Kinetic Evidence for Near Irreversible Nonionic Micellar Entrapment of N-(2′-Methoxyphenyl)phthalimide (1) under the Typical Alkaline Reaction Conditions

Table 3

Values of 𝑘_obs, 𝛿_ap, and 𝐴₀ calculated from (1) for alkaline hydrolysis of 1 in the presence of C₁₂E₂₃ micelles^a.

10^3 [C12E23]T; M	10^3 [NaOH]; M	10^3  𝑘obs; s^−1	𝛿ap; M^−1 cm^−1	10^3𝐴0	𝑘^bOH; M^−1 s^−1	𝐹IT𝟏^c	𝑅^d	𝑡^e; h	10^8  𝑘1^f; s^−1
9.9^g	7.6	64.2±0.8^h	2088±25^h	256±3^h	8.45	0.68	1.30	432	25
9.9	7.6	66.1±1.1	1691±32	267±3	8.70	0.55	1.30	600	27
10.0^i	7.6	67.8±0.5	3293±25	260±3	8.92		1.32
19.8	11.0	44.4±0.5	2127±19	303±2	4.04	0.70	1.82	623	16
19.8	11.0	35.0±0.2	1564±7	314±1	3.18	0.51	1.82	1083	18
20.0^i	11.0	51.2±0.2	3344±13	282±1	4.65		1.82
29.5	17.4	69.9±0.9	2714±45	297±5	4.02	0.89	1.70	600	5.5
29.5	17.4	70.3±0.3	2271±92	310±9	4.04	0.74	1.70	1085	7.6
30.0^i	17.0	64.8±0.3	3325±16	331±2	3.81		1.76
48.5	30.0	86.3±1.5	3302±93	291±9	2.88	1.08	1.62	622	—
48.5	30.0	88.1±1.8	2789±89	324±9	2.94	0.91	1.62	1102	2.3
48.5^i	30.0	78.6±2.5	3365±129	406±13	2.62		1.62

a[1 ₀] = 0.1 mM, 𝜆=290 nm, 𝑇=35°C, and the aqueous reaction mixture contained 2% v/v CH₃CN. ^b𝑘_OH=𝑘_obs [NaOH]. ^c𝐹_IT𝟏=𝛿_ap/𝛿_ap^avg with 𝛿_ap^avg=3058 M⁻¹ cm⁻¹. ^d𝑅 = [C₁₂E₂₃]_T/[NaOH]. ^e𝑡 is reaction time (𝑡≥𝑡_∞) where the kinetic reaction mixture was used for micellar entrapment experiment. ^fCalculated from the relationship: 𝑘₁=(1/𝑡)ln(1/𝐹_IT𝟏). ^gValue of [C₁₂E₂₃]_T after external addition of [NaOH]. ^hError limits are standard deviations. ⁱReaction mixture for kinetic run was freshly prepared, where 𝛿_ap=𝛿_ap^avg.