Cu based organic frameworks as catalysts for c c and c n coupling reactions

TABLE OF CONTENTS TABLE OF CONTENTS v LIST OF FIGURES .vii LIST OF SCHEMES .xi LIST OF TABLES xiii LIST OF ABBREVIATION xiv INTRODUCTION CHAPTER LITERATURE REVIEW: Cu3(BTC)2, Cu2(BDC)2(DABCO), Cu2(BPDC)2 (BPY), Cu(BDC) AND C-C, C-N COUPLING REACTIONS 1.1 Introduction to metal-organic frameworks .3 1.2 Cu3 (BTC)2 , Cu(BDC), Cu2(BDC)2(DABCO) and Cu2(BPDC)2(BPY) 1.2.1 Structures and properties of Cu3(BTC)2, Cu(BDC), Cu2(BDC)2(DABCO) and Cu2(BPDC)2(BPY) 1.2.2 Synthesis of Cu3(BTC)2, Cu(BDC), Cu2(BDC)2(DABCO) and Cu2 (BPDC)2(BPY) 13 1.2.3 Characterization of Cu3(BTC)2, Cu(BDC), Cu2(BDC)2(DABCO) and Cu2 (BPDC)2(BPY) 15 1.2.4 Catalytic activities of Cu3 (BTC)2, Cu(BDC), Cu2 (BDC)2 (DABCO) and Cu2 (BPDC)2(BPY) 21 1.3 CC cross coupling reactions 26 1.4 CN cross coupling reactions 33 1.5 Aims and objectives 36 CHAPTER SYNTHESIS AND CHARACTERIZATION OF Cu3(BTC)2, Cu2(BDC)2(DABCO), Cu2(BPDC)2(BPY), AND Cu(BDC) 38 2.1 Introduction 39 2.2 Experimental 40 2.2.1 Materials and instrumentation 40 2.2.2 Synthesis of Cu3(BTC)2 41 2.2.3 Synthesis of Cu2(BDC)2(DABCO) 42 2.2.4 Synthesis of Cu2(BPDC)2 (BPY) 42 v 2.2.5 2.3 Synthesis of Cu(BDC) 43 Results and discussions 43 2.3.1 Synthesis and characterization of Cu3 (BTC)2 43 2.3.2 Synthesis and characterization of Cu2 (BDC)2 (DABCO) 48 2.3.3 Synthesis and characterization of Cu2 (BPDC)2(BPY) 53 2.3.4 Synthesis and characterization of Cu(BDC) 58 2.4 Conclusion 63 CHAPTER CATALYTIC STUDIES OF Cu3 (BTC)2 , Cu2(BDC)2(DABCO), Cu2(BPDC)2 (BPY) AND Cu(BDC) ON CC AND CN COUPLING REACTIONS65 3.1 Introduction 66 3.2 Experimental 68 3.2.1 Materials and instrumentation 68 3.2.2 Catalytic studies on CC, CN cross coupling reactions 69 3.3 Results and discussions 71 3.3.1 Catalytic studies of Cu3(BTC)2 on CC cross coupling reaction (1) 71 3.3.2 (2) Catalytic studies of Cu2(BDC)2(DABCO) on CC cross coupling reaction 81 3.3.3 (3) Catalytic studies of Cu2(BPDC)2(BPY) on CC cross coupling reaction 92 3.3.4 Catalytic studies of Cu(BDC) on C-N cross coupling reaction (4) 103 3.4 Conclusion 111 CHAPTER CONCLUSION 114 4.1 Summary of current work 114 4.2 Contributions of this dissertation 115 LIST OF PUBLICATIONS 117 REFERENCES 119 APPENDECIES 131 vi LIST OF FIGURES Figure 1.1 The 3D structures of representative MOFs [7] Figure 1.2 (a) Synthesis conditions commonly used for MOFs preparation; (b) indicative summary of the percentage of MOFs synthesized using various preparation routes [8] Figure 1.3 Development of MOF fields in comparison to the MOF catalysis in Figure 1.4 Common coordination geometry of paddle wheel building units of Cu3(BTC)2, Cu2 (BDC)2 (DABCO), Cu2 (BPDC)2(BPY), Cu(BDC) and their framework structures (L = Carboxylate linker, P = N-containing bidentate pillar linker and G = Guest molecule) [44-47] Figure 1.5 