Catalytic Efficiency of [20]Paracyclophane Oxime and Cycloheptaamylose in the Decomposition of Carboxylate and Carbonate Esters

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The hydrolytic decomposition of dodecyl ρ-nitrophenyl carbonate (LPNC) and ρ-nitrophenyl dodecanoate (PNPL) as mediated by 10-hydroxy-ll-hydroxyimino[20]-paracyclophane (Oxime-I) and cycloheptaamylose (β-CD) has been investigated in aqueous media containing 9.9% (v/v) ethanol and 1.0% (v/v) acetonitrile to gain an insight into the reaction and/or substrate specificity. Both LPNC and PNPL were decomposed effectively by an equimolar amount of Oxime-I. It turned out from the analysis of kinetic data that the binding of LPNC to Oxime-I is 2.5 times tighter than that of PNPL, but the subsequent catalysis is 3.3 times more favorable for PNPL than for LPNC. Hence, the overall efficiency of Oxime-I is 1.3 times greater for PNPL, as changed from a 13-fold difference between both substrates in the simple alkaline hydrolysis. β-CD was found to be effective also in the decomposition of LPNC when added in large excess over substrate. Comparison of kinetic parameters between the two systems, Oxime-I and β-CD, indicated that the former is better in both binding and catalytic effects toward the extremely hydrophobic substrates.
長崎大学工学部,Faculty of Engineering, Nagasaki Universityの論文