HMCM-41 촉매에서 2,3-Dihydrobenzofuran 유도체의 합성

김형진; 서곤; 김정년; 최경호; Hyung Jin Kim; Gon Seo; Jung-Nyun Kim; Kyung Ho Choi

Korean Chemical Engineering Research, Vol.43, No.6, 662-667, December, 2005

Export Citation

HMCM-41 촉매에서 2,3-Dihydrobenzofuran 유도체의 합성

Synthesis of 2,3-Dihydrobenzofuran Derivatives over HMCM-41 Catalysts

김형진 ^†, 서곤 , 김정년, 최경호

전남대학교 응용화학공학부, 500-757 광주시 북구 용봉동 300

Hyung Jin Kim^†, Gon Seo , Jung-Nyun Kim, and Kyung Ho Choi

School of Applied Chemical Engineering, Chonnam National University, 300, Yongbong-dong, Puk-gu, Gwangju 500-757, Korea

E-mail:

초록

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.

Keywords:HMCM-41;Dihydrobenzofuran;Cyclization Reaction;Acid Catalyst

[References]

Breck DW, Zeolite Molecular Sieves, Wiley, New York (1974)
Dyer A, An Introduction to Zeolite Molecular Sieves, Wiley, Chichester (1988)
Holderich W, Hesse M, Naumann F, Angew. Chem.-Int. Edit., 27(2), 226 (1988)
Kim Y, Kim P, Kim C, Yi J, Korean J. Chem. Eng., 22(2), 321 (2005)
Jung KH, Chung KH, Kim MY, Kim JH, Seo G, Korean J. Chem. Eng., 16(3), 396 (1999)
Seo G, Kim TJ, Lim S, Ko CH, Ryoo R, Korean J. Chem. Eng., 15(6), 611 (1998)
Han SH, Yang JS, Choung SJ, HWAHAK KONGHAK, 38(5), 578 (2000)
Jentys A, Pham NH, Vinek H, Englisch M, Lercher JA, Microporous Mesoporous Mater., 6(1), 13 (1996)
Armengol E, Cano ML, Corma A, Garcia H, Navarro MT, J. Chem. Soc. Chem. Comm.(5), 519 (1995)
Subrahmanyam C, Viswanathan B, Varadarajan TK, J. Mol. Catal. A-Chem., 226(2), 155 (2005)
Selvam P, Dapurkar SE, Catal. Today, 96(3), 135 (2004)
Ravindra DB, Nie YT, Jaenicke S, Chuah GK, Catal. Today, 96(3), 147 (2004)
Kugita T, Jana SK, Owada T, Hashimoto N, Onaka M, Namba S, Appl. Catal. A: Gen., 245(2), 353 (2003)
Onaka M, Yamasaki R, Chem. Lett., 6(3), 259 (1998)
Mikami K, Ohmura H, Yamanaka M, J. Org. Chem., 68(3), 1081 (2003)
Yadav GD, Murkute AD, Langmuir, 20(26), 11607 (2004)
Ryoo R, Chem World, 38(11), 26 (1998)
Park SE, ibid, 38(11), 30 (1998)
Donnelly DMX, Meegan MJ, Comprehensive Heterocyclic Chemistry; Katritzky, A. R., Rees, C. W,. Eds.; Pergamon Press: Oxford, 4, 705 (1984)
Keay BA, Comprehensive Heterocyclic Chemistry, Katritzky, A. R., Rees, C. W., Scriven, E. F., Eds., Elsevier Science Ltd., New York, 2, 413-436 (1996)
Shulgin AT, Baker AW, J. Org. Chem., 28(9), 2468 (1963)
Harwood LM, J. Chem. Soc. Chem. Commun., 9, 530 (1983)
Widmer U, Hansen HJ, Schmid H, Helv. Chim. Acta, 56(7), 2644 (1973)
Nichols DE, Hoffman AJ, Oberlender RA, Riggs RM, J. Med. Chem., 29(2), 302 (1986)
Feoktistov VM, Bunina-Krivorukova LI, Bal'yan KHV, Zh. Org. Khim., 14(4), 807 (1978)
Kim KM, Kim HR, Ryu EK, Heterocycles, 36(3), 497 (1993)
Kang SK, Kim SS, Choi JK, Yum EK, Bull. Korean Chem. Soc., 18(10), 1128 (1997)
Kataoka K, Shiota T, Takeyasu T, Minoshima T, Watanabe K, Tanaka H, Mochizuki T, Taneda K, Ota M, Tanabe H, Yamaguchi H, J. Med. Chem., 39(6), 1262 (1996)
Bernard AM, Cocco MT, Onnis V, Piras PP, Synthesis, 1, 41 (1997)
Bernard AM, Cocco MT, Onnis V, Piras PP, Synthesis(3), 256 (1998)
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)
Ryu EK, Kim KM, Kim HR, Song JH, Kim JN, Kim JS, "Preparation of Herbicidal Benzofuranylcyclohexane-1,3-dione Derivatives", PCT Int. Appl., WO 9403443 (1994)
Ariamala G, Balasubramanian KK, Tetrahedron, 45(12), 3769 (1989)

