Application of mil 68 (in), fe3o (BPDC)3, MOF 235 as catalysts for c n and c o bond forming reactions

VIETNAM NATIONAL UNIVERSITY – HO CHI MINH CITY HO CHI MINH CITY UNIVERSITY OF TECHNOLOGY HA THANH MY PHUONG APPLICATION OF MIL-68(In), Fe3O(BPDC)3, MOF-235 AS CATALYST FOR C−N AND C−O BOND FORMING REACTIONS PhD THESIS HO CHI MINH CITY 2020 VIETNAM NATIONAL UNIVERSITY – HO CHI MINH CITY HO CHI MINH CITY UNIVERSITY OF TECHNOLOGY HA THANH MY PHUONG APPLICATION OF MIL-68(In), Fe3O(BPDC)3, MOF-235 AS CATALYST FOR C−N AND C−O BOND FORMING REACTIONS Major: Organic Chemical Technology Major code: 62520301 Independent examiner 1: Assoc Prof Dr Nguyen Phuong Tung Independent examiner 2: Assoc Prof Dr Hoang Thi Kim Dung Examiner 1: Assoc Prof Dr Tran Ngoc Quyen Examiner 2: Assoc Prof Dr Nguyen Thi Le Thu Examiner 3: Assoc Prof Dr Ton That Quang ADVISORS: Prof Dr Phan Thanh Son Nam Dr Le Thanh Dung DECLARATION OF ORIGINALITY I hereby declare that this is my own research study The research results and conclusions in this thesis are true, and are not copied from any other resources The literature references have been quoted with clear citation as requested Thesis Author Signature Ha Thanh My Phuong i TÓM TẮT LUẬN ÁN Luận án trình bày phương pháp tổng hợp, đặc trưng hóa lý hoạt tính xúc tác vật liệu khung kim loại Indium (In-MOF) MIL-68 (In) vật liệu khung kim sắt (Fe-MOF) bao gồm Fe3O(BPDC)3 MOF-235 Các vật liệu MOF sử dụng làm chất xúc tác dị thể cho phản ứng hình thành liên kết C−N C−O để tổng hợp hợp chất 2-nitro-3-arylimidazo[1,2-a]pyridine, 2,4-diarylpyridine α-acyloxy ether Chương luận án trình bày tổng quan tài liệu vật liệu In-MOF Fe-MOF cụ thể vật liệu MIL-68(In), Fe3O(BPDC)3 MOF-235 Tổng quan cấu trúc, tính chất, phương pháp tổng hợp, đặc tính ứng dụng xúc tác chúng Ngoài ra, chương tổng quan phản ứng hình liên kết C−N C−O để tổng hợp hợp chất 2-nitro-3-arylimidazo[1,2-a]pyridine, 2,4-diarylpyridine α-acyloxy ether Chương thứ hai luận án trình bày trình thực nghiệm tổng hợp vật liệu MIL68(In), Fe3O(BPDC)3 MOF-235 khảo sát điều kiện tổng hợp hợp chất 2nitro-3-arylimidazo[1,2-a]pyridine, 2,4-diarylpyridine α-acyloxyether với xúc tác MIL-68(In), Fe3O(BPDC)3 MOF-235 tương ứng Chương thứ ba luận án trình bày kết thảo luận vật liệu MIL-68(In), Fe3O(BPDC)3 MOF-235 tổng hợp khả ứng dụng vật liệu MOF phản ứng hình thành liên kết C−N C−O Các MOF tổng hợp phương pháp nhiệt dung mơi xác định đặc trưng hố lý phương pháp đo PXRD, SEM, TEM, TGA, FT-IR, phân bố kích thước lỗ xốp đo hấp phụ vật lý nitơ Kết thu cho thấy In-MOF Fe-MOF có hoạt tính xúc tác cao cho phản ứng hình thành liên kết C−N C−O xúc tác thu hồi tái sử dụng nhiều lần mà không bị giảm đáng kể hoạt tính xúc tác Theo hiểu biết tốt chúng tơi, chuyển hố sử dụng chất xúc tác MIL-68(In), Fe3O(BPDC)3 and MOF-235 chưa đề cập trước tài liệu ii THESIS SUMMARY This thesis describes the synthesis, characterization and catalytic applications of indiumbased metal-organicframework (In-MOF) and iron-based metal-organic frameworks (Fe-MOFs) including MIL-68(In), Fe3O(BPDC)3 and MOF-235 These MOFs were used as heterogeneous catalysts for C−N and C−Obond forming reactions to synthesize 2-nitro-3-aryl imidazo[1,2-a]pyridines, 2,4-diarylpyridines and α-acyloxy ethers The first chapter of this thesis