Journal of the Korean Industrial and Engineering Chemistry, Vol.3, No.4, 710-716, December, 1992
아닐린의 산화적 카르보닐화에 의한 에틸페닐카바메이트의 합성의 속도론적 고찰
Kinetics of Ethyl Phenylcarbamate Synthesis by the Oxidative Carbonylation of Aniline
초록
에틸페닐카바메이트를 120℃, 79atm에서 전이금속촉매와 할로겐화 알칼리금속을 조촉매로하여 아닐린의 산화적 카르보닐화반응에 의하여 합성하였다. 산화제로서 산소를 사용하였으며 반응속도를 조사하고 활성화에너지를 추정하였다. 5시간 반응후 전환율은 100%, 선택도는 95%이었고 촉매로서는 Pd촉매가 Rh촉매보다 약간 효과가 좋았으며 조촉매로서의 효율은 KI>KBr>KCl 순이었다. 75℃에서 120℃사이에서 온도의 증가에 따라 반응속도가 증가되었으며 반응은 겉보기 1차반응이었고 활성화 에너지는 5% Pd/C와 5% Rh/C에서 각각 5.647, 5,780 kcal/mol이었다.
Ethylphenyl carbarmate(EPC ) was synthesized by oxidative CO carbonylation of aniline in the presence of transition metal catalysts and alkali metal halide cocatalysts at 120℃ under the pressure of 79atm. Oxygen gas was used for oxidizing agent. Kinetics of the reaction was studied and activation energies with different catalysts were estimated. About 100% conversion to EPC and 95% selectivity was obtained in 5 hour reaction. 5% Pd/C was more effective than 5% Rh/C. Effectiveness of cocatalysts was in the order of KI>KBr>KCl. As the temperature increased from 75℃ to 120℃, the conversion rate increased. The reaction was apparent first order and the activation energies with 5% Pd/C and 5% Rh/C were 5.647 and 5.780 kcal/mol, respectively.
- Fukuoka S, Chono M, Kohno M, J. Chem. Soc.-Chem. Commun., 399 (1984)
- Kondo K, Sonoda N, Tsutsumi S, Chem. Lett., 373 (1972)
- Moy D, U.S. Patent, 4,258,201, Mar. 24 (1981)
- Becker R, Grolig J, Rasp C, U.S. Patent, 4,219,661, Oct. 27 (1981)
- Fukuoka S, Chono M, Kohno M, J. Org. Chem., 49, 1458 (1984)
- Alper H, Vasapolio G, Hartstock FW, Mlekuz M, Smith DJH, Morris GE, Organometallics, 6, 2391 (1987)
- Cenini S, Pizzotti M, Crotti C, Porta F, Monica GL, J. Chem. Soc.-Chem. Commun., 1286 (1984)
- Han SH, Geoffroy GL, Rheingold RL, Inorg. Chem., 26, 3428 (1987)
- Foster D, Adv. Org. Chem., 171, 255 (1979)
- Heck RF, J. Am. Chem. Soc., 85, 2013 (1963)
- "International Critical Table," Vol. 3, pp. 260 (1963)