NEW LARIAT ETHER-TYPE MACROCYCLES WITH CYCLOPHOSPHAZENE SUBUNITS

New side-armed ligands of lariat ether type 6-13 have been synthesized by the respective phenolysis and naphtholysis reactions of the parent isomeric ansa (2, 4) and spiro (3, 5) macrocyclosubstituted cyclophosphazenes of general formula N3P3Cl4[O(CH2CH2O)(n)] (where n = 4, 5), separated by column chromatograhy, and characterized by mass spectrometry and H-1 and P-31 NMR spectroscopies. The synthesized side-armed ligands 6-13, as well as their respective functional chlorine-containing precursors 2-5, represent crown ethers with cyclophosphazene subunits and may thus be considered as diphosphaza[16]crown-6 or PNP16C6 (2, 6, 10), diphosphaza[19]crown-7 or PNP19C7 (4, 8, 12), phospha[14]crown-5 or P14C5 (3, 7, 11), and phospha[17]crown-6 or P17C6 (5, 9, 13). The one-pot method of synthesis developed for (aryloxy)-crowns 6-13, with the phenolysis (or naphtholysis) performed in situ immediately after completing the formation of the respective chlorine-containing macrocycles 2-5, made it possible to obtain high yields of the corresponding 16- and 19-membered ansa-PNP-cyclosubstituted side-armed diphosphaza-crowns PNP16C6 and PNP19C7 (6, 8, 10, 12) and to isolate the stable 14- and 17-membered spiro-P derivatives P14C5 and P17C6 (7, 9, 11, 13), inaccessible by other synthetic routes. The diphosphaza-crowns thus obtained with beta-naphthoxy substituents (10, 12) offer promising prospects as new Ligands of the P-pivot lariat ether type, capable of complexing both alkali and transition metal cations and of potential catalytic activity in phase and electron-transfer processes.