VIETNAM NATIONAL UNIVERSITY - HO CHI MINH CITY UNIVERSITY OF TECHNOLOGY NGUYEN THI NGOC TRAN METAL-ORGANIC FRAMEWORKS AS HETEROGENEOUS CATALYSTS FOR THE SYNTHESIS OF QUINAZOLINONES AND PYRIDINES Major: Chemical engineering Major ID: 60 52 03 01 M. THESIS HO CHI MINH CITY, JAN 2019 CÔNG TRÌNH ĐƯỢC HOÀN THÀNH TẠI TRƯỜNG ĐẠI HỌC BÁCH KHOA – ĐHQG – HCM Cán bộ hướng dẫn khoa học 1 : GS. Phan Thanh Sơn Nam (Ghi rõ họ, tên, học hàm, học vị và chữ ký) Cán bộ hướng dẫn khoa học 2 :. (Ghi rõ họ, tên, học hàm, học vị và chữ ký) Cán bộ chấm nhận xét 1 : PGS.
Nguyễn Thị Phương Phong (Ghi rõ họ, tên, học hàm, học vị và chữ ký) Cán bộ chấm nhận xét 2 : TS. Lê Vũ Hà (Ghi rõ họ, tên, học hàm, học vị và chữ ký) Luận văn thạc sĩ được bảo vệ tại Trường Đại học Bách Khoa, ĐHQG TP. HCM ngày 12 tháng 01 năm 2019 Thành phần Hội đồng đánh giá luận văn thạc sĩ gồm: (Ghi rõ họ, tên, học hàm, học vị của Hội đồng chấm bảo vệ luận văn thạc sĩ) 1. Phạm Thành Quân 2.
Nguyễn Thị Phương Phong 3. Nguyễn Đình Thành 5. Nguyễn Thanh Tùng Xác nhận của Chủ tịch Hội đồng đánh giá luận văn và Trưởng Khoa quản lý chuyên ngành sau khi luận văn đã được sửa chữa (nếu có). CHỦ TỊCH HỘI ĐỒNG TRƯỞNG KHOA KTHH ĐẠI HỌC QUỐC GIA TP.HCM CỘNG HÒA XÃ HỘI CHỦ NGHĨA VIỆT NAM TRƯỜNG ĐẠI HỌC BÁCH KHOA Độc lập - Tự do - Hạnh phúc NHIỆM VỤ LUẬN VĂN THẠC SĨ Họ tên học viên: NGUYỄN THỊ NGỌC TRÂN.
Ngày, tháng, năm sinh: 19/11/1994. Nơi sinh: Long An. Chuyên ngành: Kỹ thuật hóa học. TÊN ĐỀ TÀI: Metal-organic frameworks as heterogeneous catalysts for the synthesis of quinazolinones and pyridines.
NHIỆM VỤ VÀ NỘI DUNG: - Sử dụng xúc tác dị thể Cu-MOF-74 cho phản ứng tổng hợp quinazolinones. - Sử dụng xúc tác dị thể MOF VNU-20 cho phản ứng tổng hợp pyridines. NGÀY GIAO NHIỆM VỤ : 13/08/2018 IV. NGÀY HOÀN THÀNH NHIỆM VỤ: 12/01/2019 V.
CÁN BỘ HƯỚNG DẪN Cán bộ hướng dẫn : GS. PHAN THANH SƠN NAM Tp. HCM, ngày 22 tháng 01 năm 2019. CÁN BỘ HƯỚNG DẪN CHỦ NHIỆM BỘ MÔN ĐÀO TẠO (Họ tên và chữ ký) (Họ tên và chữ ký) TRƯỞNG KHOA KỸ THUẬT HÓA HỌC (Họ tên và chữ ký) ACKNOWLEDGEMENTS First and foremost, I would like to thank Prof.
Phan Thanh Son Nam for the financial support for this project and also gave me guidance on this thesis with his comprehensive knowledge. Working with them is an honor and a valuable experience for me. Especially, my profound gratitude is expanded to all the teaching staffs of the Organic Chemistry Department, for the valuable information provided by them in their respective fields. Their unconditional love and support have always accompanied with every achievement in my life.
In addition, I would like to thank my talented and loyal friends: Mr. Pham and Mr. Nguyen, Miss Tram. Van, Miss Que.
Nguyen for their encouragement and support during my hardest time. Their advices made me always have the positive attitude and helped me complete this thesis. Finally, I would like to express my sincere gratitude to my parents. Their love, encouragement and continuous support have always been with me in every achievement I get in my life.
Ho Chi Minh City, December, 2018 Nguyen Thi Ngoc Tran ABSTRACT Generally, this thesis focuses on applying metal-organic frameworks as efficient solid catalysts for diverse transformations. According to that, two MOFs were successfully synthesized by solvothermal method. A crystalline porous copper-based metal-organic framework named Cu-MOF-74 was generated from Cu(NO3)2.5-dihydroxyterephthalic acid while a mixed-linker iron-based MOF named VNU-20 [Fe3(BTC)(NDC)2·6.65H2O] was prepared from 1,3,5-benzenetricarboxylic acid, 2,6- naphthalenedicarboxylic acid and FeCl2. Physical characterizations of the solid catalysts were obtained by several analysis techniques including powder X-ray diffraction (PXRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), Fourier transform infrared (FT-IR), and atomic absorption spectroscopy (AAS).