Reversible crystalline phase transformation of Cu(BDC) from the lamellar to the compact structure upon desorption/adsorption of DMF [40] 10 Figure 1.6 X-Ray structure of the doubly interpenetrating pillared-grid framework Cu2(BPDC)2 (BPY) [45] 11 Figure 1.7 Pore apertures of Cu2(BDC)2(DABCO) [48] 12 Figure 1.8 Solvothermal synthesis of MOFs [10] 13 Figure 1.9 PXRD patterns of Cu3(BTC)2, Cu(BDC), Cu2(BDC)2(DABCO) and Cu2(BPDC)2 (BPY) [45-47, 52] 17 Figure 1.10 In situ PXRD patterns of Cu(BDC) [10] 18 Figure 1.11 SEM images of Cu3(BTC)2, Cu(BDC), Cu2(BDC)2(DABCO) and Cu2(BPDC)2 (BPY) [10, 33, 35, 37] 19 Figure 1.12 TGA of Cu3(BTC)2, Cu(BDC), Cu2(BDC)2(DABCO) and Cu2(BPDC)2 (BPY) [33, 35-37] 20 Figure 1.13 FT-IR spectra of Cu3(BTC)2, Cu(BDC), Cu2(BDC)2(DABCO) and Cu2(BPDC)2 (BPY) [33, 35-37] 21 Figure 2.1 Structure of Cu3 (BTC)2 (a) [46], Cu(BDC) (b) [44], Cu2(BDC)2(DABCO) [117] and Cu2(BPDC)2BPY [45] 40 Figure 2.2 X-ray powder diffractograms of the simulated Cu3(BTC)2 (a) and the synthesized Cu3 (BTC)2 (b) 44 Figure 2.3 FT-IR spectra of the Cu3(BTC)2 (a) and 1,3,5-benzenetricarboxylic acid (b) 45 Figure 2.4 SEM micrograph of the Cu3(BTC)2 46 Figure 2.5 TEM micrograph of the Cu3(BTC)2 46 Figure 2.6 TGA analysis of the Cu3(BTC)2 47 Figure 2.7 H2-TPR profile of the Cu3(BTC)2 48 vii Figure 2.8 X-ray powder diffractograms of the simulated Cu2(BDC)2(DABCO) (a) and the synthesized Cu2 (BDC)2 (DABCO) 49 Figure 2.9 SEM micrograph of the Cu2(BDC)2(DABCO) 50 Figure 2.10 TEM micrograph of the Cu2(BDC)2(DABCO) 50 Figure 2.11 FT-IR spectra of 1,4-benzenedicarboxylic acid (a), diazabicyclo[2.2.2]octane (b) and the Cu2(BDC)2(DABCO) (c) 51 Figure 2.12 TGA analysis of the Cu2(BDC)2(DABCO) 52 Figure 2.13 H2-TPR profile of the Cu2 (BDC)2 (DABCO) 53 Figure 2.14 X-ray powder diffractograms of the simulated Cu2(BPDC)2(BPY) (a) and the synthesized Cu2 (BPDC)2(BPY) (b) 54 Figure 2.15 TGA of the Cu2(BPDC)2(BPY) 55 Figure 2.16 SEM micrograph of the Cu2(BPDC)2 (BPY) 56 Figure 2.17 TEM micrograph of the Cu2(BPDC)2 (BPY) 56 Figure 2.18 FT-IR spectra of 4,4’-Biphenyldicarboxylic acid (a), 4,4’-Bipyridine (b) and the Cu2(BPDC)2(BPY) (c) 57 Figure 2.19 H2-TPR profile of the Cu2 (BPDC)2(BPY) 58 Figure 2.20 X-ray powder diffractograms of the simulated Cu(BDC) (a) and the synthesized Cu(BDC) (b) 59 Figure 2.21 TGA of the Cu(BDC) 60 Figure 2.22 SEM micrograph of the Cu(BDC) 61 Figure 2.23 TEM micrograph of the Cu(BDC) 61 Figure 2.24 FT-IR spectra of 1,4-benzenedicarboxylic acid (a) and the Cu(BDC) (b) 62 Figure 2.25 H2-TPR profile of the Cu(BDC) 63 Figure 3.1 Effect of temperature on reaction conversions 73 Figure 3.2 Effect of catalyst amount on reaction conversions 73 Figure 3.3 Effect of phenylacetylene: N,N-dimethylaniline molar ratio on reaction conversions 74 Figure 3.4 Effect of oxidant on reaction conversions 74 Figure 3.5 Effect of oxidant