钛—羧酸杂化材料的制备及其在合成中的应用
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摘要
有机-无机杂化材料负载金属催化剂的应用是有机非均相催化研究中的热点之一本文以异烟酸作为杂化材料的有机配体,钛酸四丁酯为无机前体,其水解产物形成杂化材料的钛氧骨架,在反应过程加入MC12 (M=Cu, Pd, Mn),通过溶胶-凝胶(sol-gel)法制备出负载铜、钯、锰的基于钛-羧酸络合的有机-无机杂化材料。得到的杂化材料负载型催化剂利用TEM, IR, XRD, EDXS, BET, TGA, ICP-AES等分析手段进行了结构表征,并进一步应用于氮杂Michael加成反应、Suzuki偶联反应及Kabachnik-Fields反应中。
结果表明,负载铜、钯、锰的有机-无机杂化催化剂在上述反应中表现出较高的催化活性,可以多次回收套用且催化活性基本不受影响,是一种高效、环保型的新型催化剂。
The application of metal-containing organic-inorganic hybrid catalysts is one of the hot topics in heterogeneous organic catalysis. In this dissertation, three types of Ti-based organic-inorganic hybrid materials containing MCl2 (M=Cu, Pd, Mn) were prepared by simple sol-gel processes, and characterized by TEM, IR, XRD, EDXS, BET, TGA, ICP-AES and so on. In this method, isonicotinic acid was employed as organic ligand and tetrabutyl titanate was used as an organic precursor to form the inorganic frameworks through hydrolysis.
The results showed hybrid materials supported copper, palladium, manganese showed highly catalytic activities in the proof-of-concept reactions such as aza-Michael addition, Suzuki coupling and Kabachnik-Fields reaction. The recovered catalysts could be reused for several times without the loss of activity. As-synthesized organic-inorganic hybrid materials were thus proved to be a new serial of efficient and environmentally friendly catalysts which might be applied in organic synthesis.
结果表明,负载铜、钯、锰的有机-无机杂化催化剂在上述反应中表现出较高的催化活性,可以多次回收套用且催化活性基本不受影响,是一种高效、环保型的新型催化剂。
The application of metal-containing organic-inorganic hybrid catalysts is one of the hot topics in heterogeneous organic catalysis. In this dissertation, three types of Ti-based organic-inorganic hybrid materials containing MCl2 (M=Cu, Pd, Mn) were prepared by simple sol-gel processes, and characterized by TEM, IR, XRD, EDXS, BET, TGA, ICP-AES and so on. In this method, isonicotinic acid was employed as organic ligand and tetrabutyl titanate was used as an organic precursor to form the inorganic frameworks through hydrolysis.
The results showed hybrid materials supported copper, palladium, manganese showed highly catalytic activities in the proof-of-concept reactions such as aza-Michael addition, Suzuki coupling and Kabachnik-Fields reaction. The recovered catalysts could be reused for several times without the loss of activity. As-synthesized organic-inorganic hybrid materials were thus proved to be a new serial of efficient and environmentally friendly catalysts which might be applied in organic synthesis.
引文
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[54]Zhou Wen-Jun, Wang Ke-Hu, Wang Jin-Xian. Atom-efficient, palladium-catalyzed Stille coupling reactions of tetraphenylstannane with aryl iodides or aryl bromides in polyethylene glycol 400 (PEG-400)[J]. Advanced Synthesis & Catalysis,2009,351(9):1378-1382.
[55]Qin Weiwei,Yasuike Shuji, Kakusawa Naoki, etc. Palladium-catalyzed carbonylative cross-coupling reaction of triarylantimony dicarboxylates with arylboronic acids:Synthesis of biaryl ketones[J]. Journal of Organometallic Chemistry,2008,693(17):2949-2953.
[56]Saharia G. S., Sharma B. R., Univ Delhi. Hydroxy ketones. VI. Fries rearrangement of the phenolic esters of o-and m-nitrobenzoic acids and some thiophenyl esters[J]. Journal of the Indian Chemical Society,1956,33:788-790.
[57]DeVasher Rebecca B., Moore Lucas R., Shaughnessy, Kevin H. Aqueous-phase, palladium-catalyzed cross-coupling of aryl bromides under mild conditions, using water-soluble, sterically demanding alkylphosphines[J]. Journal of Organic Chemistry,2004, 69(23):7919-7927.
[58]Korolev Dmitrii N., Bumagin Nikolay A. An improved protocol for ligandless Suzuki-Miyaura coupling in water[J]. Tetrahedron Letters,2006,47(25):4225-4229.
