Metal organic frameworks as heterogeneous catalysts for the synthesis of quinazolinones and pyridines

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 ENG THESIS HO CHI MINH CITY, JAN 2019 CƠNG TRÌNH ĐƯỢC HỒN THÀNH TẠI TRƯỜNG ĐẠI HỌC BÁCH KHOA – ĐHQG – HCM Cán hướng dẫn khoa học : GS.TS Phan Thanh Sơn Nam (Ghi rõ họ, tên, học hàm, học vị chữ ký) Cán hướng dẫn khoa học : (Ghi rõ họ, tên, học hàm, học vị chữ ký) Cán chấm nhận xét : PGS.TS Nguyễn Thị Phương Phong (Ghi rõ họ, tên, học hàm, học vị chữ ký) Cán chấm nhận xét : TS Lê Vũ Hà (Ghi rõ họ, tên, học hàm, học vị chữ ký) Luận văn thạc sĩ bảo vệ 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 Hội đồng chấm bảo vệ luận văn thạc sĩ) PGS.TS Phạm Thành Quân PGS.TS Nguyễn Thị Phương Phong TS Lê Vũ Hà PGS.TS Nguyễn Đình Thành TS Nguyễn Thanh Tùng Xác nhận Chủ tịch Hội đồng đánh giá luận văn Trưởng Khoa quản lý chuyên ngành sau luận văn sửa chữa (nếu có) CHỦ TỊCH HỘI ĐỒNG TRƯỞNG KHOA KTHH ĐẠI HỌC QUỐC GIA TP.HCM TRƯỜNG ĐẠI HỌC BÁCH KHOA CỘNG HÒA XÃ HỘI CHỦ NGHĨA VIỆT NAM Độc lập - Tự - Hạnh phúc NHIỆM VỤ LUẬN VĂN THẠC SĨ Họ tên học viên: NGUYỄN THỊ NGỌC TRÂN MSHV:1770010 Ngày, tháng, năm sinh: 19/11/1994 Nơi sinh: Long An Chuyên ngành: Kỹ thuật hóa học Mã số : 60520301 I TÊN ĐỀ TÀI: Metal-organic frameworks as heterogeneous catalysts for the synthesis of quinazolinones and pyridines II 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 III NGÀY GIAO NHIỆM VỤ : 13/08/2018 IV NGÀY HOÀN THÀNH NHIỆM VỤ: 12/01/2019 V CÁN BỘ HƯỚNG DẪN Cán hướng dẫn : GS.TS PHAN THANH SƠN NAM Tp HCM, ngày 22 tháng 01 năm 2019 CÁN BỘ HƯỚNG DẪN CHỦ NHIỆM BỘ MÔN ĐÀO TẠO (Họ tên chữ ký) (Họ tên chữ ký) TRƯỞNG KHOA KỸ THUẬT HÓA HỌC (Họ tên 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 Phuc H Pham and Mr Vu H H Nguyen, Miss Tram T Van, Miss Que T D 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)2.3H2O and 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, 2,6naphthalenedicarboxylic acid and FeCl2 Physical characterizations catalysts were obtained by several analysis diffraction (PXRD), of the solid techniques including powder X-ray 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-2phenylquinazolin-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 CONTENTS ACKNOWLEDGEMENTS iv ABSTRACT v CONTENTS vi LIST OF FIGURES ix LIST OF SCHEME xi LIST OF TABLES xiv LIST OF ABBREVIATION .xv CHAPTER 1: LITERATURE REVIEW 1.1 METAL-ORGANIC FRAMEWORKS (MOFS) 1.1.1 General introduction 1.1.2 General methods for the synthesis of MOFs 1.1.3 Application of MOFs .4 1.2 INTRODUCTION TO CU-MOF-74 AS AN EFFICIENT HETEROGENEOUS CATALYST 1.3 INTRODUCTION TO IRON-BASED METAL-ORGANIC FRAMEWORKS AND IRON- BASED MOF VNU-20 [FE3(BTC)(NDC)2.6.65H2O] AS A HETEROGENEOUS CATALYST 19 1.4 THE QUINAZOLINONES SYNTHESIS OF 2-ARYLINDOLES WITH AMINES UTILIZING CU-MOF-74 AS AN EFFICIENT HETEROGENEOUS CATALYST 25 1.5 THE CYCLIZATION REACTIONS OF KETOXIME ACETATES AND DIBENZYL ETHER TO PRODUCE PYRIDINES UTILIZING MOF VNU-20 AS A HETEROGENEOUS CATALYST 35 1.6 AIMS AND OBJECTIVES 49 CHAPTER 2: EXPERIMENTAL SECTION 51 2.1 MATERIALS AND INSTRUMENTATION 51 2.2 SYNTHESIS OF THE METAL-ORGANIC FRAMWORKS (MOFS) 53 2.2.1 Synthesis of Cu-MOF-74 53 