SYNTHESIS OF MACROBICYCLIC POLYETHERS WITH NITROGEN ATOM BRIDGEHEADS

Article abstract of DOI:10.1016/S0040-4020(01)87883-2

Macrobicyclic polyethers containing two 1,4-diaza-crown compounds condensed at the diaza nitrogen atoms (the di-ptychands) have been prepared using a simple and inexpensive procedure of treating the bis((2-hydroxyethyl)diaza-derivatives of 12-crown-4 (12C4), 15-crown-5 (15C5) and 18-crown-6 (18C6) macrocycles with the ditosylate derivatives of di-, tri-, tetra-, or pentaethylene glycol.Eleven di-ptychands were prepared as follows: 12C4-15C5, 12C4-18C6, 12C4-21-crown-7 (21C7), 12C4-24-crown-8 (24C8), 15C5-15C5, 15C5-18C6 (or 18C6-15C5), 15C5-21C7, 15C5-24C8, 18C6-18C6,18C6-21C7 and 18C6-24C8.The starting bis(2-hydroxyethyl)diaza-crowns were prepared in good yields by reacting inexpensive N,N'-bis(2-hydroxyethyl)ethylenediamine with 1,2-bis(2-iodoethoxy)ethane (to give bis(2-hydroxyethyl)diaza-12-crown-4), diethylene glycol bis(2-chloroethyl)ether (to give bis(2-hydroxyethyl)diaza-15-crown-5) and the ditosylate derivative of pentaethylene glycol (to give bis(2-hydroxyethyl)diaza-18-crown-6).Log K values for di-ptychand 15C5-18C6 interactions with sodium and potassium ions were large with a selectivity factor of 6.17 +)/K (Na⁺)>.