[59]Pudovik, A. N..Addition of dialkyl phosphites to imines, New method of synthesis of esters of amino phosphonic acids[J]. Doklady Akademii Nauk SSSR,1952,83:865-868.
[60]Zahouily, Mohamed. Uncatalysed preparation of a-amino phosphonates under solvent free conditions[J].Journal of Chemical Research,2005, (5):324-327.
[61]Tian, You-Ping, Xu Feng, etc. PPh3-catalysed one-pot three-component syntheses of a-aminophosphonates under solvent-free conditions [J]. Journal of Chemical Research,2009, (2):78-80.
[62]Hosseini-Sarvari, Mona. TiO2 as a new and reusable catalyst for one-pot three-component syntheses of a-aminophosphonates in solvent-free conditions [J]. Tetrahedron,2008,64(23):5459-5466.
[63]Jiao Chong-jun, Shen Zong-xuan, Kong Li-chu, etc. One-pot three-component synthesis of a-amino phosphonates catalyzed by heteropolyacids in H2O/THF and in ether[J]. Huaxue Yanjiu,2007,18(4):27-32.
[64]Ranu Brindaban C., Hajra Alakananda. A simple and green procedure for the synthesis of a-aminophosphonate by a one-pot three-component condensation of carbonyl compound, amine and diethyl phosphite without solvent and catalyst[J]. Green Chemistry,2002,4(6): 551-554.
[65]Begum Saeedan, Choudhary M. Iqbal, Khan Khalid M. Synthesis, phytotoxic, cytotoxic, acetylcholinesterase and butyrylcholinesterase activities of N, N'-diaryl unsymmetrically substituted thioureas[J]. Natural Product Research,2009,23(18):1719-1730.
[2]MacLachlan M. J., Manners I., Ozin G. A. New(Inter) Faces:Polymers and Inorganic Materials. Adv. Mater.,2000,12 (9):675-681.
[3]Moreau J. J. E., Chi Man M. W. The Design of Selective Catalysts from Hybrid Silica-based Materials. Coord. Chem. Rev.,1998,178-180(2):1073-1084.
[4]Astruc D., Chardac F. Dendritic Catalysts and Dendrimers in Catalysis. Chem. Rev.,2001, 101(9):2991-3024.
[5]Ballard R. L., Tuman S. J., Fouquette D. J., et al. Effects of an Acid Catalyst on the Inorganic Domain of Inorganic-organic Hybrid Materials[J]. Chem. Mater.,1999,11(3): 726-735.
[6]张贻瑞,王建.基础材料与新材料.大津：天津大学出版社,1994.
[7]Dallmann K., Buffon R. Sol-gel Derived Hybrid Materials as Heterogeneous Catalysts for the Epoxidation of Olefins. Catal. Commun.,2000,1 (1-4):9-13.
[8]Lagasi M., Moggi P. Anchoring of Pd on Silica Functionalized with Nitrogen Containing Chelating Groups and Applications in Catalysis. J. Mol. Catal. A:Chem.,2002,182-183: 61-72.
[10]Lin CL, Yeh M Y, Chen C H, Sudhakar S, Luo S J, Hsu Y C, Huang C Y, Ho K C, Luh T Y. Silica-titania-based organic-inorganic hybrid materials for photovoltaic [J]. Applications Chem. Mater,2006,18(17):4157-4162.
[11]Bauer S, Bein T, Stock N. High-throughput investigation and characterization of cobalt carboxy PhosPhonates[J]. Inorg. Chem,2005,44(16):5882-5889.
[12]Okada A, Usuki A. The chemistry of polymer-clay hybrids[J]. Mater Sci Eng,1995,3: 109-115.
[13]Gilman J W. Flammability and thermal stability studies of polymer layered-silicate(clay) nanocomposites. Appl Clay Sci,1999,15(1-2):31-49.
[14]Gilman J W, Jackson C L, Morgan A B, etal. Flammability properties of polymer-layered silicate nanocomposites [J]. Chem Mater,2000,12(7):1866-1873.
[15]Godovski D Y. Electron behavior and magnetic properties of polymer nanocomposites [J]. Adv Polym Sci,1995,119:79-122.
[16]Chujo Y, Saegusa T. Organic polymer hybrids with silica gel formed by means of the sol-gel method[J]. Adv polym Sci,1992,100:11-29.