concentration on reaction conversions 75 Figure 3.6 The selectivity of reaction with different oxidant concentrations on reaction conversions 75 Figure 3.7 Effect of different solvents on reaction conversions 75 Figure 3.8 The selectivity of reaction with different solvents on reaction conversions 75 Figure 3.9 Leaching test indicated no contribution from homogeneous catalysis of active species leaching into reaction solution 76 Figure 3.10 Different Cu-MOFs catalysts for the direct CC coupling reactions 76 Figure 3.11 Catalyst recycling studies 78 Figure 3.12 FT-IR spectra of the fresh (a) and reused (b) Cu3 (BTC)2 catalyst 79 viii Figure 3.13 X-ray powder diffractograms of the fresh (a) and reused (b) Cu3 (BTC)2 catalyst 79 Figure 3.14 Effect of temperature on reaction conversions 82 Figure 3.15 Effect of catalyst amount on reaction conversions 82 Figure 3.16 Effect of phenylacetylene: N-methylaniline molar ratio on reaction conversions 84 Figure 3.17 Effect of oxidant on reaction conversions 84 Figure 3.18 Effect of oxidant concentration on reaction conversions 85 Figure 3.19 The selectivity of reaction with different oxidant concentrations on reaction conversions 85 Figure 3.20 Effect of different solvents on reaction conversions 86 Figure 3.21 The selectivity of reaction with different solvents on reaction conversions 86 Figure 3.22 Leaching test indicated no contribution from homogeneous catalysis of active species leaching into reaction solution 87 Figure 3.23 Different Cu-MOFs catalysts for the direct C-C coupling reactions 87 Figure 3.24 Catalyst recycling studies: Reaction conversion (a) and selectivity of reaction (b) 89 Figure 3.25 FT-IR spectra of the fresh (a) and reused (b) Cu2 (BDC)2 (DABCO) catalyst 90 Figure 3.26 X-ray powder diffactograms of the fresh (a) and reused (b) Cu2(DABCO)2(DABCO) 90 Figure 3.27 Effect phenylacetylene:benzaldehyde: tetrahydroisoquinoline molar ratio ratio on reaction conversions 94 Figure 3.28 Effect of temperature on reaction conversions 94 Figure 3.29 Effect of catalyst amount on reaction conversions 95 Figure 3.30 Effect of different solvents on reaction conversions 95 Figure 3.31 Different copper salts as catalyst for the C1-alkynylation reaction of tetrahydroisoquinoline 96 Figure 3.32 Different MOFs as catalyst for the C1-alkynylation reaction of tetrahydroisoquinoline 96 Figure 3.33 Effect of catalyst poison on reaction conversion 97 Figure 3.34 Adding product to the reaction mixture 97 Figure 3.35 Leaching test indicated no contribution from homogeneous catalysis of active species leaching into reaction solution 99 Figure 3.36 Catalyst recycling studies 99 Figure 3.37 FT-IR spectra of the fresh (a) and reused (b) Cu2 (BPDC)2(BPY) catalyst 100 Figure 3.38 X-ray diffractograms of the fresh (a) and reused (b) Cu2 (BPDC)2(BPY) catalyst 100 ix Figure 3.39 Effect