팔라듐 담지 다공성 폴리우레아를 불균일 촉매로 활용한 Suzuki-Miyaura 커플링 반응

소재일; 천영걸; 황소산; 진명종; 심상은; Jae Il So; Yingje Qian; Sosan Hwang; Myung Jong Jin; Sang Eun Shim

Polymer(Korea), Vol.42, No.3, 529-538, May, 2018

DOI10.7317/pk.2018.42.3.529 Export Citation

팔라듐 담지 다공성 폴리우레아를 불균일 촉매로 활용한 Suzuki-Miyaura 커플링 반응

Palladium Supported Porous Polyurea Frameworks as an Efficient Heterogeneous Catalyst for Suzuki-Miyaura Cross-coupling Reaction

소재일, 천영걸, 황소산, 진명종, 심상은^†

인하대학교 화학 및 화학공학 융합대학원

Jae Il So, Yingje Qian, Sosan Hwang, Myung Jong Jin, and Sang Eun Shim^†

Department of Chemistry & Chemical Engineering, Inha University, Incheon 22212, Korea

E-mail:

초록

다공성 고분자(porous organic polymer, POPs)는 높은 표면적을 가지는 무정형의 고분자이다. 본 연구에서는 우레아 축합반응으로 UPOP라는 다공성 고분자를 합성하였다. UPOP는 Brunauer-Emmett-Teller(BET) 분석을 통해 다공성을 확인하였고, 불균일 촉매 활용성을 보기 위하여 팔라듐을 담지하여 Pd@UPOP를 합성하였다. Pd@UPOP는 XPS 분석을 통해 Pd 담지를 확인하였고, Suzuki-Miyaura 커플링 반응을 이용하여 촉매활성을 측정하였다. Pd@UPOP의 촉매활성은 물과 ethanol이 3:1이고 K2CO3를 사용하였을 때 가장 높았다. 특히 이 조건에서 Pd@UPOP를 촉매로 사용하여 공기 중에서 반응시켰을 때 Pd 함량은 0.1 mol%였음에도 불구하고 99% 이상의 수율을 보였다. 또한 5번 재사용하였을 때도 90%의 수율을 유지하였다.

Porous organic polymers (POPs) are composed of amorphously linked bonds with high surface areas. Urea based porous organic polymer (UPOP) was synthesized by urea condensation reaction. Porous nature of UPOP was identified by Brunauer-Emmett-Teller (BET) analysis. To evaluate the possibility as heterogeneous catalysts, Pd was loaded onto UPOP, namely Pd@UPOP. XPS analysis and element mapping data confirmed that Pd was supported on Pd@UPOP, then Suzuki-Miyaura coupling reaction was performed with various aryl bromides. The optimized conditions for the catalytic activity of Pd@UPOP are using mixture of (H2O:EtOH 3:1) (v/v) as a solvent and K2CO3 as a base. In this condition, reactions reached to 99% yields with Pd only 0.1 mol% under 1 h. Also, in recycling experiments, yields were maintained above 90% during five runs.

Keywords:porous organic polymer;polyurea;Suzuki-Miyaura cross-coupling;catalyst;recycle

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[2] Gomes R, Bhanja P, Bhaumik A, Chem. Commun., 51, 10050 (2015)

[3] Guillerm V, Weselinski LJ, Alkordi M, Mohideen MIH, Belmabkhout Y, Cairns AJ, Eddaoudi M, Chem. Commun., 50, 1937 (2014)

[4] Chen Q, Wang J, Yang F, Zhou D, Bian N, Zhang X, Yan C, Han B, J. Mater. Chem., 21, 13354 (2011)

[5] Xie L, Suh MP, Chemistry-A Eur. J., 19, 11590 (2013)

[6] Farha OK, Spokoyny AM, Hauser BG, Bae Y, Brown SE, Snurr RQ, Mirkin CA, Hupp JT, Chem. Mater., 21, 3033 (2009)

[7] Farha OK, Bae Y, Hauser BG, Spokoyny AM, Snurr RQ, Mirkin CA, Hupp JT, Chem. Commun., 46, 1056 (2010)

