02501nas a2200193 4500008004100000022001400041245009300055210006900148260007100217300001400288490000700302520174800309100002802057700002102085700002502106700002102131700002902152856012602181 2007 eng d a0888-588500aEnvironmentally benign catalytic hydroformylation-oxidation route for naproxen synthesis0 aEnvironmentally benign catalytic hydroformylationoxidation route a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcDEC a8480-84890 v463 a

Hydroformylation of 6-methoxy-2-vinylnaphthalene (MVN), using homogeneous Rh(CO)acac) as a catalyst and a chelating bidentate ligand (1,2-bis-(diphenylphosphino) ethane, dppe), followed by oxidation of the product (2-(6-methoxynaphthyl) propanal, 2-MNP) has been studied as an alternative route for the synthesis Of D,L-naproxen. The feasibility of the MVN hydroformylation route has been demonstrated, and a detailed study has been reported on the key hydroformylation step. The roles of the catalyst, ligands, and solvents, as well as the effect of reaction conditions on the reaction rate and regioselectivity of the product 2-MNP, have been investigated. With Rh(CO)2(acac) as a catalyst and dppe as a ligand, > 98% selectivity to 2-MNP (an important precursor to D,L-naproxen) has been achieved. A possible mechanism to explain the variation in regioselectivity with Rh(CO)(2)(acac) as a catalyst and dppe as a ligand has been discussed. The kinetics of the hydroformylation step has been investigated and a rate equation has been proposed. The second step in the proposed route for naproxen-the oxidation of 2-MNP to 2-(6-methoxynaphthyl) propanoic acid (2-MNPA, or naproxen) - has been studied using Na2WO4 as a catalyst and tetrabutyl ammonium hydrogen sulfate (TBAHS) as the phase-transfer catalyst with H2O2 as the oxidant for the first time. Screening of the catalysts that consisted of the early transition metals, such as salts of tungsten, vanadium, and molybdenum showed that Na2WO4 gives the best performance for the oxidation step with > 80% selectivity to 2-(6-methoxynaphthyl)propanoic acid (2-MNPA/naproxen). This study would be valuable in developing a new environmentally benign route for naproxen synthesis.

1 aRajurkar, Kalpendra, B.1 aTonde, Sunil, S.1 aDidgikar, Mahesh, R.1 aJoshi, Sunil, S.1 aChaudhari, Raghunath, V. uhttps://library.ncl.res.in/content/environmentally-benign-catalytic-hydroformylation-oxidation-route-naproxen-synthesis-001839nas 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-002407nas a2200289 4500008004100000020002200041022001400063245010400077210006900181260019400250300001200444490000900456520127500465653002101740653003301761653002101794653001901815653001801834100002501852700002801877700001901905700002701924700001501951700001201966700001201978856012701990 2010 eng d a978-0-7354-0854-8 a0094-243X00aDynamic modeling of hydro- formylation of 1-decene on Rh/C catalyst in bubble colunm slurry reactor0 aDynamic modeling of hydro formylation of 1decene on RhC catalyst a2 Huntington Quadrangle, STE 1NO1, Melville, NY 11747-4501 USAbNatl Inst Technol Durgapur; SERC, Dept Sci & Technol; Caledonian Coll Engn; BRNS, Dept Atom Energy; DRDO, Minist DefencecOCT a143-1500 v12983 a

A dynamic model has been developed for the bubble column slurry reactor operating under non-isothermal conditions. The model consists of mass and heat balance equations for the gas and liquid phases and the catalyst particle. The model equations consisted of partial differential equations (PDE) which were converted to ordinary differential equations (ODE) by using finite difference relationships for the spatial derivatives and the ordinary differential equations for the time derivatives (Numerical Method of Lines-NMoL). The model was applied to describe the dynamic behaviour of bubble column slurry reactor during the hydroformylation of 1-decene on Rh/C catalyst. Model simulations were performed to obtain a meaningful path to steady state and to reproduce the other characteristics of the dynamic behaviour of the reactor. Under given conditions, the reaction required approximately 3750 seconds to reach the steady state concentrations at various reactor positions. It was observed with increase in the fluid velocities, the dynamics of the system was altered to 2500 seconds to reach the steady state condition. The effect of axial dispersion on the substrate concentration and the temperature rise along the reactor was further studied and discussed.