of different derivative be nzaldehydes on reaction conversions 101 Figure 3.40 Effect of different derivative phenylacetylenes on reaction conversions 101 Figure 3.41 Effect of temperature on reaction conversions 104 Figure 3.42 Effect of catalyst amount on reaction conversions 104 Figure 3.43 Effect of α-hydroxyacetophenone : phenylenediamine molar ratio on reaction conversions 105 Figure 3.44 Effect of different solvents on reaction conversions 105 Figure 3.45 Leaching test indicated no contribution from homogeneous catalysis of active species leaching into reaction solution 106 Figure 3.46 Effect of catalyst poison on reaction conversion 106 Figure 3.47 Different catalyst for the quinoxaline synthesis reaction 107 Figure 3.48 Effect argon on reaction conversion 107 Figure 3.49 Catalyst recycling studies 109 Figure 3.50 FT-IR spectra of the fresh (a) and reused (b) Cu(BDC) catalyst 110 Figure 3.51 X-ray powder diffractograms of the fresh (a) and reused (b) Cu(BDC) catalyst 110 Figure 3.52 The reaction between α-hydroxyacetophenone and different 1,2aryldiamines 110 x LIST OF SCHEMES Scheme 1.1 Solvothermal synthesis of Cu3(BTC)2 , Cu2(BDC)2(DABCO), Cu2(BPDC)2 (BPY) and Cu(BDC) [44-47] 13 Scheme 1.2 The reaction of various aldehydes with methanol using the Cu 3(BTC)2 as catalyst [64] 23 Scheme 1.3 The oxidation of the benzylic compounds with t-butylhydroperoxide using the Cu3(BTC)2 as catalyst [66] 23 Scheme 1.4 The 1,3-dipolar cycloaddition reaction catalyzed by various Cu- MOFs catalysts [41] 24 Scheme 1.5 The modified Friedländer reaction using the Cu(BDC) as catatalyst [37] 24 Scheme 1.6 The coupling of phenols with nitroarenes to form diaryl ethers using the Cu2(BDC)2(DABCO) as catalyst [33] 25 Scheme 1.7 The cross-dehydrogenative coupling reaction of 2-hydroxybenzaldehyde and 1,4-dioxane using Cu2(BPDC)2(BPY) as a solid catalyst [61] 25 Scheme 1.8 Aryl −Aryl bond formation by CC cross coupling [69] 27 Scheme 1.9 Aryl −Aryl bond formation by transition-metal-catalyzed direct arylation [70] 27 Scheme 1.10 Pd, Rh-Catalyzed Arylation via CH bond functionalization [71, 72] 28 Scheme 1.11 Copper-catalyzed arylation [75] 29 Scheme 1.12 A general diagram of the CC cross-coupling reaction [77] 29 Scheme 1.13 Propargylamines synthesis under transition metal catalysis [78 -80] 29 Scheme 1.14 A tentative mechanism of three-component reaction for synthesizing propargylamines [78-80] 30 Scheme 1.15 Cross-Dehydrogenative Coupling for the formation of CC bonds [82, 83] 31 Scheme 1.16 Copper-Catalyzed alkynylation of amines [94] 31 Scheme 1.17 Tentative mechanism for the direct oxidative coupling of amine with alkyne [94] 32 Scheme 1.18 General synthesis of quinoxalines [97] 33 Scheme 1.19 The mechanism for the synthesis of different quinoxalines [98] 34 Scheme 1.20 The proposed mechanism of the synthesis of quinoxaline [110] 35 Scheme 2.1 Synthesis procedure of the Cu3(BTC)2 43 Scheme 2.2 Synthesis procedure of the Cu2(BDC)2(DABCO) 49 Scheme 2.3 Synthesis procedure of the Cu2(BPDC)2(BPY) 54 Scheme 2.4 Synthesis procedure of the Cu(BDC) 59 xi Scheme 3.1 The synthesis of propargylamines 67 Scheme 3.2 The synthesis of quinoxaline 67 Scheme 3.3 The direct oxidative C-C coupling reaction between N,N-dimethylaniline and phenylacetylene using Cu3 (BTC)2 as catalyst 72 Scheme 3.4 The direct CC coupling reaction via methylation and C-H functionalization of N-methylaniline and phenylacetylene 82 Scheme 3.5 The A3 reaction of tetrahydroisoquinoline, benzaldehyde, and phenylacetylene using Cu2(BPDC)2(BPY) catalyst 93 Scheme 3.6 The oxidative cyclization reaction between α-hydroxyacetophenone and phenylenediamine using Cu(BDC) catalyst 103 xii LIST OF TABLES Table 1.1 The comparison of structural features and physicochemical properties between some common porous materials used in industry and MOFs materials [20, 31] .7 Table 1.2: Physicochemical properties of Cu3(BTC)2, Cu(BDC), Cu2 (BDC)2 (DABCO) and Cu2(BPDC)2(BPY) 12 Table 1.3: The most characteristic bond lengths from SC-XRD data of Cu3(BTC)2, Cu(BDC), Cu2(BDC)2(DABCO) and Cu2(BPDC)2 (BPY) 16 Table 1.4: List of conversion reactions and catalytic reactions used Cu 3(BTC)2, Cu(BDC), Cu2(BDC)2(DABCO) and Cu2(BPDC)2 (BPY) as heterogeneous catalysts 22 Table 3.1 Reactions scope with respect to coupling components 80 Table 3.2: The reaction conversions of the optimized synthetic conditions for reaction between N,N-dimethylaniline and phenylacetylene 81 Table 3.3 Reactions scope with respect to coupling partners 91 Table 3.4: The reaction conversions of the optimized synthetic conditions for reaction between N-methylaniline and phenylacetylene 92 Table 3.5: The reaction conversions of the optimized synthetic conditions for reaction from Tetrahydroisoquinoline, benzaldehyde and phenylacetylene 102 Table 3.6: The reaction conversions of the optimized synthetic conditions for reaction between α-hydroxyacetophenone and phenylenediamine 111 xiii LIST OF ABBREVIATION AAS atomic absorption spectrophotometry BDC benzenedicarboxylate BET Brunauer–Emmett–Teller BPDC biphenyldicarboxylate BPY 4,4’-bipyridine BTC benzenetricarboxylate CDCl3 clorofrom DABCO 1,4-diazabicyclo [2.2.2]octane DCM dichloromethane DEF diethylformamide DLS dynamic laser light scattering DMA dimethyacetamide DMF dimethylformamide FT-IR Fourier Transform Infrared Spectroscopy HKUST Hong Kong University of Science and Technology ICP-MS Inductively Coupled Plasma Mass Spectrometry IRMOF Isorecticular Metal-Organic Framework MIL Mate´riauxs de l’Institut Lavoisier NMR Nuclear Magnetic Resonance NMP N-Methyl-2-Pyrrolidone MOF Metal-Organic Framework MOP Metal-Organic Polyhedron MS Mass Spectrometry NDC 2,6-napthalenedicarboxylate