provides a literature review of In-MOF and Fe-MOFs including MIL-68(In), Fe3O(BPDC)3 and MOF-235 An overview of their structures, properties, synthesis and characterization methods and catalytic applications are described In addition, the chapter also reviews C−N and C−O bond forming reactions for the synthesis of 2-nitro-3-aryl imidazo[1,2-a]pyridines, 2,4-diarylpyridines and αacyloxy ethers The second chapter of this thesis presents the experimental process of synthesizing MIL68(In), Fe3O(BPDC)3 and MOF-235 and test catalytic activity of these MOFs on C−N and C−O bonds forming reactions The third chapter of this thesis presents the results and discussion about the synthesized MOFs and the ability to apply these MOFs on C−N and C−O bonds forming reactions These MOFs were prepared by solvothermal methods and characterized by PXRD, SEM, TEM, TGA, FT-IR, pore size distribution and nitrogen physisorption measurements These MOFs were found to be highly catalytically active for C−N and C−O bonds forming reactions The In-MOF and Fe-MOFs catalysts could be recovered and reused several times without a significant degradation in catalytic activity To the best of our knowledge, these transformations using MIL-68(In), Fe3O(BPDC)3 and MOF-235 catalysts were not previously mentioned in the literature iii ABSTRACT Three highly porous indium-based organic frameworks (In-MOF) like MIL-68(In), ironbased organic frameworks (Fe-MOFs) such as Fe3O(BPDC)3 and MOF-235 were synthesized and characterized by PXRD, SEM, TEM, TGA, FT-IR, pore size distribution and nitrogen physisorption measurements In-MOF were used as heterogeneous catalysts for C−N and C−O forming reactions to synthesize 2-nitro-3aryl imidazo[1,2-a]pyridines Fe3O(BPDC)3 was employed as heterogeneous catalyst for C−N bond forming reactions to synthesize 2,4-diaryl pyridines MOF-235 was utilized as heterogeneous catalyst for C−O bond forming reactions to synthesize αacyloxy ethers These catalytic systems offered practical approaches with high yields and selectivity Additionally, broad functionality was shown to be compatible The InMOF and Fe-MOFs catalysts could be recovered and reused several times without significant degradation in catalytic activity To the best of our knowledge, these transformations using MIL-68(In), Fe3O(BPDC)3 and MOF-235 catalysts were previously achieved under heterogeneous catalysis conditions in the literature iv ACKNOWLEDGMENT I reserve special thanks to my research advisors, Prof Dr Phan Thanh Son Nam and Dr Le Thanh Dung, who have supported me over the course of my research work Their motivation, patience, enthusiasm and immense knowledge have kept me going during the past four years I was so lucky to have such a precious opportunity to work under their guidance I really would like to learn more from such renowned and respected chemists I would aslo like to thank Assoc Prof Dr Pham Thanh Quan and Dr Phan Thi Hoang Anh for their insight and questions that have undoubtedly helped me progress to this point I would like to thank Assoc Prof Dr Le Thi Hong Nhan, Dr Truong Vu Thanh and Dr Nguyen Thanh Tung for guiding me how to recognize and find the best ways to solve the scientific problems I would be remiss if I did not acknowledge all members of my group (Lieu Ngoc