[17]Imhof A. Preparation and characterization of titania-coated polystyrene spheres and hollow titania shells[J]. Langmuir,2001,17(12):3579-3585.
[18]Tissot I, Reymond J P, Lefebvre F, et al. SiOH-functionalized polystyrene latexes. A step toward the synthesis of hollow silica nanoparticles, Chem Mater,2002,14(3):1325-1331.
[19]Choi J, Tamaki R, Laine R M. Organic/inorganic imide nanocomposites from Aminophenyl silsesquioxanes[J]. Chem. Mater,2003,15(17):3365-3375.
[20]Wight A P, Davis M E. Chem. Rev.,2002,102(10):3589-3614.
[21]DeVos D E, Dams M, Sels B F, et al. Chem Rev.,2002,102(10):3615-3640.
[22]Vinu A, Miyahara M, Ariga K. J. Nanosci. Nanotech.,2006,6(6):1501-1532.
[23]Hartmann M. Chem. Mater.,2005,17(18):4577-4593.
[24]Yiu H H P, Wright P A. J. Mater. Chem.,2005,15(35-36):3690-3700.
[25]Trong On D, Desplantier-Giscard D, Danumah C, et al. Appl. Catal. A:Gen.,2003, 253(2):545-602.
[26]Li C, Zhang H D, Jiang D M, et al. Chem Commun.,2007, (6):547-558.
[27]Yang Q H, Han D F, Yang H Q, et al. Chem. Asian J.,2008,3(8-9):1214-1229.
[28]Yu Y. Y., Chen C. Y., Chen W. C. Synthesis and Characterization of Organic/inorganic Hybrid Thin Films from Poly(acrylic) and Monodispersed Colloidal Silica. Polymer,2003, 44(3):593-601.
[29]郭军,葛科,贺深阳,等.水滑石类有机无机杂化材料的合成与嫁接作用.吉首大学学报(自然科学版),2005,26(4)：45-49.
[30]G. B. Gardner, D. Venkataraman, J. S. Moore, S. Lee, Nature 1995,374,792-795.
[31]C. Livage, C. Egger, M. Nogues, G. Ferey, J. Mater. Chem.1998,8,2743-2747.
[32]N. Guillou, S. PaStre, C. LiVage, G Ferey,. Chem. Commun.2002,2358-2359.
[33]M. Kurmoo, J. Mater. Chem.1999,2595-2598.
[34]F. Serpaggi, T. Luxbacher, A. K. Cheetham, G. Ferey, J. Solid State Chem.1999,145: 580-586.
[35]H. Li, M. Eddaoudi, M. O'Keeffe, O. M. Yaghi, Nature 1999,402,276-279.
[36]H. K. Chae, D.Y Siberio-Perez, J. Kim, Y. Go, et al, Nature 2004,427:523-527.
[37]G. Alberti, U. Constantino, S. Allulli, et al. crystalline Zr(R-PO3)2 and Zr(R-OPO3)2 Compounds(R=organic radical). J. Inorg. Nucl.,1987,40:1113-1117.
[38]A. Choudhury, S. Natarajan, C. N. R. Rao, Chem Commun,1999,1305-1306.
[39]C. Lei, J. G. Mao, Y. Q. Sun, et al. Inorg, Chem.2003,42:6157-6159.
[40]M. I. Khan., L. M. Meyer., R. C. Haushalter., et al. Dye, Chem Mater,1996,8:43-53.
[41]J. Y Sun., L. H. Weng., Y. M. Zhou., et al. Angew. Chem. Int. Ed.2002,41:4471-4473.
[42]Cle'ment Sanchez, Beatriz Julia'n, Philippe Belleville, et al. Applications of hybrid organic-inorganic nanocomposites[J]. J. Mater. Chem.,2005,15:3559-3592.
[43]Vaia R A, Gianelis E P. Laticem Model of polymer melt intercalation in organically-modified layered silicates[J]. Marcomolecules,1997,30(25):7990-7999.
[44]Wu J, Lerner M. Chem. Mater[J].1993,5:835-838.
[45]瞿雄伟,罗艳红,丁会利.Poly (Vinyl Chloride)/Clay Nanocomposites by Melt Intercalation Process[J].2002,4:9-23.
[46]张心亚,黎永津,傅和青.无机-有机杂化纳米材料的控制合成与结构组装研究进展[J].材料导报,2007(05).
[47]刘华蓉,葛学武,倪永红.无机-有机纳米复合材料的研究进展[J].化学进展,2001,13(5)：403-409.