NU Northwestern University SBUs Secondary Building Units SC- XRD Single-Crystal X-ray Diffraction SEM Scanning Electron Microscopy xiv Figure S20 1H NMR spectra a) and 13 C NMR b) of N-(3-phenylprop-2nyl)benzenamine in CDCl3 N-(3-phenylprop-2-ynyl)benzenamine (B) Phenylacetylene (0.11 mL, 1.0 mmol), N-Methylaniline (0.22 mL, 2.0 mmol), Cu2(BDC)2(DABCO) (0.014g, mol%), tert-butyl hydroperoxide (0.41 mL, 3.0 mmol), N,N-Dimethylacetamide (4 mL) After chromatography (diethyl ether/hexane = 1:20), 29 mg yellow oil was obtained (14 %) Rf = 0.27 1H NMR (500 MHz, CDCl 3, ppm): δ = 7.40-7.38 (m, 2H), 7.29-7.27 (m, 3H), 7.24-7.21 (m, 2H), 6.80-6.77 (m, 1H), 6.74-6.72 (m, 1H), 4.15 (s, 2H), 4.00-3.90 (s, 1H) 13 C NMR (125 MHz, CDCl3 , ppm): δ = 147.1, 131.7, 129.2, 128.2, 128.2, 122.9, 118.5, 113.6, 86.3, 83.3, 34.6 20 mmol scale reaction: Phenylacetylene (2.20 mL, 20 mmol), N-Methylaniline (4.40 mL, 40 mmol), Cu2(BDC)2(DABCO) (0.28 g, mol%), tert-butyl hydroperoxide (8.20 mL, 60 mmol), N,N-Dimethylacetamide (80 mL) After chromatography (diethyl ether/hexane = 1:20), 0.54 g yellow oil was obtained (13 %) 150 151 Figure S21 1H NMR spectra a) and 13 C NMR b) of N-(3-(4-methoxyphenyl)prop-2yn-1-yl)-N-methylaniline in CDCl3 N-(3-(4-methoxyphenyl)prop-2-yn-1-yl)-N-methylaniline 4-ethynylanisole (0.13 mL, 1.0 mmol), N-Methylaniline (0.22 mL, 2.0 mmol), Cu2(BDC)2(DABCO) (0.014g, mol%), tert-butyl hydroperoxide (0.41 mL, 3.0 mmol), N,N- Dimethylacetamide (4 mL) After chromatography (diethyl ether/hexane = 1:20), 181 mg pale white solid was obtained (72 %) Rf = 0.26 1H NMR (500 MHz, CDCl 3, ppm): δ = 7.31-7.24 (m, 4H), 6.90 (dd, J=8.0 Hz, J=1.0 Hz, 2H), 6.86-6.76 (m, 3H), 4.23 (s, 2H), 3.76 (s, 3H), 3.01 (s, 3H) 13 C NMR (125 MHz, CDCl3 , ppm): δ = 159.4, 149.4, 133.1, 129.0, 118.0, 115.2, 114.3, 113.8, 84.0, 83.5, 55.2, 43.3, 38.6 152 153 Figure S22 1H NMR spectra a) and 13 C NMR b) of N-methyl-N-(3-(p-tolyl)prop-2-yn1-yl)aniline in CDCl3 N-methyl-N-(3-(p-tolyl)prop-2-yn-1-yl)aniline p-Tolylacetylene (0.11 mL, 1.0 mmol), N-Methylaniline (0.22 mL, 2.0 mmol), Cu2 (BDC)2 (DABCO) (0.014g, mol%), tert-butyl hydroperoxide (0.41 mL, 3.0 mmol), N,N-Dimethylacetamide (4 mL) After chromatography (diethyl ether/hexane = 1:15), 167 mg yellow oil was obtained (71 %) Rf = 0.43 1H NMR (500 MHz, CDCl 3, ppm): δ = 7.28-7.25 (m, 4H), 7.06 (d, J=8.0 Hz, 2H), 6.90 (dd, J=8.0 Hz, J=1.0 Hz, 2H), 6.80 (t, J=7.8 Hz, 1H), 4.24 (s, 2H), 3.03 (s, 3H), 2.31 (s, 3H) 13 C NMR (125 MHz, CDCl3, ppm): δ = 149.4, 138.1, 133.6, 129.1, 128.9, 120.0, 118.1, 114.4, 84.3, 84.2, 43.3, 38.7, 21.4 154 155 Figure S23 1H NMR spectra a) and 13 C NMR b) of N-methyl-N-(non-2-yn-1yl)aniline in CDCl3 N-methyl-N-(non-2-yn-1-yl)aniline 1-octyne (0.15 mL, 1.0 mmol), N- Methylaniline (0.22 mL, 2.0 mmol), Cu2(BDC)2(DABCO) (0.014g, mol%), tertbutyl hydroperoxide (0.41 mL, 3.0 