@article {49418,
	title = {Kinetic investigation on palladium-catalyzed carbonylation of allyl alcohol},
	journal = {International Journal of Chemical Kinetics},
	volume = {57},
	year = {2025},
	month = {OCT},
	pages = {153-163},
	type = {Article},
	abstract = {<p>
	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.</p>
},
	keywords = {allyl alcohol, Carbonylation, halide promoters, kinetics, Mechanism, Palladium},
	issn = {0538-8066},
	doi = {10.1002/kin.21767},
	author = {Tonde, Sunil S. and Rajurkar, Kalpendra B. and Pagar, Nitin S.}
}
@article {50223,
	title = {Kinetics of palladium catalyzed methoxycarbonylation of vinyl acetate to methyl-2-acetoxypropionate for the synthesis of lactic acid},
	journal = {International Journal of Chemical Kinetics},
	volume = {58},
	year = {2026},
	month = {SEP},
	pages = {627-636},
	type = {Article},
	abstract = {<p>
	Lactic acid is crucial for food production and energy generation in body. It also has been a key monomer of poly lactic acid, biodegradable plastic. As methoxy carbonylation of vinyl acetate (VAM) produces methyl-2-acetoxypropionate, and methyl lactate as intermediates for lactic acid, its kinetic investigations are important to understand the reaction behavior. In this paper a study was conducted on the kinetics of methoxyarbonylation for vinyl acetate in a semi-batch slurry reactor across a temperature range of 363-383K, utilizing [PdCl2(PPh3)2] catalyst. The effect of catalyst, methanol, vinyl acetate monomer (VAM) concentration and partial pressure of carbon monoxide (CO) on the reactants and products concentration was investigated with respect to time. Catalytic methoxycarbonylation of VAM produces methyl acetoxy propionate which further forms methyl lactate and methyl acetate through consecutive reaction. Methyl acetoxy propionate and methyl lactate thus formed can be converted to lactic acid through hydrolysis. The methoxycarbonylation conditions produce byproducts dimethyl acetate and methyl acetate through parallel reaction. Based on the initial rate data of formations of lactic acid precursors through methoxycarbonylation and consecutive reaction byproducts through parallel reaction, and trend behavior of initial rates with concentrations of reactants, different empirical rate equations were evaluated. The integral concentration-time data was fitted to evaluate the kinetic parameters at various temperatures. General elimination method and thermodynamic principles were used to suggest an appropriate empirical rate equation as shown below.r1, r2, and r3 are rates of methoxycarbonylation reaction (methyl-2-acetoxypropionate formation), consecutive reaction (methyl lactate formation) and parallel reaction (dimethyl acetal formation) respectively. k1, k2, and k3 are equilibrium constants for the reactions r1, r2, and r3 respectively. KB and KC are equilibrium constants for VAM and methanol CA, CB, CC, CD and CW are concentration of dissolved CO in the liquid phase, VAM, methanol, methyl-2-acetoxypropionate and catalyst respectively. For catalyst and CO, the methoxycarbonylation reaction rate was observed to be first order, while for VAM and methanol, it was first order with a tendency to zero order. Energy of activation needed for the catalytic reaction was 81.62 kJ/mol. For a catalytic reaction, selectivity towards the required product is desirable. Kinetic investigations can be utilized to achieve maximum selectivity towards the desired products at optimum reaction rate. The proposed model suggests that 95\%-97\% selectivity towards the combined carbonylated products (methyl-2-acetoxypropionate and methyl lactate) can be achieved.</p>
},
	keywords = {Hydrolysis, kinetics, Lactic acid, Methoxycarbonylation, methyl lactate, methyl-2-acetoxypropionate, palladium catalyst, VAM},
	issn = {0538-8066},
	doi = {10.1002/kin.70072},
	author = {Tonde, Sunil S. and Rajurkar, Kalpendra B. and Pagar, Nitin S.}
}
