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Received August 19, 2005
Accepted October 27, 2005
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HMCM-41 촉매에서 2,3-Dihydrobenzofuran 유도체의 합성
Synthesis of 2,3-Dihydrobenzofuran Derivatives over HMCM-41 Catalysts
전남대학교 응용화학공학부, 500-757 광주시 북구 용봉동 300
School of Applied Chemical Engineering, Chonnam National University, 300, Yongbong-dong, Puk-gu, Gwangju 500-757, Korea
Korean Chemical Engineering Research, December 2005, 43(6), 662-667(6), NONE Epub 23 January 2006
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Abstract
HMCM-41 중간세공 물질(mesoporous material) 촉매를 사용하여 aryl methallyl ether로부터 의약품과 농약의 주요 중간체인 2,3-dihydrobenzofuran 유도체를 합성하였다. 산점 농도가 촉매 활성에 미치는 영향을 비교하기 위하여 Si/Al 몰비가 40과 50으로 다른 촉매를 제조하였으며, aryl methallyl ether에 다양한 치환기를 도입하여 벤젠 고리의 전자 밀도가 전환율과 수율에 미치는 효과를 조사하였다. 산점이 많아질수록 전환율은 높아졌으나, 2,3-dihydorbenzofuran 유도체의 수율과 직접 연관짓기는 어려웠다. 전자공여기의 치환으로 벤젠 고리의 전자 밀도가 높아지면 claisen 자리옮김 반응이 빨라져서 2,3-dihydrobenzofuran 유도체가 많이 생성되었다. 반면, 전자흡인기가 치환되어 벤젠 고리의 전자 밀도가 낮아지면 산 촉매에 의해 aryl methallyl ether 분해 반응이 촉진되어 2,3-dihydrobenzofuran 유도체 대신 phenol 유도체가 생성되었다.
2,3-Dihydrobenzofuran derivatives, important intermediates of medicines and agricultural chemicals, were prepared from aryl methallyl ethers over MCM-41 mesoporous material catalysts. Two mesoporous materials with Si/Al mole ratios of 40 and 50 were prepared to investigate the effect of acid site concentration on their catalytic activities. Aryl methallyl ethers with various substituents on their benzene rings were used to investigate the effect of electron density on benzene ring on the conversion of the ethers and the yield of 2,3-dihydorbenzofuran derivatives. The catalyst with a high acid site concentration showed high conversions, but it is difficult to correlate the yield of the derivatives with the acid site concentration. The increase in the electron density of the benzene ring by introducing electron-donating groups accelerated Claisen rearrangement reaction, resulting in the enhanced yield of the derivatives. On the other hand, the decrease in the electron density by introducing electron-attracting groups accelerated the cracking reaction of aryl methallyl ether by acid catalysts, producing phenol derivatives rather than 2,3-dihydrobenzofuran derivatives.
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Widmer U, Hansen HJ, Schmid H, Helv. Chim. Acta, 56(7), 2644 (1973)
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Kim KM, Kim HR, Ryu EK, Heterocycles, 36(3), 497 (1993)
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Kim HJ, Seo G, Kim JN, Choi KH, Bull. Korean Chem. Soc., 25, 1726 (2004)
Hartmann M, Poppl A, Kevan L, J. Phys. Chem., 99(49), 17494 (1995)
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