The discovery of the crown ethers stemmed from efforts to control the catalytic activity of vanadium and copper by complexation with multidentate ligands. The first crown ether, 2,3,11,12-dibenzo-1,4,7,10,13,16-hexaoxacyclo-octadeca-2,11-diene, was obtained in 0.4% yield during an attempt to prepare a phenolic ligand from catechol and bis(2-chloroethyl)ether. This compound, which complexed with the sodium cation, was the first compound known to display such activity and became known as dibenzo-18-crown-6, an 18-atom heterocycle containing 6 oxygen atoms. Some 60 related compounds were made involving heterocyclic rings containing 12 to 60 atoms including 4 and 10 oxygen atoms. There are optimum polyether ring sizes for the different alkali metal cations: 15 to 18 for sodium, 18 for potassium, and 18 to 21 for cesium. Complexes having polyether to cation ratios of 1:1, 3:2, and 2:1 were prepared. Solubilization of inorganic salts in aprotic solvents, especially by saturated crown ethers, was demonstrated.