Thien, Doan Hoai Son) for the stimulating discussions in Organic Chemistry Division Additionally, I wish to acknowledge three undergraduate students (Phan Thi Bao Trang, Le Thi Thanh Binh, To Chi Trung) and and graduated student (Le Duc Thuan) for their helps during the time they studied in laboratory I also thank to my colleagues in Chemical Engineering Department at TayDo University for their encouragement My deepest gratitude to my family The support and love from my family is of inestimable value v TABLE OF CONTENTS TABLE OF CONTENTS .vi LIST OF FIGURES viii LIST OF SCHEMES xii LIST OF TABLES .xiv LIST OF ABBREVIATION xv INTRODUCTION CHAPTER LITERATURE REVIEW OF MIL-68(In), Fe3O(BPDC)3, MOF-235 AND C−N, C−O BOND FORMING REACTIONS 1 Metal-organic frameworks Synthesis and structure of MIL-68(In), MOF-235 and Fe3O(BPDC)3 11 1.2 Synthesis and structure of MIL-68(In) 13 1.2 Synthesis and structure of MOF-235 15 1.2 Synthesis and structure of Fe3O(BPDC)3 17 Application of MIL-68 (In), MOF-235 and Fe3O(PBDC)3 in catalysis 18 C−N and C−O bond forming reactions 24 1.4.1 C−N bond formation in synthesis of 2-nitro-3-arylimidazo[1,2-a]pyridine derivatives 25 1.4.2 C−N bond formation for synthesis of aryl substituted pyridines 28 1.4.3 C−O bond formation for synthesis of α-acyloxy ethers 34 EXPERIMENTAL 40 2.1 Introduction 40 2.2 Synthesis of MIL-68(In), Fe3O(BPDC)3 and MOF-235 41 2.2.1 Materials and instrumentation 41 2.2.2 Catalyst synthesis 41 2.3 Catalyitic studies of MIL-68(In), Fe3O(BPDC)3 and MOF 235 on C−N and C−O bond forming reactions 44 2.3 Materials and instrumentation 44 2.3 Catalytic studies of MIL-68(In) on C−N bond formation reaction between 2-aminopyridines and nitroalkenes 45 2.3 Catalytic studies of Fe3O(BPDC)3 on C−N bond formation reaction between N,N-dialkylanilines with ketoxime carboxylates 46 vi 2.3 Catalytic studies of MOF-235 on C−O bond formation reaction for the direct esterification of carboxylic acids with C(sp3)−H bonds to form α-acyloxy ethers 46 RESULT AND DISCUSSION 48 Characterization of MIL-68(In), MOF-235 and Fe3O(BPDC)3 48 3.1.1 Characterization of MIL-68(In) 48 3.1.2 Characterization of MOF-235 53 3.1.3 Characterization of Fe3O(BPDC)3 58 Catalyitic studies of MIL-68(In), Fe3O(BPDC)3 and MOF 235 on C−N and C−O bond forming reactions 63 3.2.1 Catalytic studies of MIL-68(In) on CN bond formation reactions (1) 63 3.2.2 Catalytic studies of Fe3O(BPDC)3 on CN bond formation reactions (2) 83 3.2.3 Catalytic studies of MOF-235 on CO bond forming reaction (3) .103 CONCLUSION AND RECOMMENDATIONS 124 Summary of current work 124 Contributions of this thesis 124 Recommendations 125 LIST OF PUBLICATIONS 127 LIST OF OTHER PUBLICATIONS 128 REFERENCES 129 APPENDICES .139 vii LIST OF FIGURES Figure 1.1 Example Metal-Organic Framework (MOF) The yellow sphere represents the pore space within the crystal structure [5] Figure 1.2 Year wise publication status from 2000 to 2015 of various aspects of MOFs (a) MOFs, (b) MOFs as luminescent materials, (c) MOFs for gas storage, (d) MOFs as magnets, (e) MOFs for drug delivery and (f) MOFs as catalyst (data source: Sci-finder, retrieved on October, 12 2015) [6] Figure 1.3 Potential polytopic organic acids as linkers in MOFs [6] Figure 1.4 Coordination geometries of transition metal