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Study on the Deactivation Kinetics of Pd(PPh_3)_2Cl_2 in the Monocarbonylation of Benzyl Chloride 被引量:2

Study on the Deactivation Kinetics of Pd(PPh_3)_2Cl_2 in the Monocarbonylation of Benzyl Chloride
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摘要 The deactivation kinetics of Pd(PPh3)2Cl2 in the monocarbonylation of benzyl chloride to synthesize phenylacetic acid is studied in this paper. Solid 1-(2-pyridylazo)-2-naphthol (PAN) is used as the colouring agent, and the concentration of Pd(PPh3)2Cl2 in the system is measured through absorptiometry. The result shows that the optimum condition of the chromogenic reaction between Pd2+ and PAN is: 0.5 ml of 0.04% PAN added to 10 ml of Pd2+ solution (1.0×10-6-2.0×10-5 mol/L), and heated in a constant temperature water bath at 40℃ for about 30 min, with pH of the solution being about 3.0. The molar coefficient of absorption is 1.384×104 L/(mol·cm); the orders of the hydrolytic reaction to the concentration of Pd(PPh3)2Cl2, PPh3, phenylacetic acid and NaOH are 0.5, minus 0.8, 2 and 1.2, respectively. The activation energy (E) of the hydrolytic reaction is 75.59 kJ/mol, and the pre-exponential factor is 1.68×1012. The deactivation kinetics of Pd(PPh3)2Cl2 in the monocarbonylation of benzyl chloride to synthesize phenylacetic acid is studied in this paper. Solid 1-(2-pyridylazo)-2-naphthol (PAN) is used as the colouring agent, and the concentration of Pd(PPh3)2Cl2 in the system is measured through absorptiometry. The result shows that the optimum condition of the chromogenic reaction between Pd2+ and PAN is: 0.5 ml of 0.04% PAN added to 10 ml of Pd2+ solution (1.0×10-6-2.0×10-5 mol/L), and heated in a constant temperature water bath at 40℃ for about 30 min, with pH of the solution being about 3.0. The molar coefficient of absorption is 1.384×104 L/(mol·cm); the orders of the hydrolytic reaction to the concentration of Pd(PPh3)2Cl2, PPh3, phenylacetic acid and NaOH are 0.5, minus 0.8, 2 and 1.2, respectively. The activation energy (E) of the hydrolytic reaction is 75.59 kJ/mol, and the pre-exponential factor is 1.68×1012.
出处 《Journal of Natural Gas Chemistry》 CAS CSCD 2004年第3期177-183,共7页 天然气化学杂志(英文版)
基金 Project supported by the Foundation of Scientific and Technological from the Ministry of Education (No. 03071), of Natural Science Foundation of Jiangxi Province (No. 0320013) of the Youth Foundation of Nanchang University.
关键词 dichloro-bistriphenylphosphine palladium deactivation kinetics HYDROLYSIS ABSORPTIOMETRY dichloro-bistriphenylphosphine palladium, deactivation kinetics, hydrolysis, absorptiometry
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  • 1Hiroshi Itatani,John C. Bailar.Homogenous catalysis in the reactions of olefinic substances. V. Hydrogenation of soybean oil methyl ester with triphenylphosphine and triphenylarsine palladium catalysts[J].Journal of the American Oil Chemists’ Society.1967(2)
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