Utilizing cu MOF 74 and Cu2(OBA)2BPY materials as heterogeneous catalysts in systhesis of 1,4 benzothiazines and 3 aroylquinolines

VIETNAM NATIONAL UNIVERSITY HO CHI MINH CITY BACH KHOA UNIVERSITY - DANG VAN HA UTILIZING Cu-MOF-74 AND Cu2(OBA)2BPY MATERIALS AS HETEROGENEOUS CATALYSTS IN SYNTHESIS OF 1,4-BENZOTHIAZINES AND 3-AROYLQUINOLINES Major: Chemical Engineering Number: 60.52.03.01 MASTER THESIS HO CHI MINH CITY, AUGUST 2018 ACKNOWLEDGEMENT The success and final outcome of this thesis required a lot of guidance and assistance from many people and I am extremely privileged to have got this all along the completion of my project All that I have done is only owing to such supervision and assistance and I would not forget to thank them First of all, I respect and thank our adviser, Prof Dr Phan Thanh Son Nam for providing me an opportunity to the thesis work in Manar lab and giving me all support and guidance which made me complete the project duty I am extremely thankful to him for providing such a nice encouragement, guidance and financial support, although he had busy schedule managing the department affairs Furthermore, our profound gratitude is expanded to all the staffs and co-workers in our laboratory, especially Mr Ha Quang Hiep, Ms Nguyen Thi Kim Oanh, Mr Nguyen Thai Anh, Mr Nguyen Kim Chung, Mr Doan Hoai Son, for teaching me valuable lessons when I were still clueless about this field Moreover, we also want to express our fortune for having a chance to work with my friends at MANAR LAB I not think that I would be able to complete this work to this state without your help Last but not least, I would like to express special thanks to my family Words cannot express how grateful I am to our parents for all sacrifices that they have made on your behalf Their constant encouragement gave me the important strength to successfully finish this research work i ABSTRACT A crystalline porous metal-organic framework Cu-MOF-74 and Cu2(OBA)2(BPY) were solvothermally synthesized and then characterized by X-ray powder diffraction (XRD), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), Thermogravimetric analysis (TGA), Fourier transform infrared (FT-IR), and Nitrogen physisorption measurements The obtained Cu-MOF-74 was utilized as a reusable heterogeneous catalyst for the synthesis of substitued benzo[b][1,4]thiazine-4-carbonitriles from 2- aminobenzothiazole and terminal alkyne with the presence of base and oxidant The product of the reaction was separated and predicted the structure using Gas chromatography with Mass spectroscopic detector and NMR spectroscopy From the best of our knowledge, this was the first time that the reaction was carried out in under the catalysis of heterogeneous catalyst This broaden a great potential improvement of the reaction in terms of separation and reusability of the catalyst The Cu2(OBA)2(BPY) is demonstrated as an efficient heterogeneous catalyst for the formation of 3-acylquinolines from 2-aminoaryl methanols and saturated ketones The optimal