A NEW ROUTE TO THE ASYMMETRIC CYLINDRICAL MACROTRICYCLIC LIGANDS

New asymmeric cylindrical macrotricyclic ligands have been prepared co ntaining two diaza-12-crown-4 units connected by diethyleneoxy or trie thyleneoxy and mera- or para-xylylene bridges, 2-4. These materials we re prepared in three steps by first treating 6-tosyl-6-aza-3,9-dioxa-1 ,11-undecanediyl ditosylate with 3-oxa-1,5-pentanediamine or 3,6-dioxa -1,8-octanediamine to form ditosyl-substituted bis(diaza-12-crown-4)s connected by a diethyleneoxy or triethylencoxy bridge. These latter co mpounds were detosylated and treated with either para- or mera-alpha,a lpha'-dibromoxylene to give new asymmetric cylindrical macrotricycIes 2-4. The solid state structure of one of these ligands, 3, has been de termined by X-ray diffraction