2.2.2 Synthesis of VNU-20 54 2.3 CATALYTIC TESTS 54 2.3.1 Catalytic studies in the expansion reaction to produce 2-arylquinazolinones 54 2.3.2 Catalytic studies in the cyclization reaction of ketoxime acetates and dibenzyl ether to synthesize 2,4,6-triphenyl pyridine .55 CHAPTER RESULT AND DISCUSSION 58 3.1 THE CU-MOF-74-CATALYZED BAEYER-VILLIGER OXIDATION EXPANSION REACTION TO SYNTHESIZE 2-ARYLQUINAZOLINONES 58 3.1.1 Synthesis and characterization of Cu-MOF-74 58 3.1.2 Catalytic studies in the synthesis of 2-arylquinazolinones 63 3.1.2.1 Effect of temperature on the reaction 64 3.1.2.2 Effect of solvent on the reaction 66 3.1.2.3 Effect of reactant molar ratio on the reaction yield .67 3.1.2.4 Effect of catalyst quantity on the reaction yield 68 3.1.2.5 Effect of different catalysts on the reaction yield 69 3.1.2.6 Leaching test 71 3.1.2.7 Catalyst reusability 72 3.1.2.8 Effect of different substituents on the reaction 75 3.1.2.9 Conclusion .77 3.2 THE MIXED-LINKER MOF VNU-20-CATALYZED CYCLIZATION REACTIONS OF KETOXIME ACETATES AND DIBENZYL ETHER TO PRODUCE SYMMETRICAL PYRIDINES 77 3.2.1 Synthesis and characterization of VNU-20 77 3.2.2 Catalytic studies in the synthesis of symmetrical pyridines 78 3.2.2.1 Effect of temperature on the reaction 79 3.2.2.2 Effect of solvent on the reaction 80 3.2.2.3 Effect of ratio reactants on the reaction 82 3.2.2.4 Effect of catalyst amount on the reaction 83 3.2.2.5 Effect of time on the reaction 84 3.2.2.6 Effect of oxidant on the reaction 85 3.2.2.7 Effect of oxidant amount on the reaction 86 3.2.2.8 Effect of antioxidant on the reaction .87 3.2.2.9 Leaching test 89 3.2.2.10 Pyridine test 90 3.2.2.11 Catalyst reusability 91 3.2.2.12 Effect of different catalysts on the reaction 93 3.2.2.13 Effect of different atmospheres on the reaction .96 3.2.2.14 Effect of different substituents on the reaction 97 3.2.2.15 Plausible mechanism 101 3.2.2.16 Conclusion 105 CHAPTER CONCLUSION 107 REFERENCES 109 APPENDIX A: CALIBRATION CURVE 118 APPENDIX B: GC YIELD .121 APPENDIX C: CHARACTERIZATION DATA 129 LIST OF FIGURES Figure 1: Progress in the synthesis of ultrahigh porosity MOFs The values in parentheses represent the pore volume (m3/ g) of these materials [4] Figure 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) .2 Figure 3: Overview of synthesis methods, possible reaction temperatures, and final reaction products in MOFs synthesis [10] Figure 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] .6 Figure 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] Figure 6: General structure and selected examples of ligands containing coordinative and reactive functional groups [22] .8 Figure 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] 10 Figure 8: Solvothermal synthesis of MOF structures [35] 11 Figure 9: CO2 adsorption–desorption isotherms at different temperatures of Cu2(dhtp) [34] 13 Figure 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 14 Figure 11: Comparison of different types of acid catalysts for the acylation of anisole [36] .15 Figure 12: Pores in the M2dobdc MOF (brown = carbon; orange = metal; red = oxygen).