Abstract.
The bis phenoxide forms of (1,2)bis(2-hydroxybenzamido)ethane(I), (1,5)bis(2-hydroxybenzamido)3-azapentane(II), (1,3)bis(2-hydroxybenzamido)propane(III), and (1,8)bis(2-hydroxybenzamido)3,6-diazaoctane(IV) undergo facile hydrolysis of one of the amide groups (0.02 ≤ [OH − ]T (mol dm − 3) ≤ 0.5, 10% MeOH (v/v) + H2O medium) without exhibiting [OH − ] dependence. The reactivity trend follows I ~ II > > III ~ IV with low activation enthalpy {25.7 ± 2.8 ≤ ΔH≠ (kJ mol − 1) ≤ 64.8 ± 7.0}. The high negative and comparable values of activation entropy {− 234 ± 8 ≤ ΔS≠ (J K − 1 mol − 1) ≤ −127 ± 20} are consistent with closely similar, and ordered transition states which can be assembled by favourably oriented phenoxide groups. The solvent kinetic isotope effect for I, k H2O/k D2O + H2O ~1 (20 and 50 volume% D2O), indicates that proton transfer is not involved as a part of the rate controlling process. The observed slowing down of the rate of this reaction for I in the micellar pseudo phase of CTABr also supports the proposed mechanism. Under pre-micellar conditions, however, rate acceleration is observed, a consequence believed to be associated with the capping effect of the hydrophobic tail of the surfactant cation forming the reactive ion-pair, CTA + , (I-2H)2 − exclusively in the aqueous pseudo phase.
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DASH, S.C., DASH, A.C. Proximity effect on the general base catalysed hydrolysis of amide linkage: The role of cationic surfactant, CTABr. J Chem Sci 123, 497–507 (2011). https://doi.org/10.1007/s12039-011-0084-5
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DOI: https://doi.org/10.1007/s12039-011-0084-5