01985nas a2200169 4500008004100000022001400041245011900055210006900174260007100243300001400314490000700328520128100335100001201616700002701628700002901655856013101684 2005 eng d a0888-588500aKinetic modeling of reductive alkylation of aniline with acetone using Pd/Al2O3 catalyst in a batch slurry reactor0 aKinetic modeling of reductive alkylation of aniline with acetone a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcJUL a5388-53960 v443 a

The kinetics of reductive alkylation of aniline with acetone was studied in a slurry reactor under isothermal conditions in a temperature range of 378-408 K using 3% Pd/Al2O3 catalyst. Experimental data on concentration-time as well as hydrogen consumption-time profiles were obtained to study the effect of concentration of aniline, catalyst loading, and partial pressure of hydrogen. Separate controlled experiments were performed to understand the nature of the condensation reaction between aniline and acetone, which forms the Shiff's base intermediate. From the concentration-time profiles and the effect of reaction conditions, it was found that the noncatalytic equilibrium formation of the Shiff base intermediate was the slowest step in the multistep reaction sequence. Several rate equations were considered to fit the batch slurry reactor data, and rate models based on competitive dissociative adsorption of hydrogen and the reactive substrates in the rate-limiting catalytic steps were found to represent the experimental data. The kinetic parameters were evaluated by fitting the integral batch reactor data at different temperatures. The activation energies, heat of adsorption, and entropy of adsorption of all the reactant species were also evaluated.

1 aRoy, D.1 aJaganathan, Rengaswamy1 aChaudhari, Raghunath, V. uhttps://library.ncl.res.in/content/kinetic-modeling-reductive-alkylation-aniline-acetone-using-pdal2o3-catalyst-batch-slurry-001924nas a2200181 4500008004100000022001400041245013100055210006900186260007100255300001400326490000700340520117800347100002401525700001601549700002401565700002901589856012401618 2007 eng d a0888-588500aKinetics of reductive alkylation of p-phenylenediamine with methyl ethyl ketone using 3% Pt/Al2O3 catalyst in a slurry reactor0 aKinetics of reductive alkylation of pphenylenediamine with methy a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcMAY a3243-32540 v463 a

Intrinsic kinetics of reductive alkylation of p-phenylenediamine (PPDA) with methyl ethyl ketone (MEK) using 3% Pt/Al2O3 catalyst was studied in a slurry reactor. The overall reaction involves a combination of parallel and consecutive reactions involving equilibrium noncatalytic (homogeneous) and catalytic (heterogeneous) steps. For the purpose of kinetic modeling, the effects of PPDA concentration, catalyst loading, agitation speed, and partial pressure of hydrogen were studied in a temperature range of 373-413 K. Quantitative criteria were used to ensure that the reaction occurred in the kinetic regime. Different rate equations have been considered based on the elementary steps involving catalytic and noncatalytic reactions, which lay stress on the different types of interactions occurring between the reactants and the active catalyst sites. The best-fit rate model has been proposed by rigorous optimization and model discrimination procedures, by simulating the experimental concentration-time data. For the best-fit model, the agreement between the predicted and experimental data was found to be very good over a wide range of operating conditions.

1 aPatil, Narendra, G.1 aRoy, Debdut1 aChaudhari, Amit, S.1 aChaudhari, Raghunath, V. uhttps://library.ncl.res.in/content/kinetics-reductive-alkylation-p-phenylenediamine-methyl-ethyl-ketone-using-3-ptal2o301839nas a2200229 4500008004100000022001400041245010200055210006900157260007300226300001200299490000800311520099700319653001401316653001801330653001301348653001701361100002101378700002801399700002501427700002901452856012801481 2009 eng d a1381-116900aKinetics of arylation of 3-bromo-benzophenone with n-butylacrylate using NC palladacycle catalyst0 aKinetics of arylation of 3bromobenzophenone with nbutylacrylate  aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcAUG a111-1160 v3093 a

The kinetics of arylation of n-butylacrylate (n-BA) with 3-bromo-benzophenone (BBP) using a monomeric palladacycle complex [Pd(ppy)(PPh(3))(OTs)](ppy=2-phenylpyridine) catalyst has been studied. The effect of concentration of the substrate, base (NaOAc), and catalyst was studied at three different temperatures (413-433 K). The rate was found to be first order with respect to catalyst, first order tending to zero order with respect to n-butylacrylate and NaOAc concentrations. The rate passed through a maximum with variation of BBP concentration. The observed results have been explained on the basis of formation of Pd species (PdX(2), PdX(3)(-), PdX(4)(2-), and Pd(2)X(6)(2-)) which are inactive for the Heck reaction. Various empirical rate equations were considered to fit the rate data and the best fitting model has been selected. The rates predicted by model were found to be in good agreement with the observed experimental data. (C) 2009 Elsevier B.V. All rights reserved.

10aArylation10aHeck reaction10akinetics10aPalladacycle1 aAtla, Shashi, B.1 aRajurkar, Kalpendra, B.1 aKelkar, Ashutosh, A.1 aChaudhari, Raghunath, V. uhttps://library.ncl.res.in/content/kinetics-arylation-3-bromo-benzophenone-n-butylacrylate-using-nc-palladacycle-catalyst-002098nas a2200253 4500008004100000022001400041245010300055210006900158260010600227300001200333490000700345520115900352653001001511653001401521653001301535653002501548653002201573653002501595653002501620100001601645700002401661700002901685856013001714 2010 eng d a0009-250900aKinetics of reductive alkylations of phenylenediamines: influence of substrates isomeric structure0 aKinetics of reductive alkylations of phenylenediamines influence aTHE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLANDbPERGAMON-ELSEVIER SCIENCE LTDcJAN a232-2390 v653 a

Reductive alkylation of ortho-, meta- and para-phenylenediamines (PDAs) with methyl ethyl ketone (MEK) has been studied in a semi-batch slurry reactor in the presence of a commercial 3% Pt/Al(2)O(3) catalyst. It was observed that the PDA isomers differ remarkably from each other in their activity in reductive alkylation and product distribution. The activity was found to decrease in the following order: PPDA > OPDA > MPDA. To understand the substrate structure-activity correlation, the homogeneous equilibrium reactions involved in the alkylation step and the overall catalytic reactions were studied separately. Kinetics of reductive alkylation of PDAs with MEK as a solvent and alkylating agent with 3% Pt/Al(2)O(3) catalyst was studied in a semi-batch slurry reactor over a temperature range of 373-453K and pressure range of 2.07-6.21 MPa. Semi-batch slurry reactor models were developed and kinetic parameters were estimated by fitting the integral batch reactor data at different temperatures to understand the influence of different reaction steps on the activity and selectivity of different products. Published by Elsevier Ltd.

10aBatch10acatalysis10akinetics10aMultiphase reactions10aPhenylenediamines10aReaction engineering10aReductive alkylation1 aRoy, Debdut1 aChaudhari, Amit, S.1 aChaudhari, Raghunath, V. uhttps://library.ncl.res.in/content/kinetics-reductive-alkylations-phenylenediamines-influence-substrates-isomeric-structure-0