Cesium Ion Pair Acidities of some N,N-Dialkylacetamides and Aggregation of Their Cesium Enolates in Tetrahydrofuran.

Cesium ion pair acidities are reported of some N,N-dialkylacetamides at 25 degrees C in tetrahydrofuran. The cesium enolates of alpha-arylacetamides are essentially monomeric at concentrations of about 10(-)(4) M, but small amounts of dimers are present for the enolates of N,N-dimethyl- and N,N-diethyl(4-biphenylyl)acetamide (K(dimer) is approximately 400 M(-)(1)). The cesium enolate of N,N-dimethyldiphenylacetamide forms small amounts of dimers, but the dimerization constant of <100 M(-)(1) is near the limit of detection of our methods. The enolate of N,N-diethylacetamide has an average aggregation number of 3.3, consistent with a mixture of dimers and tetramers. The cesium ion pair pKs of the alpha-arylacetamides are about 25-26, and that of N,N-diethylacetamide is greater than 33.7. The acidity data are in good agreement with measurements that have been reported in the literature for similar systems.