ions [6] Figure 1.5 Examples of SBUs from carboxylate MOFs O, red; N, green; C, black [27] Figure 1.6 The values in parentheses represent the pore volume (cm3.g-1) of these materials [29] Figure 1.7 Aspects of crystallization in synthesis of solid compounds [32] Figure 1.8 (a) Synthesis conditions commonly used for MOF preparation; (b) indicative summary of the percentage of MOFs synthesized using the various preparation routes [33] 11 Figure 1.9 MIL-68(In) SBU (gray: carbon; red: oxygen; teal: indium) [42] 14 Figure 1.10 View of the structure of MIL-68(In) along the c axis [42] 14 Figure 1.11 View of a chain of InO4(OH)2 octahedra in MIL-68(In) [42] 15 Figure 1.12 The structures of MOF-235 (Fe, blue; O, red; Cl, teal; C, gray) [53] 16 Figure 1.13 Inorganic and organic building units used to assemble MOF-235: (a) oxygen-centered iron-carboxylate trimer (Fe, blue;O, red; C, gray) shown in ball-andstick and polyhedral representations of trigonal prismatic geometry (blue) and (b) ditopic links, 1,4-benzenedicarboxylate (BDC) [53] 16 Figure 1.14 The basic unit of MOF-235 in solvent (a) and activated (b) [53] 17 Figure 1.15 Organization of the two orthogonally interpenetrated trigonal bipyramidalbuilding units of of Fe3O(BPDC)3 [45] 18 Figure 1.16 Proposed mechanisms for the Strecker reaction catalyzed by In-MOF [65] 20 Figure 1.17 Some biologically active heterocycles containing 3-aryl substituted imidazopyridines [86-88] 25 Figure 1.18 Selected bioactive agents containing the poly-arylated pyridine structure [95, 96] 29 Figure 1.19 Selected examples of α-acyloxy ethers [103] 35 Figure 3.1 X-ray powder diffractograms of the MIL-68(In) 49 Figure 3.2 SEM and TEM micrograph of the MIL-68(In) 49 viii Fig.S32 13C-NMR spectrum of 1,4-dioxan-2-yl 2-phenylacetate Characterization data for 1,4-dioxan-2-yl 2-phenylacetate Prepared as shown in the general experimental procedure and purified by silica gel column chromatography (petroleum ether/dichloromethane): White solid, 53% Yield (116 mg) 1H-NMR (500 MHz, CDCl3) 3.56 - 3.58 (m, 1H), 3.70 - 3.78 (m, 6H), 3.99 4.04 (m, 1H), 5.85 (s, 1H), 7.25 -7.28 (m, 1H), 7.31 - 7.34 (m, 4H) 13C NMR (CDCl3, 125 MHz) δ(ppm) 41.3, 61.6, 66.0, 67.6, 89.6, 127.2, 128.6, 129.3, 133.5, 170.3 208 Fig.S33 Heteronuclear multiple-bond correlation spectroscopy (HMBC) spectrum of 1,4-dioxan-2-yl 2-phenylacetate 209 Fig.S34 Heteronuclear single-quantum correlation spectroscopy (HSQC) spectrum of 1,4-dioxan-2-yl 2-phenylacetate 210 Fig.S35 1H-NMR spectrum of 1,4-dioxan-2-yl 6-bromohexanoate 211 Fig.S36 13C-NMR spectrum of 1,4-dioxan-2-yl 6-bromohexanoate Characterization data for 1,4-dioxan-2-yl 6-bromohexanoate Prepared as shown in the general experimental procedure and purified by silica gel column chromatography (petroleum ether/dichloromethane): Colorless oil, 27% yield (76 mg) 1H-NMR (500 MHz, CDCl3) 1.49-1.54 (m, 2H), 1.67-1.73 (m, 2H), 1.86-1.92 (m, 2H), 2.41-2.44 (m, 2H), 3.40 (t, 2H), 3.61 (dt, 1H), 3.70-3.80 (m, 4H), 4.08-4.13 (m, 1H), 5.85 (t, 1H) 13C NMR (CDCl3, 125 MHz) δ(ppm) 23.9, 27.5, 32.3, 33.4, 34.0, 61.7, 66.0, 67.7, 89.2, 172.1 212 Fig.S37 1H-NMR spectrum of 1,3-dioxolan-4-yl biphenyl-3-carboxylate 213 Fig.S38 13C-NMR spectrum of 1,3-dioxolan-4-yl biphenyl-3-carboxylate Characterization data for 