[31] 16 Figure 13: Three types of Quinazolinones 25 Figure 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 6.0 × 8.7 Å2 (c) Atom colors: Fe, blue and orange polyhedra; C, black; O, red All H atoms are omitted for clarity [67] 20 Figure 15: Pyridine core and several pyridine derivatives [87, 88] 36 Figure 1: PXRD patterns of the simulated (a) and synthesized (b) Cu-MOF-74 58 Figure 2: FT-IR spectra of terephthalic acid and the Cu-MOF-74 60 Figure 3: TGA curve of the Cu-MOF-74 61 Figure 4: SEM micrograph of the Cu-MOF-74 61 Figure 5: TEM micrograph of Cu-MOF-74 at 500nm and 100nm 62 Figure 6: Pore size distribution of Cu-MOF-74 .62 Figure 7: Isotherm linear plot of Cu-MOF-74 63 Figure 8: Effect of temperature on the reaction yield 65 Figure 9: Effect of solvent on the reaction yield 66 Figure 10: Effect of reactant molar ratio on the reaction yield 68 Figure 11: Effect of catalyst quantity on the reaction yield .69 Figure 12: Effect of homogeneous catalysts on the reaction yield 70 Figure 13: Effect of heterogeneous catalysts on the reaction yield 71 Figure 14: Leaching test indicated no contribution from homogeneous catalysis of active species leaching into reaction solution 71 Figure 15: Catalyst recycling studies .72 Figure 16: PXRD patterns of the simulated (a) and synthesized (b) Cu-MOF-74 74 Figure 17: FT-IR spectra of the Cu-MOF-74 74 Figure 18: Effect of different temperatures on the reaction yield 79 Figure 19: Effect of solvent to the reaction 80 Figure 20: Effect of molar ratio of dibenzyl ether /(E)-acetophenone O-acetyl oxime acetate on the reaction yield .82 Figure 21: Effect of catalyst amount on the reaction yield 83 Figure 22: Effect of time on the reaction 84 Figure 23: Effect of oxidant on the reaction 85 Figure 24: Effect of oxidant amount on the reaction 86 Figure 25: Effect of antioxidant on the reaction 88 Figure 26: Leaching test indicated no contribution from homogeneous catalysis of active species leaching into reaction solution 89 Figure 27: Pyridine test 90 Figure 28: Catalyst reusing studies .91 Figure 29: FT-IR analyses of the new (a) and recovered (b) catalyst 92 Figure 30: PXRD determination of the new (a) and recovered (b) catalyst 93 Figure 31: Effect of different homogeneous catalyst on the reaction 93 Figure 32: Effect of different heterogeneous catalyst on the reaction 95 Figure 33: Effect of different atmospheres on reaction yield 96 Appendices Figure AC 43 1H-NMR spectra of for 2,4,6-triphenylpyridine 171 Appendices Figure AC 44 13C-NMR spectra of for 2,4,6-triphenylpyridine 2,4,6-triphenylpyridine (15) Prepared as shown in the general experimental procedure and purified on silica gel (230-400 mesh or 37-63 µm, ethyl acetate/hexane = 1:40 (v./v.), TLC silica gel 60 F254, Rf = 0.35): White solid, 85% yield (26.1 mg) 1HNMR (500 MHz, CDCl3) δ(ppm) 7.45 – 7.53 (m, 9H), 7.74 – 7.76 (m, 2H), 7.89 (s, 1H), 8.20 – 8.22 (m, 4H) 13 C NMR (CDCl3, 125 MHz) δ(ppm) 117.5, 127.5, 127.6, 129.1, 129.4, 129.5, 139.5, 140.0, 150.6, 157.9 172 Appendices Figure AC 45 1H-NMR spectra of for 4-phenyl-2,6-di(thiophen-2-yl)pyridine 173 Appendices Figure AC 46 13C-NMR spectra of for 4-phenyl-2,6-di(thiophen-2-yl)pyridine 4-phenyl-2,6-di(thiophen-2-yl)pyridine (16) Prepared as shown in the general experimental