02168nas a2200241 4500008004100000022001400041245012000055210006900175260007300244300001200317490000800329520127700337653001801614653002401632653001301656653002201669653001901691653001401710100002101724700002501745700002901770856012701799 2009 eng d a1381-116900aHydroesterification of 2-vinyl-6-methoxynaphthalene using palladium complexes containing chelating nitrogen ligands0 aHydroesterification of 2vinyl6methoxynaphthalene using palladium aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcJUL a134-1410 v3073 a

Hydroesterification of 2-vinyl-6-methoxynaphthalene (VMN) to methyl ester of 6-methoxy naphthyl propionic acid (ester of naproxen) has been investigated using palladium complexes containing the chelating N(boolean AND)O and N(boolean AND)N ligands (pyridine-2-carboxylate, 2-acetylpyridine, 2-pyridine-carboxaldehyde, and bipyridine) as catalysts. Palladium complex containing 2-acetylpyridine as the ligand was found to be superior to other Pd-complexes. Both acid and halide promoters were necessary for high activity and selectivity. As an acid promoter, benzenesulfonic acid was found to be more effective compared to p-toluenesulfonic acid. Formation of ether 2-methoxy-6-(1-methoxyethyl)naphthalene and a polymer of VMN was observed in all the reactions. It was observed that active catalytic species generated during carbonylation reaction was responsible for the polymer formation. The effect of various parameters such as solvents, CO pressure, and alcohols on the catalytic activity as well as the selectivity was investigated. The turnover frequency using the complex Pd(acpy)(PPh(3))(OTs)(2) (acpy = 2-acetylpyridine) catalyst was found to be 42 h(-1), which is the highest for the hydroesterification of VMN. (C) 2009 Elsevier B.V. All rights reserved.

10aCarbonylation10aHydroesterification10aNaproxen10aPalladium complex10aPolymer of VMN10aPromoters1 aAtla, Shashi, B.1 aKelkar, Ashutosh, A.1 aChaudhari, Raghunath, V. uhttps://library.ncl.res.in/content/hydroesterification-2-vinyl-6-methoxynaphthalene-using-palladium-complexes-containing-002395nas a2200169 4500008004100000022001400041245011900055210006900174260007100243300001400314490000700328520168200335100002302017700002502040700002902065856013102094 2009 eng d a0888-588500aHydroformylation of 1,4-diacetoxy-2-butene using HRh(CO)(PPh3)(3) tethered on alumina as a catalyst: kinetic study0 aHydroformylation of 14diacetoxy2butene using HRhCOPPh33 tethered a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcNOV a9479-94890 v483 a

Hydroformylation of 1,4-diacetoxy-2-butene (DAB) was studied using [HRh(CO)(PPh3)(3)] complex catalyst tethered on alumina using phosphotungstic acid (PTA) as an anchoring agent, with the aim to understand the product distribution, selectivity, and intrinsic kinetics. It was observed that with the tethered heterogeneous catalyst a simultaneous hydroformylation followed by deacetoxylation steps was possible, which is relevant for combining two steps in the sequence of synthesis of vitamin-A intermediate [2-formyl-4-acetoxy butene (FAB)]. P-31 cross-polarization magic angle spinning nuclear magnetic resonance (CP MAS NMR) and infrared (IR) instrumental techniques were found be the most effective techniques to establish the catalyst structure and true heterogeneity. On the basis of the spectroscopic evidence, we postulate the loss of a PPh3 group during tethering to give HRh(CO)(PPh3)(2)-PTA-Al2O3 as a heterogeneous complex catalyst. Experimental data on the concentration-time and CO/H-2 consumption-time profiles were obtained and the effects of DAB concentration, CO partial pressure, H-2 partial pressure, and catalyst loading were studied in a 50 mL stirred batch reactor over a temperature range of 338-358 K. The analysis of solid-liquid-gas mass transfer effects was investigated to ensure that the reaction was operating in the kinetic regime Various models were developed, and the best model was chosen by a model discrimination procedure. The agreement between the model prediction and the experimental data was found to be excellent. The activation energies for the hydroformylation and deacetoxylation steps were found to be 42.5 and 80.2 kJ/mol.

1 aChansarkar, Rashmi1 aKelkar, Ashutosh, A.1 aChaudhari, Raghunath, V. uhttps://library.ncl.res.in/content/hydroformylation-14-diacetoxy-2-butene-using-hrhcopph33-tethered-alumina-catalyst-kinetic-001537nas a2200193 4500008004100000022001400041245014600055210006900201260007100270300001600341490000700357520072900364100001701093700002901110700002901139700002501168700001801193856013201211 2010 eng d a0888-588500aHydroformylation of 1-octene using [Bmim][PF6]-decane biphasic media and rhodium complex catalyst: thermodynamic properties and kinetic study0 aHydroformylation of 1octene using BmimPF6decane biphasic media a a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcNOV a10698-107060 v493 a

A chemical reaction engineering approach is reported to investigate the biphasic hydroformylation of I-octene using [bmim][PF6] ionic liquid. It is based both on a process parameter investigation (temperature, concentrations, and pressures) and a thermodynamic study of the reaction medium (gas liquid and liquid liquid equilibria). Initial rate data show complex behavior with respect to operating parameters and are best described by a rate equation based on a mechanistic model. Complete reaction scheme including isomerization is then modeled accounting from the time dependent concentration of the organic substrates measured in organic phase and recalculated in ionic liquid phase from liquid liquid equilibria.

1 aSharma, Amit1 aLebigue, Carine, Julcour1 aDeshpande, Raj, Madhukar1 aKelkar, Ashutosh, A.1 aDelmas, Henri uhttps://library.ncl.res.in/content/hydroformylation-1-octene-using-bmimpf6-decane-biphasic-media-and-rhodium-complex-catalyst-0