The results indicated that the desired structures of the MOFs were obtained. For the first time, the Cu-MOF-74 was used as a heterogeneous catalyst for the reaction between 2-phenylindole and phenethylamine to afford the 3-phenethyl-2- phenylquinazolin-4(3H)-one in excellent conversion. Indeed, the reaction offered many advantages as compared to previous works including low catalyst loading, and milder conditions. VNU-20 was found to be more active for the cyclization of ketoxime carboxylates and dibenzyl ether than several conventional molecular and MOF-based heterogeneous catalysts, which has not mentioned in previous reports yet.
These MOFs not only exhibited high catalytic possibilities but also could be reused for several times without any considerable decline in efficiency. Due to the benefits of quinazolinone and pyridine derivatives in pharmaceutical and chemical industry, the scope of the reactions was expanded by varying many substrates to obtain a broad range of desired products. vi LIST OF FIGURES. ix LIST OF SCHEME.
xi LIST OF TABLES. xiv LIST OF ABBREVIATION .xv CHAPTER 1: LITERATURE REVIEW .1 METAL-ORGANIC FRAMEWORKS (MOFS) .2 General methods for the synthesis of MOFs .3 Application of MOFs .2 INTRODUCTION TO CU-MOF-74 AS AN EFFICIENT HETEROGENEOUS CATALYST .3 INTRODUCTION TO IRON-BASED METAL-ORGANIC FRAMEWORKS AND IRON- BASED MOF VNU-20 [FE3(BTC)(NDC)2.65H2O] AS A HETEROGENEOUS CATALYST .4 THE QUINAZOLINONES SYNTHESIS OF 2-ARYLINDOLES WITH AMINES UTILIZING CU-MOF-74 AS AN EFFICIENT HETEROGENEOUS CATALYST .5 THE CYCLIZATION REACTIONS OF KETOXIME ACETATES AND DIBENZYL ETHER TO PRODUCE PYRIDINES UTILIZING MOF VNU-20 AS A HETEROGENEOUS CATALYST .6 AIMS AND OBJECTIVES .49 CHAPTER 2: EXPERIMENTAL SECTION. MATERIALS AND INSTRUMENTATION. SYNTHESIS OF THE METAL-ORGANIC FRAMWORKS (MOFS) .1 Synthesis of Cu-MOF-74.2 Synthesis of VNU-20.1 Catalytic studies in the expansion reaction to produce 2-arylquinazolinones 54 2.2 Catalytic studies in the cyclization reaction of ketoxime acetates and dibenzyl ether to synthesize 2,4,6-triphenyl pyridine.
RESULT AND DISCUSSION .1 THE CU-MOF-74-CATALYZED BAEYER-VILLIGER OXIDATION EXPANSION REACTION TO SYNTHESIZE 2-ARYLQUINAZOLINONES .1 Synthesis and characterization of Cu-MOF-74 .2 Catalytic studies in the synthesis of 2-arylquinazolinones .1 Effect of temperature on the reaction .2 Effect of solvent on the reaction .3 Effect of reactant molar ratio on the reaction yield .4 Effect of catalyst quantity on the reaction yield .5 Effect of different catalysts on the reaction yield .8 Effect of different substituents on the reaction .2 THE MIXED-LINKER MOF VNU-20-CATALYZED CYCLIZATION REACTIONS OF KETOXIME ACETATES AND DIBENZYL ETHER TO PRODUCE SYMMETRICAL PYRIDINES .1 Synthesis and characterization of VNU-20 .2 Catalytic studies in the synthesis of symmetrical pyridines .1 Effect of temperature on the reaction .2 Effect of solvent on the reaction .3 Effect of ratio reactants on the reaction .4 Effect of catalyst amount on the reaction .5 Effect of time on the reaction .6 Effect of oxidant on the reaction .7 Effect of oxidant amount on the reaction .8 Effect of antioxidant on the reaction .12 Effect of different catalysts on the reaction .13 Effect of different atmospheres on the reaction .14 Effect of different substituents on the reaction .109 APPENDIX A: CALIBRATION CURVE .118 APPENDIX B: GC YIELD .121 APPENDIX C: CHARACTERIZATION DATA .129 LIST OF FIGURES Figure 1. 1: Progress in the synthesis of ultrahigh porosity MOFs. The values in parentheses represent the pore volume (m3/ g) of these materials [4]. 2: Growth of the Cambridge Structural Database (CSD) and MOF entries since 1972 [5].
The inset shows the MOF self-assembly process from building blocks: metals (red spheres) and organic ligands (blue struts). 3: Overview of synthesis methods, possible reaction temperatures, and final reaction products in MOFs synthesis [10]. 4: Interaction of a substrate molecule, S, with a metal site, M, through (a) expansion of the coordination sphere around the metal ion; or (b) (reversible) displacement of one of the ligands [22]. 5: Color changes during the dehydration of Cu3(BTC)2(H2O)3.xH2O to give Cu3(BTC)2, and subsequent readsorption of the aldehyde to give Cu3(BTC)2(C6H5CHO)x [24].