conditions employed 2, 2, 6, 6-Tetramethyl-1-piperidinyloxy (TEMPO) as the oxidant and pyridine as ligand in N,N-dimethylformamide at 120oC Furthermore, leaching test was also conducted to investigate the heterogeneity Satisfyingly, the catalyst can be facilely recycled several times under optimal conditions without significant degradation in the catalytic activity This work dedicated to the ideal of green chemistry, which is the vision of current and future chemistry ii CONTENTS ACKNOWLEDGEMENT i ABSTRACT ii CONTENTS iii LIST OF FIGURES v LIST OF TABLES viii LIST OF SCHEMES ix ABBREVIATIONS AND SYMBOLS xi CHAPTER 1: LITERATURE REVIEWS 1.1 1.2 Introduction to metal-organic frameworks 1.1.1 General introduction 1.1.2 General methods for the synthesis of metal-organic frameworks 1.1.3 Applications of metal–organic frameworks Copper-based metal-organic frameworks as heterogeneous catalyst CHAPTER 2: RESEARCH OF CATALYTIC ACTIVITY OF COPPERBASED METAL-ORGANIC FRAMEWORK Cu-MOF-74 IN THE SYNTHESIS OF 1,4-BENZOTHIAZINE 13 2.1 The Cu-MOF-74 metal-organic framework 13 2.1.1 Structure and properties 13 2.1.2 Application in catalysis 14 2.2 The 1,4-benzothiazines and conventional synthesis 16 2.3 Experimental 18 2.3.1 Chemicals and instruments 18 2.3.2 Synthesis of Cu-MOF-74 20 2.3.3 Catalytic studies on the synthesis of 3-phenyl-4H-benzo[b][1,4]thiazine- 4-carbonitrile 20 2.4 Results and discussions 20 2.4.1 Synthesis of Cu-MOF-74 21 2.4.2 Catalytic studies on the synthesis of 3-phenyl-4H-benzo[b][1,4]thiazine- 4-carbonitrile 25 2.5 Conclusions 45 iii CHAPTER 3: COPPER-CATALYZED ONE-POT DOMINO REACTIONS VIA C-H BOND ACTIVATION: SYNTHESIS OF 3-AROYLQUINOLINES FROM 2-AMINOBENZYLALCOHOLS AND PROPIOPHENONES UNDER METAL-ORGANIC FRAMEWORK CU(OBA)2BPY CATALYSIS 46 3.1 3.2 3.3 The Cu2(OBA)2(BPY) metal-organic framework 46 3.1.1 Structure and Properties of Cu2(OBA)2(BPY) 46 3.1.2 Applications of Cu2(OBA)2(BPY) in catalysis 47 The quinoline derivatives 49 3.2.1 Introduction 49 3.2.2 Synthesis route of quinoline derivatives 50 Experimental 57 3.3.1 Materials and Instrumentations 57 3.3.2 Synthesis of Cu2(OBA)2(BPY) catalyst 59 3.3.3 The catalytic studies on the synthesis of phenyl(quinolin-3- yl)methanone 60 3.4 Results and discussions 61 3.4.1 Synthesis and characterization of Cu2(OBA)2(BPY) 61 3.4.2 The catalytic studies on the synthesis of phenyl(quinolin-3- yl)methanone 66 3.5 Conclusions 89 REFERENCES 90 APPENDIX A: CALIBRATION CURVE 99 APPENDIX B: GC AND MS RESULTS 102 APPENDIX C: NMR OF 1,4-BENZOTHIAZINE 105 APPENDIX D: NMR OF 3-ACYLQUINOLINES 145 iv LIST OF FIGURES Figure 2.1 Crystal structure of a MOF-74 (left) and the metal oxide chains connected by organic linkers (right) O, red; C, black; H, white; metal, blue 13 Figure 2.2 Structure of Cu-MOF-74 before and after activation 14 Figure 2.3 Antipsychotic and antihistaminic drugs from phenothiazines 16 Figure 2.4 Powder X-ray diffraction patterns of Cu-MOF-74 21 Figure 2.5 FT-IR spectra of the Cu-MOF-74 and dihydroxyterephtalic acid 22 Figure 