A novel synthetic route to and a polymerization procedure for 0x0-crown ethers 2,ll -dioxo-18-crown-6 (l), 2-0x0-12-crown-4(2) and 2-0x0-2 1-crown-7 (3) are described. Cyclization of the o-hydroxycarboxylic acid precursors of 1-3 has been achieved by heating these precursors in the presence of a Lewis acid catalyst (CoClZ) and a template salt (MCl). Cyclization yields up to 82% were reached, using CsCl as template salt. 0x0-crown ethers 1-3 have been polymerized using SnOctz as catalyst, giving polymers with molecular weights of approximately 5 kg/mol and dispersities of ca. 1.8 (measured with polyethylene oxide standards). The polymerization of 2 was monitored with 'H-NMR and SEC giving information about (a) the influence of monomerkatalyst ratio and temperature on polymerization rate and (b) the influence of temperature on molecular weight (distribution). The possibility of introducing endgroups into poly(2-0x0-12-crown-4) using SnOctz-catalyzed polymerization was also studied. 1 2 3 and 7 b were obtained in isolated vields of 55% and 76%. CO) e, O J L O J L J O L J w 0 Acta Polymer., 47,485491 (19%) 0 VCH Verlagsgesellschaft mbH, D-69451 Weinheim, 1996