01668nas a2200157   4500008004100000022001400041245012100055210006900176260000900245300001400254490000700268520107300275100001901348700001601367856012701383       2017                        eng d  a1463-907600aThermodynamic and molecular origin of interfacial rate enhancements and endo-selectivities of a Diels-Alder reaction0 aThermodynamic and molecular origin of interfacial rate enhanceme  cFEB   a4297-43060 v193 a<p>Organic reactions in general display large rate accelerations when performed under interfacial conditions, such as on water or at ionic liquid interfaces. However, a clear picture of the physicochemical factors responsible for this large rate enhancements is not available. To gain an understanding of the thermodynamic and molecular origin of these large rate enhancements, we performed a Diels-Alder reaction between cyclopentadiene and methyl acrylate at ionic liquid/n-hexane interfaces. This study describes, for the first time, a methodology for the calculation of the activation parameters of an interfacial reaction. It has been seen that the energy of activation for an interfacial reaction is much smaller than that of the corresponding homogeneous reaction, resulting into the large rate acceleration for the interfacial reaction. Furthermore, the study describes the effects of the alkyl chain length of ionic liquid cations, the extent of heterogeneity, and the polarity of ionic liquids on the rate constants and stereoselectivity of the reaction.</p>1 aBeniwal, Vijay1 aKumar, Anil  uhttps://library.ncl.res.in/content/thermodynamic-and-molecular-origin-interfacial-rate-enhancements-and-endo-selectivities