mmol), N,N-Dimethylacetamide (4 mL) After chromatography (used hexane as eluent), 133 mg yellow oil was obtained (58 %) Rf = 0.3 1H NMR (500 MHz, CDCl 3, ppm): δ = 7.26-7.25 (m, 2H), 6.85 (d, J=8.0 Hz, 2H), 6.78 (t, J=7.5 Hz, 1H), 4.00 (s, 2H), 2.95 (s, 3H), 2.14-2.11 (m, 2H), 1.45-1.42 (m, 2H), 1.33-1.21 (m, 6H), 0.86 (t, J=7.0 Hz , 3H) 13C NMR (125 MHz, CDCl3, ppm): δ = 149.5, 129.0, 117.9, 114.3, 84.5, 75.3, 42.9, 38.5, 31.3, 28.7, 28.4, 22.5, 18.7, 14.0 156 Figure S24 1H NMR spectra of 4-methoxy-N-methyl-N-(3-phenylprop-2-yn-1yl)aniline in CDCl3 4-methoxy-N-methyl-N-(3-phenylprop-2-yn-1-yl)aniline (0.11 mL, 1.0 mmol), N-methyl-p-anisidine (0.274g, Phenylacetylene 2.0 mmol), Cu2(BDC)2(DABCO) (0.014g, mol%), tert-butyl hydroperoxide (0.41 mL, 3.0 mmol), N,N-Dimethylacetamide (4 mL) After chromatography (ethyl acetate/hexane = 1: 9), 181 mg yellow oil was obtained (72 %) Rf =0.27 1H NMR (300 MHz, CDCl 3, ppm): δ = 7.40-7.28 (m, 5H), 6.97-6.86 (m, 4H), 4.19 (s, 2H), 3.79 (s, 3H), 2.98 (s, 3H) 157 Figure S25 1H NMR spectra of 4-chloro-N-methyl-N-(3-phenylprop-2-yn-1yl)aniline in CDCl3 4-chloro-N-methyl-N-(3-phenylprop-2-yn-1-yl)aniline (0.11 mL, 1.0 mmol), 4-cloro-N-Methylaniline (0.24 Phenylacetylene mL, 2.0 mmol), Cu2(BDC)2(DABCO) (0.014g, mol%), tert-butyl hydroperoxide (0.41 mL, 3.0 mmol), N,N-Dimethylacetamide (4 mL) After chromatography (diethyl ether/ hexane = 1: 15), 196 mg yellow oil was obtained (77 %) R f = 0.43 1H NMR (300 MHz, CDCl3, ppm): δ = 7.38 (dd, J=6.6 Hz, J=3.0 Hz, 2H), 7.29 -7.22 (m, 5H), 6.84 (d, J=9.3 Hz, 2H), 4.25 (s, 2H), 3.03 (s, 3H) 158 Reaction (3) 159 Figure S26 1H NMR a) and 13C NMR spectra b) of 2-benzyl-1-(phenylethynyl)1,2,3,4-tetrahydroisoquinoline in CDCl3 2-benzyl-1-(phenylethynyl)-1,2,3,4-tetrahydroisoquinoline Phenylacetylene (0.11 mL, 1.0 mmol), Benzaldehyde (0.11 mL, 1.1 mmol), Tetrahydroisoquinoline (0.141 mL, 1.1 mmol), Cu2(BPDC)2(BPY) (0.020g, mol%), toluene (4 mL) After chromatography (ethyl acetate/hexane = 1:20), 281mg colorless oil was obtained (87 %) Rf = 0.30 H NMR (500 MHz, CDCl , ppm): δ = 7.47-7.42 (m, 4H), 7.33 (t, J=7.5 Hz, 2H), 7.29-7.22 (m, 5H), 7.18-7.11 (m, 3H), 4.79 (s, 1H), 3.95 (d, J=13.0 Hz, 1H), 3.91 (t, J=13.0 Hz, 1H), 3.11-2.99 (m, 2H), 2.84-2.77 (m, 2H) 13C NMR (125 MHz, CDCl3, ppm): δ = 138.3, 135.5, 134.1, 131.8, 129.3, 129.0, 128.3, 128.2, 128.0, 127.8, 127.2, 126.9, 125.8, 123.3, 87.5, 86.8, 59.6, 54.4, 45.8, 29.0 160 Figure S27 HMBC spectrum of 2-benzyl-1-(phenylethynyl)-1,2,3,4tetrahydroisoquinoline in CDCl3 161 Reaction (4) Cu(BDC) CuCl2.2H2O CuCl Cu(NO3)2 Conversion (%) 100 80 60 40 20 0 30 60 90 120 150 180 Time (min) Figure S28 Different copper salts as catalyst for the quinoxaline synthesis reaction 162 163 Figure S29 1H NMR spectra a) and 2-phenylquinoxaline 13 C NMR b) of 2-phenylquinoxaline in CDCl3 -hydroxyacetophenone (0.136 g, 