Effects of mixed aqueous‐organic solvents on the rate of intramolecular carboxylic group‐catalyzed cleavage of N‐(4′‐methoxyphenyl)phthalamic acid

Abstract

AbstractKinetic study on the cleavage of N‐(4′‐methoxyphenyl)phthalamic acid (NMPPAH) in mixed H2O‐CH3CN and H2O‐1,4‐dioxan solvents containing 0.05 M HCl reveals the formation of phthalic anhydride (PAn)/phthalic acid (PA) as the sole or major product. Pseudo first‐order rate constants (k1) for the conversion of NMPPAH to PAn decrease nonlinearly from 60.4 × 10−5 to 2.64 × 10−5 s−1 with the increase in the contents of 1,4‐dioxan from 10 to 80% v/v in mixed aqueous solvents. The rate of cleavage of NMPPAH in mixed H2O‐CH3CN solvents at ≥50% v/v CH3CN follows an irreversible consecutive reaction path: NMPPAH PA. The values of k1 are larger in H2O‐CH3CN than in H2O‐1,4‐dioxan solvents. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 316–325, 2004