[Related Articles]

[1] Breck DW, Zeolite Molecular Sieves, Wiley, New York (1974)

[2] Dyer A, An Introduction to Zeolite Molecular Sieves, Wiley, Chichester (1988)

[3] Holderich W, Hesse M, Naumann F, Angew. Chem.-Int. Edit., 27(2), 226 (1988)

[4] Kim Y, Kim P, Kim C, Yi J, Korean J. Chem. Eng., 22(2), 321 (2005)

[5] Jung KH, Chung KH, Kim MY, Kim JH, Seo G, Korean J. Chem. Eng., 16(3), 396 (1999)

[6] Seo G, Kim TJ, Lim S, Ko CH, Ryoo R, Korean J. Chem. Eng., 15(6), 611 (1998)

[7] Han SH, Yang JS, Choung SJ, HWAHAK KONGHAK, 38(5), 578 (2000)

[8] Jentys A, Pham NH, Vinek H, Englisch M, Lercher JA, Microporous Mesoporous Mater., 6(1), 13 (1996)

[9] Armengol E, Cano ML, Corma A, Garcia H, Navarro MT, J. Chem. Soc. Chem. Comm.(5), 519 (1995)

[10] Subrahmanyam C, Viswanathan B, Varadarajan TK, J. Mol. Catal. A-Chem., 226(2), 155 (2005)

[11] Selvam P, Dapurkar SE, Catal. Today, 96(3), 135 (2004)

[12] Ravindra DB, Nie YT, Jaenicke S, Chuah GK, Catal. Today, 96(3), 147 (2004)

[13] Kugita T, Jana SK, Owada T, Hashimoto N, Onaka M, Namba S, Appl. Catal. A: Gen., 245(2), 353 (2003)

[14] Onaka M, Yamasaki R, Chem. Lett., 6(3), 259 (1998)

[15] Mikami K, Ohmura H, Yamanaka M, J. Org. Chem., 68(3), 1081 (2003)

[16] Yadav GD, Murkute AD, Langmuir, 20(26), 11607 (2004)

[17] Ryoo R, Chem World, 38(11), 26 (1998)

[18] Park SE, ibid, 38(11), 30 (1998)

[19] Donnelly DMX, Meegan MJ, Comprehensive Heterocyclic Chemistry; Katritzky, A. R., Rees, C. W,. Eds.; Pergamon Press: Oxford, 4, 705 (1984)

[20] Keay BA, Comprehensive Heterocyclic Chemistry, Katritzky, A. R., Rees, C. W., Scriven, E. F., Eds., Elsevier Science Ltd., New York, 2, 413-436 (1996)

[21] Shulgin AT, Baker AW, J. Org. Chem., 28(9), 2468 (1963)

[22] Harwood LM, J. Chem. Soc. Chem. Commun., 9, 530 (1983)

[23] Widmer U, Hansen HJ, Schmid H, Helv. Chim. Acta, 56(7), 2644 (1973)

[24] Nichols DE, Hoffman AJ, Oberlender RA, Riggs RM, J. Med. Chem., 29(2), 302 (1986)

[25] Feoktistov VM, Bunina-Krivorukova LI, Bal'yan KHV, Zh. Org. Khim., 14(4), 807 (1978)

[26] Kim KM, Kim HR, Ryu EK, Heterocycles, 36(3), 497 (1993)

[27] Kang SK, Kim SS, Choi JK, Yum EK, Bull. Korean Chem. Soc., 18(10), 1128 (1997)

[28] Kataoka K, Shiota T, Takeyasu T, Minoshima T, Watanabe K, Tanaka H, Mochizuki T, Taneda K, Ota M, Tanabe H, Yamaguchi H, J. Med. Chem., 39(6), 1262 (1996)

[29] Bernard AM, Cocco MT, Onnis V, Piras PP, Synthesis, 1, 41 (1997)

[30] Bernard AM, Cocco MT, Onnis V, Piras PP, Synthesis(3), 256 (1998)

[31] Kim HJ, Seo G, Kim JN, Choi KH, Bull. Korean Chem. Soc., 25, 1726 (2004)

[32] Hartmann M, Poppl A, Kevan L, J. Phys. Chem., 99(49), 17494 (1995)

[33] Ryu EK, Kim KM, Kim HR, Song JH, Kim JN, Kim JS, "Preparation of Herbicidal Benzofuranylcyclohexane-1,3-dione Derivatives", PCT Int. Appl., WO 9403443 (1994)

[34] Ariamala G, Balasubramanian KK, Tetrahedron, 45(12), 3769 (1989)