01747nas a2200157   4500008004100000022001400041245009100055210006900146260011000215300001400325490000600339520109300345100001701438700001601455856011801471       2015                        eng d  a2046-206900aKinetic and mechanistic investigations of the Baylis-Hillman reaction in ionic liquids0 aKinetic and mechanistic investigations of the BaylisHillman reac  aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcNOV  a2994-30040 v53 a<p>We report here a quantitative study of the kinetics and mechanism of the Baylis-Hillman reaction in the presence of ionic liquids as solvent media. Apparently, a simple Baylis-Hillman reaction can occur by two different exclusive mechanisms in ionic liquids. The delicate balance of these mechanisms is maintained by the ionic environment employed. The main features of the possible mechanism have been described here along with interesting kinetic consequences. The measurement of rate constants and activation energy parameters demonstrate that as the medium becomes basic, the order of the reaction changes from 1 to 2. An unexpected change in the mechanism of the reaction is observed with a change in the nature of the ionic liquid. The Linear Solvation Energy Relationship has also been used as an investigating tool to delineate the respective contributions of the cation and anion of the ionic liquid. The observation strongly dictates the dependency of the mechanism of the Baylis-Hillman reaction on the nature of the anion of the ionic liquids undertaken for this study.</p>1 aSingh, Anshu1 aKumar, Anil  uhttps://library.ncl.res.in/content/kinetic-and-mechanistic-investigations-baylis-hillman-reaction-ionic-liquids-001863nas a2200157   4500008004100000245015100041210006900192260000800261300001400269490000600283520122300289100002601512700002601538700001601564856012501580       2017                        eng d00aKinetic profile and catalytic activity of transition metal-based ionic liquids for reduction of nitroarenes via in situ formation of nanoparticles0 aKinetic profile and catalytic activity of transition metalbased   cAUG  a6833-68430 v23 a<p>The experimentally determined apparent rate constant (k(app)) shows that the [BmIm](2)[PdCl4] and [BmIm](2)[NiCl4] act as effective catalysts for the reduction of nitroarenes to aminoarenes in the presence of NaBH4. The TEM, XPS, XRD and dynamic light scattering studies show that there is in situ formation of Pd and Ni metal Nanoparticles (NPs) from the reduction of [BmIm](2)[PdCl4] and [BmIm](2)[NiCl4], respectively which are responsible for the enhancement in the catalytic activity. Thus, in the presence of the ionic liquid stabilized metal NPs show higher catalytic activity in comparison to the NPs stabilized with other capping agents as reported. The order of k(app) as 1) PNP &gt; 2-BrPNP &gt; 2-APNP and 2) PNP &gt; ONP &gt; 2-NR for reduction of nitroarenes using [BmIm](2)[PdCl4] and [BmIm](2)[NiCl4] and its correlation explained on the basis of electronic structure and hydrogen bonding ability of nitroarenes. The thermodynamic parameters such as E-a, Delta H-#, Delta S-# and Delta G(#) are in agreement with the surface catalyzed reduction reaction of PNP in the presence of NPs as catalyst. The kapp values illustrated the reduction reaction follow the LangmuirHinshelwood (L-H) mechanism.</p>1 aThawarkar, Sachin, R.1 aKhupse, Nageshwar, D.1 aKumar, Anil  uhttps://library.ncl.res.in/content/kinetic-profile-and-catalytic-activity-transition-metal-based-ionic-liquids-reduction