2.6 SEM and TEM micrographs of Cu-MOF-74 22 Figure 2.7 Isotherm linear plot of Cu-MOF-74 23 Figure 2.8 Poresize distribution of Cu-MOF-74 24 Figure 2.9 TGA curve of the Cu-MOF-74 24 Figure 2.10 Yield of 3-phenyl-4H-benzo[b][1,4]thiazine-4-carbonitrile vs reaction time at different temperatures 26 Figure 2.11 Yield of 3-phenyl-4H-benzo[b][1,4]thiazine-4-carbonitrile vs time in different solvents 27 Figure 2.12 Yield of 3-phenyl-4H-benzo[b][1,4]thiazine-4-carbonitrile vs time at different catalyst concentrations 28 Figure 2.13 Yield of 3-phenyl-4H-benzo[b][1,4]thiazine-4-carbonitrile vs time at different reactant molar ratios 29 Figure 2.14 Yield of 3-phenyl-4H-benzo[b][1,4]thiazine-4-carbonitrile vs time with different oxidants 30 Figure 2.15 Yield of 3-phenyl-4H-benzo[b][1,4]thiazine-4-carbonitrile vs time at different DTBP amounts 31 Figure 2.16 Yield of 3-phenyl-4H-benzo[b][1,4]thiazine-4-carbonitrile vs time with different bases 32 Figure 2.17 Yield of 3-phenyl-4H-benzo[b][1,4]thiazine-4-carbonitrile vs time at different Cs2CO3 amounts 33 Figure 2.18 Leaching test showed that 3-phenyl-4H-benzo[b][1,4]thiazine-4carbonitrile was not produced after the isolation of the catalyst 34 v Figure 2.19 Yield of 3-phenyl-4H-benzo[b][1,4]thiazine-4-carbonitrile vs time with different homogeneous catalysts 35 Figure 2.20 Yield of 3-phenyl-4H-benzo[b][1,4]thiazine-4-carbonitrile vs time with different heterogeneous catalysts 36 Figure 2.21 Catalyst reutilizing studies 37 Figure 2.22 FT-IR results of the new (a) and reutilized (b) catalyst 38 Figure 2.23 XRD results of the new (a) and reutilized (b) catalyst 38 Figure 3.1 The structure of Cu(OBA)2BPY………………………………… 47 Figure 3.2 Biologically active molecules containing 3-substituted quinolones 49 Figure 3.3 X-ray powder diffractograms of the Cu2(OBA)2(BPY) 62 Figure 3.4 FT-IR spectra of the Cu2(OBA)2(BPY), H2OBA, 4,4-bipyridine 63 Figure 3.5 TGA analysis of the Cu2(OBA)2(BPY) 64 Figure 3.6 Pore size distribution of the fresh Cu2(OBA)2(BPY) 65 Figure 3.7 Nitrogen adsorption/desorption isotherm of the Cu2(OBA)2(BPY) Adsorption data are shown as closed circles and desorption data as open circles 65 Figure 3.8 SEM (a) and TEM (b) micrograph of Cu2(OBA)2(BPY) 66 Figure 3.9 Effect of temperature on reaction yield 67 Figure 3.10 Effect of different solvents on reaction yield 69 Figure 3.11 Effect of amount of DMF on the reaction yield 70 Figure 3.12 Effect of the 2-aminobenzyl alcohol : propiophenone molar ratio on the reaction yield 71 Figure 3.13 Effect of catalyst amount on the reaction yield 72 Figure 3.14 Effect of time on the reaction yield 73 Figure 3.15 Effect of different oxidants on the reaction yield 73 Figure 3.16 Effect of oxidant amount on the reaction yield 75 Figure 3.17 Effect of different ligands on the reaction yield 76 Figure 3.18 Effect of pyridine amount on reaction yield 77 Figure 3.19 Effect of different heterogeneous catalysts on the reaction 78 Figure 3.20 Effect of different homogeneous catalysts on the reaction 79 Figure 3.21 