Synthesis of crowned triazolephthalocyanines

The synthesis of triazolephthalocyanines bearing crown ether and aza-crown ether substituents is described. Different substituents have been introduce d on the nitrogen atom of the aza-crown moiety to improve the solubility an d the intrinsic amphiphilic character of these macrocycles. The crowned tri azolephthalocyanines described have been prepared by a statistical procedur e, and also by different variations of a stepwise method. Preliminary studi es of the aggregation properties of one representative of this new family o f compounds have also been carried out. An exhaustive study of the synthesi s of the corresponding dicyano derivative precursors of the triazolephthalo cyanines is displayed. Two different approaches have been used for this goa l: The first one inserts the cyano groups prior to the synthesis of the cro wn ether moiety, while the second one builds the crown ether part of the mo lecule in advance of the cyanation process. The incompatibility of the Rose mund-von-Braun cyanation conditions and the presence of nitrogen atoms in t he molecule is the main difficulty of the synthesis of these precursors.