2-Methyl-4-methoxydiphenylamine 합성을 위한 촉매반응의 최적화

조정우; 김은석; 김기석; 김성훈

Journal of the Korean Industrial and Engineering Chemistry, Vol.10, No.2, 293-298, April, 1999

Export Citation

2-Methyl-4-methoxydiphenylamine 합성을 위한 촉매반응의 최적화

Optimization of Catalytic Reaction for Synthesis of 2-Methyl-4-methoxydiphenylamine

조정우, 김은석, 김기석, 김성훈

초록

Fluoran계 감열색소의 중간체인 2-Methyl-4-methoxydiphenylamine(MMDPA)을 합성하는 촉매반응의 반응기구를 규명하고 반응조건을 최적화하였다. 반응물질로서는 2-methyl-4-methoxyaniline(MMA), 3-methyl-4-nitroanisole(MNA), 그리고 cyclohexanone의 혼합물을 사용하였으며, 5 wt% Pd/C를 촉매로 사용하였다. 반응실험은 reflux condenser가 부착된 개방형 slurry reactor에서 진행시켰으며, 생성물은 GC/MS와 NMR에 의해서 분석하였다. 반응조건을 최적화 시킨 결과 xylene용매 속에서 0.01 gmoles MMA 투입기준으로 MMA:MNA:cyclohexanone=1:2:150의 반응물조성, 160℃의 반응온도, 0.5g 촉매량 조건에서 8∼10시간 경과 후 90 mole %의 MMDPA수율을 얻을 수 있었다. MMA와 cyclohexanone간의 축합반응에 의해 생성된 중간생성물의 탈수소화 반응단계가 총괄반응을 율속함을 알 수 있었다. MNA를 MMA와 함께 반응물에 투입함으로써 hydrogen transfer반응에 의하여 총괄반응속도와 MMDPA수율이 증대되었다. 반응물에 과량으로 투입된 cyclohexanone은 MMA와의 축합반응을 촉진시키는 역할을 하였다.

Reaction mechanism was elucidated and reaction condition were optimized for the catalytic reaction synthesizing 2-methyl-4-methoxy-diphenylamine (MMDPA) which is an intermediate of Fluoran heat-sensitive dyestuff. Reactants consisted of 2-methyl-4-methoxyaniline (MMA), 3-methyl-4-nitroanisole (MNA), and cyclohexanone, and 5 wt % Pd/C was used as a catalyst. Experiments were run in an open slurry reactor equipped with reflux condenser, and products were analyzed by means of GC/MS and NMR. MMDPA yield of 90 mole % could be obtained after reaction time of 8∼10 hours under the optimal reaction conditions comprising the reaction mass composition of MMA:MNA:cyclohexanone=1:2:150 based on MMA input of 0.01 gmoles in xylene solvent, reaction temperature of 160℃, and catalyst amount of 0.5 g. It was found that the rate-determining step of overall reaction was dehydrogenation of the intermediate product obtained from condensation of MMA and cyclohexanone. Overall reaction rate and MMDPA yield were enhanced owing to hydrogen transfer reaction by introducing MNA together with MMA in the reaction mass. Excess cyclohexanone in the reaction mass played an important role of promoting the condensation of MMA and cyclohexanone.

Keywords:2-Methyl-4-methoxydiphenylamine;Rate-determining Step;Hydrogen-transfer reaction;Cyclohexanone

[References]

Nagata T, Kusuda C, Wada M, U.S. Patent, 5,545,752 (1996)
Friedrich WC, Heinz UB, U.S. Patent, 4,265,833 (1981)
Otto IK, Gerhard D, Hans JB, U.S. Patent, 5,338,885 (1994)
Kondo M, Iwasaki H, Kanda N, Omatsu M, Omura H, European Patent, 89,752 (1983)
Ito H, Jinno Y, Nagata T, Yokomachi I, 일본특허 特開昭 61-218,560 (1986)
Akamatsu T, 일본특허 特開平 05-117,214 (1993)
Marsohik JF, Rylander PN, U.S. Patent, 3,517,021 (1970)
Ricoh Co., Ltd., 일본특허 特開昭 60-51,157 (1985)
Rylander PN, Hydrogenation Methods, Academic Press, London (1985)
Augustine RL, Catalytic Hydrogenation, Marcel Dekker, New York (1985)
ICI, U.S. Patent, 3,270,057 (1966)
Rylander PN, Greenfield H, Catalysis of Organic Reactions, Marcel Dekker, New York (1987)

[1] Nagata T, Kusuda C, Wada M, U.S. Patent, 5,545,752 (1996)

[2] Friedrich WC, Heinz UB, U.S. Patent, 4,265,833 (1981)

[3] Otto IK, Gerhard D, Hans JB, U.S. Patent, 5,338,885 (1994)

[4] Kondo M, Iwasaki H, Kanda N, Omatsu M, Omura H, European Patent, 89,752 (1983)

[5] Ito H, Jinno Y, Nagata T, Yokomachi I, 일본특허 特開昭 61-218,560 (1986)

[6] Akamatsu T, 일본특허 特開平 05-117,214 (1993)

[7] Marsohik JF, Rylander PN, U.S. Patent, 3,517,021 (1970)

[8] Ricoh Co., Ltd., 일본특허 特開昭 60-51,157 (1985)

[9] Rylander PN, Hydrogenation Methods, Academic Press, London (1985)

[10] Augustine RL, Catalytic Hydrogenation, Marcel Dekker, New York (1985)

[11] ICI, U.S. Patent, 3,270,057 (1966)

[12] Rylander PN, Greenfield H, Catalysis of Organic Reactions, Marcel Dekker, New York (1987)