title: Kinetic coupled with UV spectral evidence for near-irreversible nonionic micellar binding of N-benzylphthalimide under the typical reaction conditions: an observation against a major assumption of the pseudophase micellar model.
abstract: Pseudo-first-order rate constants (k(obs)) for alkaline hydrolysis of N-benzylphthalimide (1) show a nonlinear decrease with the increase in [C(m)E(n)]T (total concentration of Brij 58, m = 16, n = 20 and Brij 56, m = 16, n = 10) at constant [CH(3)CN] and [NaOH]. These nonionic micellar effects, within the certain typical reaction conditions, have been explained in terms of the pseudophase micellar (PM) model. The values of micellar binding constants (KS) of 1 are 1.04 x 10(3) M(-1) (at 1.0 x 10(-3) M NaOH) and 1.08 x 10(3) M(-1) (at 2.0 x 10(-3) M NaOH) for C(16)E(20) as well as 600 M(-1) (at 7.6 x 10(-4) M NaOH) and 670 M(-1) (at 1.0 x 10(-3) M NaOH) for C(16)E(10) micelles. The pseudo-first-order rate constants (kM) for hydrolysis of 1 in C(16)E(20) micellar pseudophase are approximately 90-fold smaller than those (kW) in water phase. The values of kM for hydrolysis of 1 in C(16)E(10) micelles are almost zero. Kinetic coupled with UV spectral data reveals significant irreversible nonionic micellar binding of 1 molecules in the micellar environment of nearly zero hydroxide ion concentration at >or=0.14 M C(16)E(20) and 1.0 x 10(-3) M NaOH while such observations could not be detected at <or=0.17 M C(16)E(20) and 2.0 x 10(-3) M NaOH. Significantly, such irreversible C(16)E(10) micellar binding of 1 molecules could be detected at 8.8 x 10(-2) M C(16)E(10) and 1.0 x 10(-3) M NaOH as well as at >or=3 x 10(-3) M C(16)E(10) and 7.6 x 10(-4) M NaOH, while the rate of hydrolysis of 1 is completely ceased at >or=0.05 M C(16)E(10) and 7.6 x 10(-4) M NaOH. The rate of hydrolysis of 1 at 5.0 x 10(-2) and 8.8 x 10(-2) M C(16)E(10) and 1.0 x 10(-3) M NaOH reveals the formation of presumably phthalic anhydride, whereas such observation was not observed in the C(16)E(20) micellar system under similar experimental conditions.
authors.affiliation: Department of Chemistry, Faculty of Science, University of Malaya, 50603 Kuala Lumpur, Malaysia.
authors.forename: May Ye
authors.initials: MY
authors.lastname: Cheong
authors.forename: Azhar
authors.initials: A
authors.lastname: Ariffin
authors.forename: M Niyaz
authors.initials: MN
authors.lastname: Khan
mesh_terms: D001555:Benzene Derivatives / Q000737:chemistry*; D006868:Hydrolysis; D007700:Kinetics; D008823:Micelles; D008956:Models, Chemical; D010797:Phthalimides / Q000737:chemistry*; D013056:Spectrophotometry, Ultraviolet
chemical_list: D001555:Benzene Derivatives; D008823:Micelles; D010797:Phthalimides