[8] Zhu X, Mahurin SM, An S, Do-Thanh C, Tian C, Li Y, Gill LW, Hagaman EW, Bian Z, Zhou J, Chem. Commun., 50, 7933 (2014)

[9] Wood CD, Tan B, Trewin A, Su F, Rosseinsky MJ, Bradshaw D, Sun Y, Zhou L, Cooper AI, Adv. Mater., 20(10), 1916 (2008)

[10] Xie Y, Wang TT, Liu XH, Zou K, Deng WQ, Nat. Commun., 4, 1960 (2013)

[11] Bhunia S, Chatterjee N, Das S, Saha KD, Bhaumik A, ACS Appl. Mater. Interf., 6, 22569 (2014)

[12] Wibowo SH, Sulistio A, Wong EHH, Blencowe A, Qiao GG, Adv. Funct. Mater., 25(21), 3147 (2015)

[13] Xu YH, Chen L, Guo ZQ, Nagai A, Jiang DL, J. Am. Chem. Soc., 133(44), 17622 (2011)

[14] Patra A, Scherf U, Chem. Eur. J., 18, 10074 (2012)

[15] Kohler A, Wilson JS, Friend RH, Adv. Eng. Mater., 4, 453 (2002)

[16] Kaur P, Hupp JT, Nguyen ST, ACS Catalysis, 1, 819 (2011)

[17] Bronstein LM, Goerigk G, Kostylev M, Pink M, Khotina IA, Valetsky PM, Matveeva VG, Sulman EM, Sulman MG, Bykov AV, Lakina NV, Spontak RJ, J. Phys. Chem. B, 108(47), 18234 (2004)

[18] Hasell T, Wood CD, Clowes R, Jones JT, Khimyak YZ, Adams DJ, Cooper AI, Chem. Mater., 22, 557 (2009)

[19] Du X, Sun Y, Tan B, Teng Q, Yao X, Su C, Wang W, Chem. Commun., 46, 970 (2010)

[20] Jiang J, Wang C, Laybourn A, Hasell T, Clowes R, Khimyak YZ, Xiao J, Higgins SJ, Adams DJ, Cooper AI, Angew. Chem.-Int. Edit., 50, 1072 (2011)

[21] Li L, Chen Z, Zhong H, Wang R, Chem. Eur. J., 20, 3050 (2014)

[22] Billingsley K, Buchwald SL, J. Am. Chem. Soc., 129(11), 3358 (2007)

[23] Hoshi T, Saitoh I, Nakazawa T, Suzuki T, Sakai J, Hagiwara H, J. Org. Chem., 74, 4013 (2009)

[24] Minato A, Tamao K, Hayashi T, Suzuki K, Kumada M, Tetrahedron Lett., 22, 5319 (1981)

[25] Shahnaz N, Banik B, Das P, Tetrahedron Lett., 54, 2886 (2013)

[26] Kostas ID, Steele BR, Terzis A, Amosova SV, Martynov AV, Makhaeva NA, Eur. J. Inorg. Chem., 2006, 2642 (2006)

[27] Banik B, Tairai A, Shahnaz N, Das P, Tetrahedron Lett., 53, 5627 (2012)

[28] Navidi M, Rezaei N, Movassagh B, J. Org. Chem., 743, 63 (2013)

[29] Mino T, Shirae Y, Sakamoto M, Fujita T, J. Org. Chem., 70, 2191 (2005)

[30] Mino T, Shirae Y, Sakamoto M, Fujita T, Synlett, 2003, 0882 (2003)

[31] Tao B, Boykin DW, J. Org. Chem., 69, 4330 (2004)

[32] Rangel-Vazquez N, Sanchez-Lopez C, Felix FR, Polimeros, 24, 453 (2014)

[33] Yang L, Tang Y, Yan D, Liu T, Liu C, Luo S, ACS Appl. Mater. Interf., 8, 169 (2015)

[34] Kutubi M, Sato K, Wada K, Yamamoto T, Matsumura S, Kusada K, Kobayashi H, Kitagawa H, Nagaoka K, ChemCatChem, 7, 3887 (2015)