procedure and purified on silica gel (230-400 mesh or 37-63 µm, ethyl acetate/hexane = 1:40 (v./v.), TLC silica gel 60 F254, Rf = 0.35): White solid, 58% yield (18.5 mg) 1H-NMR (500 MHz, CDCl3) δ(ppm) 7.12 – 7.14 (t, J = 4.5 Hz, 2H), 7.41 – 7.42 (d, J = Hz, 2H), 7.45 –7.53 (m, 3H), 7.68 (s, 2H), 7.69 – 7.71 (m, 4H) 13 C- NMR (CDCl3, 125 MHz) δ(ppm) 115.2, 125.0, 127.2, 127.9, 128.1, 129.2, 138.7, 145.0, 150.3, 152.8 174 Appendices Figure AC 47 1H-NMR spectra of for 2,6-bis(4-Methoxyphenyl)-4-phenylpyridine 175 Appendices Figure AC 48 13C-NMR spectra of for 2,6-bis(4-Methoxyphenyl)-4-phenylpyridine 2,6-bis(4-Methoxyphenyl)-4-phenylpyridine (17) Prepared as shown in the general experimental procedure and purified on silica gel (230-400 mesh or 37-63 µm, ethyl acetate/hexane = 1:40 (v./v.), TLC silica gel 60 F254, Rf = 0.35): White solid, 79% yield (29.0 mg) 1H-NMR (500 MHz, CDCl3) δ(ppm) 3.89 (s, 6H), 7.02 – 7.04 (m, 4H), 7.45 – 7.47 (m, 1H), 7.50 – 7.53 (m, 2H), 7.73 – 7.74 (m, 2H), 7.77 (s, 2H), 8.14 – 8.17 (m, 4H) 13C NMR (CDCl3, 125 MHz) δ(ppm) 55.5, 114.2, 115.8, 127.3, 128.5, 128.9, 129.2, 132.5, 139.5, 150.1, 157.1, 160.6 176 Appendices  Charaterization of VNU-20 Figure AC 49: PXRD patterns of VNU-20 177 Appendices Figure AC 50: The Pawley refinements of activated VNU-20: The experimental (red), refined (black), and difference (green) patterns The Bragg positions are marked as blue bars The powder XR diffraction pattern of MOF VNU-20 in this experiment was confirmed relatively the same as the simulated and as-synthesized samples (Figure AC 49) Obviously, there was a very sharp peak at 2 of approximately 7o in the PXRD patterns of the activated VNU-20, indicating that a highly crystalline material was obtained After washing with solvent and then activating under dynamic vacuum, the structural maintenance of VNU-20 was proven by PXRD analysis (Figure AC 50) 178 Appendices Figure AC 51: Fourier transform infrared analysis (FT-IR) of H3BTC (a), H2NDC (b) and activated VNU-20 (c) Fourier transformed infrared (FT-IR) spectroscopy analysis was also conducted, in which, the peak at 1614 cm-1 was assigned to vC=O stretch of coordinated carboxylate (Figure AC 51) To be more specific, the absence of the strong peak at 1681 cm-1 as well as 1720 cm-1 and appearance of peak stretching vibration at 1614 cm-1 in FT-IR spectrum of activated VNU-20 crystal demonstrated the reaction of –COOH groups with metal ions The broad bands at 3600–3200 cm−1 were indicative of the presence of water in the metal coordination sphere 179 Appendices Figure AC 52: TGA analysis of VNU-20 The thermogravimetric analysis (TGA) has shown the change in thermal stability of the VNU-20 As a result, the initial weight loss of about 2.5% below 250 °C resulted from the evacuation of excess solvents such as DMF, methanol and water utilizing for the synthesis The second weight loss of about 7% in the range 250 °C to 330 °C, probably associated with the progressive departure of coordinated water molecules and residual free acid moieties The last weight loss of over 60% between 330 oC and 400 °C was ascribable to the destruction of organic linkers and degradation of framework Finally, the residue