Basicity and structure of 2,6-pyrido-crown ethers; the effect of ringsize, solvent interactions, and hydrogen bonding

Abstract
The acidity of 2,6-pyridinium-crown ethers (1) varies with the ringsize [pKa 4.88(15-membered ring), 4.95 (18-), 4.16(21-), 3.95 (24-), 3.70(27-), 3.53(30-); H2O, 25.0 °C]; X-ray analyses of the 2,6-pyrido-18-crown-6·H2O·HClO4 complex and the free 2,6-pyrido-18-crown-6 point to specific intra-annular hydration.

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