Leaching test 81 Figure 3.22 Catalyst recycling studies 82 vi Figure 3.23 X-ray powder diffractograms of the fresh (a) and reused (b) Cu2(OBA)2(BPY) catalyst 83 Figure 3.24 FT-IR spectra of the fresh (red) and reused (black) Cu2(OBA)2(BPY) catalyst 84 Figure 3.25 Yields of phenyl(quinolin-3-yl)methanone in the presence of ascorbic acid 85 vii Fig D19 1H-NMR spectra of (7-bromoquinolin-3-yl)(phenyl)methanone (table 3.2, entry 10) 163 Fig D20 13C-NMR spectra of (7-bromoquinolin-3-yl)(phenyl)methanone (table 3.2, entry 10) Characterization data for (7-bromoquinolin-3-yl)(phenyl)methanone Prepared as shown in the general experimental procedure and purified on silica gel (hexane/ ethyl acetate =7/ 3): yellow solid, 87% yield 1H NMR (500 MHz, CDCl3) δ 9.31 (d, J = 1.3 Hz, 1H), 8.46 (d, J = 1.8 Hz, 1H), 8.09 (dd, J = 7.5, 5.7 Hz, 2H), 7.92 (dd, J = 9.0, 2.1 Hz, 1H), 7.87 – 7.84 (m, 2H), 7.70 – 7.66 (m, 1H), 7.55 (t, J = 7.7 Hz, 2H) 13C NMR (126 MHz, CDCl3) δ 194.6, 150.7, 148.0, 137.8, 136.9, 135.4, 133.5, 131.3, 131.1, 131.0, 130.2, 128.9, 127.9, 121.8 164 Fig D21 1H-NMR spectra of (6-bromoquinolin-3-yl)(phenyl)methanone (table 3.2, entry 11) 165 Fig D22 13C-NMR spectra of (6-bromoquinolin-3-yl)(phenyl)methanone (table 3.2, entry 11) Characterization data for (6-bromoquinolin-3-yl)(phenyl)methanone Prepared as shown in the general experimental procedure and purified on silica gel (hexane/ ethyl acetate =7/ 3): yellow solid, 85% yield 1H NMR (500 MHz, CDCl3) δ 9.32 (s, 1H), 8.47 (d, J = 1.9 Hz, 1H), 8.11 – 8.06 (m, 2H), 7.92 (dd, J = 9.0, 2.2 Hz, 1H), 7.86 (dd, J = 8.2, 1.2 Hz, 2H), 7.67 (dd, J = 10.6, 4.3 Hz, 1H), 7.55 (t, J = 7.8 Hz, 2H) 13C NMR (126 MHz, CDCl3) δ 194.5, 150.6, 147.9, 137.9, 136.8, 135.5, 133.5, 131.2, 131.0, 130.2, 128.9, 128.0, 121.9 166 Fig D23 1H-NMR spectra of (3-chlorophenyl)(8-methylquinolin-3-yl)methanone (table 3.2, entry 12) 167 Fig D24 13C-NMR spectra of (3-chlorophenyl)(8-methylquinolin-3-yl)methanone (table 3.2, entry 12) Characterization data for (3-chlorophenyl)(8-methylquinolin-3-yl)methanone Prepared as shown in the general experimental procedure and purified on silica gel (hexane/ ethyl acetate = 10/1): light yellow solid, 65% yield 1H NMR (500 MHz, CDCl3) δ 9.30 (d, J = 2.2 Hz, 1H), 8.53 (d, J = 2.2 Hz, 1H), 7.84 (t, J = 1.8 Hz, 1H), 7.77 (d, J = 8.1 Hz, 1H), 7.74 – 7.69 (m, 2H), 7.64 – 7.60 (m, 1H), 7.56 – 7.51 (m, 1H), 7.47 (t, J = 7.8 Hz, 1H), 2.85 (s, 3H) 13C NMR (126 MHz, CDCl3) δ 193.7, 149.1, 147.5, 139.3, 139.0, 137.8, 137.6, 133.1, 132.5, 130.1, 130.0, 129.4, 128.3, 127.7, 127.4, 126.8, 18.3 168 Fig D25 1H-NMR spectra of (7-chloroquinolin-3-yl)(4-fluorophenyl)methanone (table 3.2, entry 13) 169 Fig D26 13C-NMR spectra of (7-chloroquinolin-3-yl)(4-fluorophenyl)methanone (table 3.2, entry 13) Characterization data for (7-chloroquinolin-3-yl)(4-fluorophenyl)methanone Prepared as shown in the general experimental procedure and purified on silica gel (hexane/ ethyl acetate = 4/1): yellow solid, 92% yield 1H NMR (500 MHz, CDCl3) δ 9.13 (d, J = 1.7 