mass percentage of approximately 30% was attributed to an amount of Fe2O3 and carbon in the treated VNU-20, which was in consistency with those from model structure (Figure AC 52) 180 Appendices Figure AC 53: N2 uptake of VNU-20 at 77 K The closed and open circles represent the adsorption and desorption branches of the isotherm, respectively Figure AC 54: Pore size distribution of VNU-20 Nitrogen physisorption measurements were also carried out to determine surface area and pore size distribution of the VNU-20 By collecting high resolution nitrogen sorption isotherms at 77 K, the permanent porosity of the VNU-20 was confirmed with BET surface areas of 680 m2g-1 (Figure AC 53) Additionally, the Horvath-Kawazoe 181 Appendices method showed a pore volume of 0.24 cm3g-1 and an average pore diameter of around 6.8 Å (Figure AC 54) Figure AC 55: SEM (a) and TEM (b) micrograph of VNU-20 The morphology of VNU-20 was described through Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) (Figure AC 55) As the results, VNU-20 has a block form To sum up, a mixed-linker iron based MOF VNU-20 was successfully obtained by the combination of H3BTC, H2NDC and the sinusoidal [Fe3(CO2)7]∞ iron-rod SBU The characterization of VNU-20 was revealed through a diversity of modern technological equipments such as FT-IR, TEM, SEM, XRD, TGA and nitrogen physisorption measurements According to that, VNU-20 has a highly crystalline structure with relatively high thermal stability Moreover, the outstanding properties of VNU-20 has also been discovered that VNU-20 has a porous structure with BET surface areas of 680 m2g-1, a pore volume of 0.24 cm3g-1 and an average pore diameter of around 6.8 Å In comparison with previous synthesized MOFs and other materials such as zeolites and activated carbon, a mixed-linker iron based MOF VNU-20 is the promising heterogeneous catalyst for many application in the future 182 Appendices MY PROJECTS The article “Synthesis of 2-arylquinazolinones via ring expansion reaction of 2arylindole with amines under metal-organic framework catalysis” was published in Viet Nam Journal of Catalysis and Adsorption, 7-issue 1(2018) The article “Metal-Organic Framework Cu2(OBA)2(BPY) as efficient catalyst for C–O bond formation via oxidative cross-coupling reaction of benzaldehyde and 1,4-dioxane” was published in Viet Nam Journal of Catalysis and Adsorption, 7-issue 2(2018) 2-9 The article “Alternative routes to triphenylpyridines utilizing ketoximes as building blocks via cascade reactions under iron-organic framework catalysis” 183 Appendices  184 Appendices 185 ... used, because of their low affinities for cationic metal ions [8] Literature Reviews 1.1.2 General methods for the synthesis of MOFs During the last two decades, the synthesis of MOFs has attracted... transformation, as well as, as- synthesized active MOFs Coordination of the substrate to the metal requires either an expansion of the coordination sphere of the metal ion, or a displacement of. .. TÀI: Metal- organic frameworks as heterogeneous catalysts for the synthesis of quinazolinones and pyridines II NHIỆM VỤ VÀ NỘI DUNG: - Sử dụng xúc tác dị thể Cu-MOF-74 cho phản ứng tổng hợp quinazolinones