‐closure reactions with paraformaldehyde in aqueous HCl in the presence of copper(I) chloride afforded pyrimidinophanes which can be considered macrocyclic counterparts of the acyclic triuracils. By X‐ray diffraction data the structures of the macrocycles in the solid state are characterised by a close arrangement of the uracil units, but there are no π‐π contacts between them. On the contrary, significant hypochromism of the macrocyclic triuracils compared with their acyclic counterparts indicates stacking between the thymine and 3,6‐dimethyluracil units in chloroform and H2O solutions. The conformational behaviour of the acyclic and macrocyclic compounds in solution has been determined by NMR, UV and computational methods. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)