Unexpected behavior of 6H,13H-5:12,7:14-dimethanedibenzo[d,i][1,3,6,8]tetraazecine (DMDBTA) toward phenols

A new 20-membered octaazamacrocyclic compound named 1:4,6:9,11:14,16:19-tetramethylentetrabenzo[b,g,l,q][1,4,6,9,11,14,16,19]octaazaeicocine (TTBOE) (9) has been prepared by means of in situ one-pot synthesis between the aminal 6H,13H-5:12,7:14-dimethanedibenzo[d,i][1,3,6,8]tetraazecine (DMDBTA) (3) and electron-deficient phenols. Otherwise, electron-rich phenols such as 4-chloro-3,5-dimethylphenol or 2-naphthol produce an ortho-regioselective aminomethylation resulting in 2-(1H-benzimidazol-1-ylmethyl)-4-chloro-3,5-dimethylphenol (7) and 1-(1H-benzimidazol-1-ylmethyl)-2-naphthol (8) in a Mannich type reaction in a basic medium. Moreover, obtainment of 1,1′-methylenbis(1H-benzimidazole) (15) from TTBOE is discussed.