Correlation of the Rates of Solvolysis of 1-Piperidincarbonyl Chloride Using the Extended Grunwald-Winstein Equation

Abstract

The specific rates of sovolysis of 1-piperidincarbonyl chloride (1) have been determined in 26 pure and binary solvents at 25.0 degrees C. Comparison of the specific rates of solvolyses of 1 with those for p-methoxybenzoyl chloride and those for 4-morpholinecarbonyl chloride in terms of linear free energy relationships (LFER) are helpful in mechanistic considerations, as is also treatment in terms of the extended Grunwald-Winstein equation. It is proposed that the solvolyses of 1 in binary aqueous solvent mixtures proceed through an ionization [I] pathway rather than through an S(N)1/S(N)2 and/or ionization/(ionization-elimination) = [I/(I-E)] pathway.