Hz, 1H), 8.37 (d, J = 1.7 Hz, 1H), 8.05 (s, 1H), 7.84 – 7.69 (m, 3H), 7.46 (dd, J = 8.7, 1.9 Hz, 1H), 7.06 – 7.11 (m, 2H) 13C NMR (126 MHz, CDCl3) δ 193.1, 167.0, 151.3, 149.9, 138.4, 138.2, 133.3, 132.9, 132.8, 130.4, 130.3, 129.1, 128.8, 116.2 170 Fig D27 1H-NMR spectra of (6-bromoquinolin-3-yl)(4-(trifluoromethyl)phenyl)methanone (table 3.2, entry 14) 171 Fig D28 13C-NMR spectra of (6-bromoquinolin-3-yl)(4 (trifluoromethyl)phenyl)methanone (table 3.2, entry 14) Characterization data for (6-bromoquinolin-3-yl)(4- (trifluoromethyl)phenyl)methanone Prepared as shown in the general experimental procedure and purified on silica gel (hexane/ ethyl acetate = 4/1): yellow solid, 83% yield 1H NMR (500 MHz, CDCl3) δ 9.33 (s, 1H), 8.46 (s, 1H), 8.08 – 8.10(m, 2H), 7.95 (t, J = 7.4 Hz, 3H), 7.83 (d, J = 8.0 Hz, 2H) 13 C NMR (126 MHz, CDCl3) δ 193.6, 150.4, 150.4, 139.9, 138.0, 135.8, 131.4, 131.2, 130.3, 126.0, 126.0, 126.0, 125.9, 122.1 172 Fig D29 1H-NMR spectra of (7-bromoquinolin-3-yl)(thiophen-2-yl)methanone (table 3.2, entry 15) 173 Fig D30 13C-NMR spectra of (7-bromoquinolin-3-yl)(thiophen-2-yl)methanone (table 3.2, entry 15) Characterization data for (7-bromoquinolin-3-yl)(thiophen-2-yl)methanone Prepared as shown in the general experimental procedure and purified on silica gel (hexane/ ethyl acetate = 4/1): yellow solid, 87% yield 1H NMR (500 MHz, CDCl3) δ 9.34 (d, J = 1.8 Hz, 1H), 8.56 (d, J = 1.6 Hz, 1H), 8.12 (d, J = 2.0 Hz, 1H), 8.08 (d, J = 9.0 Hz, 1H), 7.92 (dd, J = 9.0, 2.1 Hz, 1H), 7.83 (dd, J = 4.9, 0.9 Hz, 1H), 7.73 – 7.68 (m, 1H), 7.23 (dd, J = 4.8, 3.9 Hz, 1H) 13 C NMR (126 MHz, CDCl3) δ 185.9, 150.0, 148.1, 143.1, 136.7, 135.5, 135.3, 131.6, 131.3, 131.1, 128.6, 128.0, 121.9 174 Fig D31 1H-NMR spectra of (4-phenylquinolin-3-yl)(p-tolyl)methanone (table 3.2, entry 16) 175 Fig D32 13C-NMR spectra of (4-phenylquinolin-3-yl)(p-tolyl)methanone (table 3.2, entry 16) Characterization data for (4-phenylquinolin-3-yl)(p-tolyl)methanone Prepared as shown in the general experimental procedure and purified on silica gel (hexane/ ethyl acetate = 4/1): yellow liquid, 63% yield 1H NMR (500 MHz, CDCl3) δ 8.96 (s, 1H), 8.27 (d, J = 8.3 Hz, 1H), 7.18 – 7.83 (m, 2H), 7.54 – 7.57 (m, 3H), 7.30 – 7.32 (m, 5H), 7.11 (d, J = 7.9 Hz, 2H), 2.34 (s, 3H) 13C NMR (126 MHz, CDCl3) δ 196.2, 148.3, 147.3, 144.5, 135.1, 134.9, 130.7, 130.2, 130.1, 129.7, 129.4, 129.2, 128.7, 128.5, 128.4, 127.7, 126.9, 126.7, 21.8 176 177 ... micrographs of Cu- MOF- 74 22 Figure 2.7 Isotherm linear plot of Cu- MOF- 74 23 Figure 2.8 Poresize distribution of Cu- MOF- 74 24 Figure 2.9 TGA curve of the Cu- MOF- 74 24... channels 13 Figure 2.2 Structure of Cu- MOF- 74 before and after activation 2.1.2 Application in catalysis In the past decades, Cu- MOFs, more specifically Cu- MOF- 74, have been rising as one of the... other Cu- MOFs such as Cu3 (BTC)2, Cu( BDC), Cu( EDB), Cu2 (BPDC)2(BPY), Cu2 (BDC)2(DABCO), and Cu2 (EDB)2(BPY) The Cu- MOF- 74 also exhibited advantages as compared to several copper-based salts, including