ALKALINE-EARTH METAL-ION CATALYSIS OF ALCOHOLYSIS OF CROWN-ETHER ARYL ACETATES - EFFECT OF THE BASE SOLVENT SYSTEM

The effect of strontium and barium ions on the acyl transfer reaction to ethoxide ion from 2-acetoxy-1,3-xylyl-15-crown-4, 2-acetoxy-1,3-xylyl-18-crown-5, 2-acetoxy-1,3-xylyl-21-crown-6 and the model compound phenyl acetate was investigated in ethanol at 25-degrees-C. Significant catalytic effects were observed in all of the studied reactions as a result of stronger metal ion associations with the transition states than with reactants. The rate enhancements observed with the crown ether substrates are much larger than those observed with phenyl acetate, the largest acceleration being displayed by 2-acetoxy-1,3-xylyl-21-crown-6, which reacts with EtOBaBr 5 x 10(5) times faster than with EtONMe4. These findings provide strong evidence that cooperation of electrostatic binding to the negative charge developing at the carbonyl oxygen and coordinative binding to the polyether chain is highly efficient in the metal-bound transition state. Comparison of rate data reported here with analogous data obtained in methanol solution clearly shows that both modes of interaction contributing to the stability of the metal-bound transition state are much more efficient in ethanol than in methanol solution.