1,3-dioxolan-4-yl biphenyl-3-carboxylate Prepared as shown in the general experimental procedure and purified by silica gel column chromatography (petroleum ether/dichloromethane): Colorless oil, 83% yield H-NMR (500 MHz, CDCl3) 3.68-3.72 (m, 1H), 3.82-3.84 (m, 2H), 3.91-3.97 (m, 2H), 4.22-4.27 (m, 1H), 6.19 (t, 1H), 7.48-7.54 (m, 2H),7.60-7.63 (m, 1H), 7.86 (d, 1H), 8.02 (d, 1H), 8.33-8.34 (m, 1H), 9.00 (d, 1H) 13 C NMR (CDCl3, 125 MHz) δ(ppm) 61.9, 66.2, 67.9 89.9, 124.4, 125.8 126.2, 126.3, 128.0, 128.6, 130.9, 131.6, 133.9, 134.0, 165.9 214 Fig.S39 1H-NMR spectrum of 1,3-dioxolan-4-yl 4-methoxybenzoate 215 Fig.S40 13C-NMR spectrum of 1,3-dioxolan-4-yl 4-methoxybenzoate Characterization data for 1,3-dioxolan-4-yl 4-methoxybenzoate Prepared as shown in the general experimental procedure and purified by silica gel column chromatography (petroleum ether/dichloromethane): Colorless oil, 84% yield H NMR (500 MHz, CDCl3) 3.86 (s, 3H), 4.09-4.12 (m, 2H), 4.14-4.18 (m, 1H), 5.15 (d, 2H), 6.56 (dd, 1.5 Hz , 1H), 6.91-6.93 (m, 2H),7.99-8.01 (m, 2H) 13C NMR (CDCl3, 125 MHz) δ(ppm) 55.4, 70.7, 94.4 95.8, 113.7, 121.8, 131.9, 163.8, 165.5 216 Fig.S41 1H-NMR spectrum of 1,3-dioxolan-4-yl 3,4-dimethoxybenzoate 217 Fig.S42 13C-NMR spectrum of 1,3-dioxolan-4-yl 3,4-dimethoxybenzoate Characterization data for 1,3-dioxolan-4-yl 3,4-dimethoxybenzoate Prepared as shown in the general experimental procedure and purified by silica gel column chromatography (petroleum ether/dichloromethane): Colorless oil, 78% yield (198 mg) 1H NMR (500 MHz, CDCl3) 3.93 (d, 6H), 4.11 (dd, 1H), 4.16 (dd, 1H), 5.15 (s,1H), 5.20 (s,1H), 6.56 (dd, Hz, 1H), 6.88 (d, 1H), 7.53 (d, 1H), 7.68 (dd, 1H) 13C NMR (CDCl3, 125 MHz) δ(ppm) 56.0, 70.7, 94.6, 95.8, 110.2, 112.0, 121.8, 124.0, 148.7, 153.5, 165.6 218 Fig.S43 Heteronuclear multiple-bond correlation spectroscopy (HMBC)spectrum of 1,3-dioxolan-4-yl 3,4-dimethoxybenzoate 219 Fig.S44 Heteronuclear single-quantum correlation spectroscopy (HSQC) spectrum of 1,3-dioxolan-4-yl 3,4-dimethoxybenzoate 220 Fig.S45 1H-NMR spectrum of cyclopentyloxymethyl 4-methoxybenzoate 221 Fig.S46 13C-NMR spectrum of cyclopentyloxymethyl 4-methoxybenzoate Characterization data for cyclopentyloxymethyl 4-methoxybenzoate Prepared as shown in the general experimental procedure and purified by silica gel column chromatography (petroleum ether/dichloromethane): brown oil, 83% yield (207 mg) 1H NMR (500 MHz, CDCl3): 1.53-1.58 (m, 2H), 1.72-1.80 (m, 6H), 3.86 (s, 3H), 4.25-4.27 ( m, 1H), 5.52 (s, 2H), 6.92 (d, 2H), 8.02 (d, 2H) 13C NMR (125 MHz, CDCl3) δ(ppm) 23.3, 32.8, 55.4, 81.9, 88.7, 113.6, 122.5, 131.8, 163.5, 165.8 222 ... following subsection will cover the C? ? ?N and C? ? ?O bond forming reactions C? ? ?N and C? ? ?O bond forming reactions Imidazo[1,2-a]pyridines represent a prominent collection of biologically active nitrogen-containing... Synthesis and structure of Fe 3O( BPDC)3 17 Application of MIL- 68 (In), MOF- 235 and Fe 3O( PBDC)3 in catalysis 18 C? ? ?N and C? ? ?O bond forming reactions 24 1.4.1 C? ? ?N bond formation in synthesis...VIETNAM NATIONAL UNIVERSITY – HO CHI MINH CITY HO CHI MINH CITY UNIVERSITY OF TECHNOLOGY HA THANH MY PHUONG APPLICATION OF MIL- 68( In), Fe 3O( BPDC)3, MOF- 235 AS CATALYST FOR C? ? ?N AND C? ? ?O BOND FORMING