10aaxial dispersion10abubble column slurry reactor10aDynamic modeling10amethod of line10aPDE solutions1 aUpkare, Makarand, M.1 aRajurkar, Kalpendra, B.1 aDas, Samir, K.1 aJaganathan, Rengaswamy1 aParuya, S.1 aKar, S.1 aRoy, S. uhttps://library.ncl.res.in/content/dynamic-modeling-hydro-formylation-1-decene-rhc-catalyst-bubble-colunm-slurry-reactor-001740nas a2200265 4500008004100000020002200041022001400063245011200077210006900189260019400258300001200452490000900464520062700473653002401100653002601124653005201150100002501202700002801227700002201255700002701277700001501304700001201319700001101331856013201342 2010 eng d a978-0-7354-0854-8 a0094-243X00aMathematical modeling and simulation of bubble column reactor for aerial liquid phase cyclohexane oxidation0 aMathematical modeling and simulation of bubble column reactor fo a2 Huntington Quadrangle, STE 1no1, Melville, NY 11747-4501 USAbNatl Inst Technol Durgapur; SERC, Dept Sci & Technol; Caledonian Coll Engn; BRNS, Dept Atom Energy; DRDO, Minist DefencecOCT a151-1590 v12983 a

Cyclohexane oxidation is an important but complex commercial reaction, wherein the desired product, K-A oil appears as an intermediates of the reaction sequence. A mathematical model has been developed for the bubble column reactor operating under isothermal conditions. The mass and energy model equations consisted of stiff ODEs. The model was applied to describe the behavior of bubble column reactor for aerial liquid phase cyclohexane oxidation. Effect of initial substrate concentration, catalyst loading and temperature was studied and discussed in detail. Conclusions were presented at the end of the study.

10aK-A Oil Selectivity10aMathematical modeling10asubstrate conversion and product yield analysis1 aUpkare, Makarand, M.1 aRajurkar, Kalpendra, B.1 aGupta, Pankaj, R.1 aJaganathan, Rengaswamy1 aParuya, S.1 aKar, S.1 aRoy, S uhttps://library.ncl.res.in/content/mathematical-modeling-and-simulation-bubble-column-reactor-aerial-liquid-phase-cyclohexane-001621nas a2200229 4500008004100000022001400041245007800055210006900133260000800202300001200210490000700222520089800229653001301127653001601140653002101156653001301177653002201190100002101212700002801233700002301261856010701284 2020 eng d a0538-806600aKinetics of hydroformylation of camphene using rhodium-phosphite catalyst0 aKinetics of hydroformylation of camphene using rhodiumphosphite  cJUL a485-4950 v523 a

Kinetics of hydroformylation of camphene was investigated in the presence of [Rh(CO)(2)(acac)]/P(OPh)(3) catalyst in a temperature range of 363-383 K. The influence of parameters such as stirring speed, camphene, catalyst, ligand concentrations, and partial pressures of H-2 and CO on the activity and selectivity of the catalyst has been studied. The rate showed a first-order dependence with respect to catalyst and camphene concentrations. The effect of partial pressure of hydrogen showed fractional order dependence. The plots of rate versus excess ligand, that is, (P(OPh)(3)) concentration and rate versus CO partial pressure passed through maxima and showed typical substrate/ligand inhibited kinetics. An empirical rate equation has been proposed and found to be in good agreement with the observed rate data. The kinetic parameters and activation energy were also evaluated.

10acamphene10ahomogeneous10aHydroformylation10akinetics10arhodium-phosphite1 aPagar, Nitin, S.1 aRajurkar, Kalpendra, B.1 aDeshpande, Raj, M. uhttps://library.ncl.res.in/content/kinetics-hydroformylation-camphene-using-rhodium-phosphite-catalyst01490nas a2200241 4500008004100000022001400041245008000055210006900135260000800204300001200212490000700224520074000231653001800971653001800989653002101007653001301028653001401041653001401055100002101069700002801090700002101118856010901139 2025 eng d a0538-806600aKinetic investigation on palladium-catalyzed carbonylation of allyl alcohol0 aKinetic investigation on palladiumcatalyzed carbonylation of all cOCT a153-1630 v573 a

Palladium-catalyzed carbonylation of allyl alcohol to 3-butenoic acid has been investigated. A significant effect of halide promoters, p-tolylsulfonic acid (TsOH), water, solvents, and PPh3 concentration activity and selectivity has been studied. Detailed kinetics of this reaction was investigated in a temperature range of 363-383 K. The influence of parameters such as stirring speed, allyl alcohol, catalyst, benzyltriethylammonium chloride (BTEAC), TsOH concentrations, and CO partial pressures on the activity and selectivity has been studied. An empirical rate equation was suggested and found to be fairly consistent with observed rate data. In addition, the activation energy and kinetic parameters were evaluated.

10aallyl alcohol10aCarbonylation10ahalide promoters10akinetics10aMechanism10aPalladium1 aTonde, Sunil, S.1 aRajurkar, Kalpendra, B.1 aPagar, Nitin, S. uhttps://library.ncl.res.in/content/kinetic-investigation-palladium-catalyzed-carbonylation-allyl-alcohol