6: General structure and selected examples of ligands containing coordinative and reactive functional groups [22]. 7: Crystal structure of a MOF-74 (left) and metal oxide chains connected by organic linkers (right). O, red; C, black, H, white; metal, blue [33]. 8: Solvothermal synthesis of MOF structures [35].
9: CO2 adsorption–desorption isotherms at different temperatures of Cu2(dhtp) [34]. 10: Total yields of the products that result from the oxidation of cyclohexene in the presence of M–MOF-74 and without catalyst (blank) with TBHP. 11: Comparison of different types of acid catalysts for the acylation of anisole [36]. 12: Pores in the M2dobdc MOF (brown = carbon; orange = metal; red = oxygen).
13: Three types of Quinazolinones. 14: The crystal structure of VNU-20 (b) are linked horizontally and vertically by BTC3− and NDC2−, respectively (a, e and f) to form the orange-red crystals (d) with structure highlighted with a rectangular window of 6. Atom colors: Fe, blue and orange polyhedra; C, black; O, red. All H atoms are omitted for clarity [67].
15: Pyridine core and several pyridine derivatives [87, 88]. 1: PXRD patterns of the simulated (a) and synthesized (b) Cu-MOF-74 58 Figure 3. 2: FT-IR spectra of terephthalic acid and the Cu-MOF-74. 3: TGA curve of the Cu-MOF-74.
4: SEM micrograph of the Cu-MOF-74. 5: TEM micrograph of Cu-MOF-74 at 500nm and 100nm. 6: Pore size distribution of Cu-MOF-74. 7: Isotherm linear plot of Cu-MOF-74.
8: Effect of temperature on the reaction yield. 9: Effect of solvent on the reaction yield. 10: Effect of reactant molar ratio on the reaction yield. 11: Effect of catalyst quantity on the reaction yield.
12: Effect of homogeneous catalysts on the reaction yield. 13: Effect of heterogeneous catalysts on the reaction yield. 14: Leaching test indicated no contribution from homogeneous catalysis of active species leaching into reaction solution. 15: Catalyst recycling studies.
16: PXRD patterns of the simulated (a) and synthesized (b) Cu-MOF-74. 17: FT-IR spectra of the Cu-MOF-74. 18: Effect of different temperatures on the reaction yield. 19: Effect of solvent to the reaction.
20: Effect of molar ratio of dibenzyl ether /(E)-acetophenone O-acetyl oxime acetate on the reaction yield. 21: Effect of catalyst amount on the reaction yield. 22: Effect of time on the reaction. 23: Effect of oxidant on the reaction.
24: Effect of oxidant amount on the reaction. 25: Effect of antioxidant on the reaction. 26: Leaching test indicated no contribution from homogeneous catalysis of active species leaching into reaction solution. 28: Catalyst reusing studies.
29: FT-IR analyses of the new (a) and recovered (b) catalyst. 30: PXRD determination of the new (a) and recovered (b) catalyst. 31: Effect of different homogeneous catalyst on the reaction. 32: Effect of different heterogeneous catalyst on the reaction.
33: Effect of different atmospheres on reaction yield.96 LIST OF SCHEME Scheme 1. 1: The photolysis of o-methyl dibenzyl ketone carried out inside the pores of [Co3(4,40-BPhDC)3(4,40-bpy)] [30]. 2: The oxidation of cyclohexene [37]. 3: Simplified reaction for the acylation of anisole with acetyl chloride [36].
4: The catalytic activity of Cu-MOF-74 in some typically base-catalyzed reactions, a) Knoevengel condensation rection. 5: The coupling reaction of amines and -carbonyl aldehydes [39]. 6: The reaction between dibenzyl ether and 2-acetyl phenol utilizing Cu- MOF-74 catalyst [40]. 7: The three-component coupling reaction of 2-pyridincarboxaldehyde, piperidine, and phenylacetylene using Cu-MOF-74 catalyst [41].
8: The synthesis of imidazo[1,5-a]pyridines via oxidative amination of the C(sp3)–H bond using Cu-MOF-74 [42]. 9: The hydroacylation of 1-alkynes with glyoxal derivatives using the Cu- MOF-74 catalyst [43]. 25: 1,5-benzodiazepine synthesis via cyclocondensation of 1,2-diamines with ketones using MOF-235 as an efficient heterogeneous catalyst [48]. 26: Direct C-C coupling of indoles with alkylamides via oxidative C−H functionalization using Fe3O(BDC)3 as a productive heterogeneous catalyst [49].
27: Direct arylation of benzoazoles with aldehydes utilizing metal–organic framework Fe3O(BDC)3 as a recyclable heterogeneous catalyst [50]. 28: Synthesis of 2-alkenylazaarenes using the direct alkenylation of 2- substituted azaarenes with carbonyls via C−H bond activation [51].