S Ramalakshmi
Articles written in Journal of Chemical Sciences
Volume 120 Issue 5 September 2008 pp 475-480
Micellar catalysis in the retro-Knoevenagel reaction of ethyl-𝛼-cyanocinnamates
K Rajasekaran A Sarathi S Ramalakshmi
Kinetics of base catalysed hydrolytic cleavage of ethyl 𝛼-cyanocinnamate (ECC) and several para-substituted ECC have been investigated spectrophotometrically in the presence of anionic surfactant sodium laurylsulphate (NaLS). The rate of cleavage of ECC was retarded by NaLS. The pseudo-first order rate constants, $k_{\text{obs}}$, correlate with the Hammett $\sigma^+_p$ - constants. The $\rho^+$ value (0.86) in aqueous medium is less than $\rho^+$ value (1.11) in 0.02 M NaLS. Kinetic data were analysed by Menger-Portnoy and Piszkiwicz model. The substrate-micelle binding constants, $K_s$, correlate with the Hammett 𝜎-constants and Hansch hydrophobicity constants - 𝜋 of the substituents.
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