ChemInform Abstract: A Single Transition State in the Transfer of the Methoxycarbonyl Group Between Isoquinoline and Substituted Pyridines in Aqueous Solution.

ChemInform Abstract

The acyl adduct (III) of isoquinoline (I) and methyl chloroformate (II) readily hydrates to form a pseudobase (IV). The transfer of the methoxycarbonyl group from (III) to 25 pyridines (V) by nucleophilic attack to form pyridinium adducts (VI) is studied kinetically using a spectrophotometric method; AcO- and HPO₄^2- are also used as nucleophiles. The kinetics of hydrolysis of (III) and (VIa), (VIb) are examined as well as the kinetics of E-transfer from the (VIb) adducts to parent pyridine (Va).