HEXAAZA AND OCTAAZA MACROCYCLES WITH 2-HYDROXY-3,5-DIMETHYLBENZYL PENDANT ARMS

New 18-membered hexaaza (3 and 4) and 24-membered octaaza (7 and 8) ma crocycles with 2-hydroxy-3,5-dimethylbenzyl pendant arms have been pre pared via a Mannich type reaction of the corresponding macrocycles [(1 and 2) and (5 and 6) respectively] with 2,4-dimethylphenol in the pre sence of methanal in a methanolic solution. X-Ray structure analysis s hows the tetramethyl substituted hexaaza macrocycle with 2-hydroxy-3,5 -dimethylbenzyl pendant arms 4 and its precursor [H(4)2](4+) both have centrosymmetric molecules with step conformation. Differences in conf ormation arise from hydrogen bonding interactions; in [H(4)2](4+) bond ing between amino nitrogen atoms and water molecules appears to tie th e backbone chain of the macrocycle together, and in 4 strong intramole cular hydrogen bonding with each 2-hydroxybenzylamino unit dictates th e orientation of the pendant arms.