Correlation of the Rates of Solvolyses of 4-Methylthiophene-2-carbonyl Chloride Using the Extended Grunwald-Winstein Equation

摘要

The specific rates of sovolysis of 4-methylthiophene-2-carbonyl chloride (1) have been determined in 26 pure and binary solvents at 25.0 oC. Product selectivities are reported for solvolyses of 1 in aqueous ethanol and methanol binary mixtures. Comparison of the specific rates of solvolyses of 1 with those for p-methoxybenzoyl chloride (2) 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 SN1 and/or ionization (I) pathway rather than through an associative SN2 and/or addition-elimination (A-E) pathway.