[48]G. J. de A. A. Soler-Illia, C. Sanchez, B. Lebeau and J. Patarin, Chem. Rev.,2002,102: 4093.
[49]C. Sanchez, H. Arribart and M. M. Giraud-Guille, Nature Mater.,2005,4:277.
[50]S. Mann, S. L. Burkett, S. A. Davis, C. E. Fowler, N. H. Mendelson, S. D. Sims, D. Walsh and N. T. Whilton, Chem. Mater.,1997,9:2300.
[51]Granauer M, Fricke J. Acoustic properties of microporous SiO2-aerogel. Acustia,1996, 59(1):177-121.
[52]Jayabalakrishnan C., Karvembu R., Natarajan K. Ruthenium(Ⅲ) Schiff Base Complexes: Catalytic Activity in Aryl-Aryl Coupling Reaction and Antimicrobial Activity[J]. Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry,2003,33(9):1535-1553.
[53]Zhang Liyuan, Wang Lei, Li Hongji, etc. Application of Highly Efficient, Recyclable Organic-Inorganic Hybrid Material Immobilized Palladium Catalyst in Amine-and Phosphine-Free Suzuki-Miyaura Reaction[J]. Synthetic Communications,2008,38(10): 1498-1511.
[54]Zhou Wen-Jun, Wang Ke-Hu, Wang Jin-Xian. Atom-efficient, palladium-catalyzed Stille coupling reactions of tetraphenylstannane with aryl iodides or aryl bromides in polyethylene glycol 400 (PEG-400)[J]. Advanced Synthesis & Catalysis,2009,351(9):1378-1382.
[55]Qin Weiwei,Yasuike Shuji, Kakusawa Naoki, etc. Palladium-catalyzed carbonylative cross-coupling reaction of triarylantimony dicarboxylates with arylboronic acids:Synthesis of biaryl ketones[J]. Journal of Organometallic Chemistry,2008,693(17):2949-2953.
[56]Saharia G. S., Sharma B. R., Univ Delhi. Hydroxy ketones. VI. Fries rearrangement of the phenolic esters of o-and m-nitrobenzoic acids and some thiophenyl esters[J]. Journal of the Indian Chemical Society,1956,33:788-790.
[57]DeVasher Rebecca B., Moore Lucas R., Shaughnessy, Kevin H. Aqueous-phase, palladium-catalyzed cross-coupling of aryl bromides under mild conditions, using water-soluble, sterically demanding alkylphosphines[J]. Journal of Organic Chemistry,2004, 69(23):7919-7927.
[58]Korolev Dmitrii N., Bumagin Nikolay A. An improved protocol for ligandless Suzuki-Miyaura coupling in water[J]. Tetrahedron Letters,2006,47(25):4225-4229.
[59]Pudovik, A. N..Addition of dialkyl phosphites to imines, New method of synthesis of esters of amino phosphonic acids[J]. Doklady Akademii Nauk SSSR,1952,83:865-868.
[60]Zahouily, Mohamed. Uncatalysed preparation of a-amino phosphonates under solvent free conditions[J].Journal of Chemical Research,2005, (5):324-327.
[61]Tian, You-Ping, Xu Feng, etc. PPh3-catalysed one-pot three-component syntheses of a-aminophosphonates under solvent-free conditions [J]. Journal of Chemical Research,2009, (2):78-80.
[62]Hosseini-Sarvari, Mona. TiO2 as a new and reusable catalyst for one-pot three-component syntheses of a-aminophosphonates in solvent-free conditions [J]. Tetrahedron,2008,64(23):5459-5466.
[63]Jiao Chong-jun, Shen Zong-xuan, Kong Li-chu, etc. One-pot three-component synthesis of a-amino phosphonates catalyzed by heteropolyacids in H2O/THF and in ether[J]. Huaxue Yanjiu,2007,18(4):27-32.
[64]Ranu Brindaban C., Hajra Alakananda. A simple and green procedure for the synthesis of a-aminophosphonate by a one-pot three-component condensation of carbonyl compound, amine and diethyl phosphite without solvent and catalyst[J]. Green Chemistry,2002,4(6): 551-554.
[65]Begum Saeedan, Choudhary M. Iqbal, Khan Khalid M. Synthesis, phytotoxic, cytotoxic, acetylcholinesterase and butyrylcholinesterase activities of N, N'-diaryl unsymmetrically substituted thioureas[J]. Natural Product Research,2009,23(18):1719-1730.