1.0 mmol), phenylenediamine (0.119 g, 1.1 mmol), Cu(BDC) (0.010g, mol%) After chromatography (dichloromethane/hexane = 2:1), 196 mg yellow solid was obtained (95 %) Rf =0.3 This compound is known 1H NMR (500 MHz, CDCl 3, ppm): δ = 9.31 (s, 1H), 8.19 (dd, J = 7.0 Hz, J = 1.5 Hz, 1H), 8.15 (dd, J = 8.3 Hz, J = 1.3 Hz, 1H), 8.11 (dd, J = 8.3 Hz, J = 1.3 Hz, 1H), 7.78-7.71 (m, 2H), 7.57-7.49 (m, 3H) 13C NMR (125 MHz, CDCl3, ppm): δ = 151.8, 143.3, 142.2, 141.5, 136.7, 130.2, 130.1, 129.6, 129.5, 129.1, 129.1, 127.5 164 [...]... been discussed 1.2 Cu3 (BTC)2, Cu( BDC), Cu2 (BDC)2(DABCO) and Cu2 (BPDC)2 (BPY) 1.2.1 Structures and properties of Cu3 (BTC)2, Cu( BDC), Cu2 (BDC)2(DABCO) and Cu2 (BPDC)2(BPY) Cu3 (BTC)2 [46], Cu( BDC) [44], Cu2 (BDC)2(DABCO) [47] and Cu2 (BPDC)2(BPY) [45] constitute Cu- MOFs that contain common SBUs of two 5-coordinate copper cations bridged in a paddle wheel-type configuration (Fig 1.4) 8 Figure 1.4 Common coordination... mentioned in the literature The first purpose of this thesis is to synthesize Cu- MOFs including Cu3 (BTC)2, Cu( BDC), Cu2 (BDC)2(DABCO) and Cu2 (BPDC)2(BPY) The second objective is to study their use as heterogeneous catalysts for the direct C C and C N coupling reactions to form proparylamines and quinoxalines 2 CHAPTER 1 LITERATURE REVIEW: Cu3 (BTC)2, Cu2 (BDC)2(DABCO), Cu2 (BPDC)2(BPY), Cu( BDC) AND C- C, C- N COUPLING. .. (BTC)2, Cu( BDC), Cu2 (BDC)2(DABCO) and Cu2 (BPDC)2 (BPY), which are constructed from copper salts and 1,4-benzenedicarboxylic acid (BDC), 1,3,5-benzenetricarboxylic acid (BTC) and 4,4’-biphenyldicarboxylic acid (BPDC), exhibit many advantages for catalytic application Those organic linkers are commercial and relatively cheap These CuMOFs have surface areas higher than 1000 m2/g (except for Cu( BDC)) and. .. mesopores, surface area, pore volume and pore size distribution The content of metal can be measured by inductively coupled plasma mass spectrometry (ICP-MS) After synthesis and characterization, the applications of Cu3 (BTC)2, Cu( BDC), Cu2 (BDC)2(DABCO) and Cu2 (BPDC)2(BPY) should be investigated In the next section, catalytic applications of Cu3 (BTC)2, Cu( BDC), Cu2 (BDC)2 (DABCO) and Cu2 (BPDC)2 (BPY) will... various CuMOFs (i.e Cu( 2-pymo)2, Cu( im)2, Cu3 (BTC)2 , Cu( BDC)) are all efficient catalysts for ‘‘click” reactions (1,3-dipolar cycloaddition reactions) with activities and selectivities being as high as the case of using homogeneous catalysts [41] (Scheme 1.4) However, it should be noted that MOFs containing CuN4 are more active than those with CuO4 centers It means that the organic component of the... Cu3 (BTC)2, Cu( BDC), Cu2 (BDC)2(DABCO) and Cu2 (BPDC)2(BPY) [33, 35-37] Fourier-Transform Infra-Red (FT-IR) spectroscopy is a fast, non-destructive method for identifying functional groups and coordination modes in MOFs materials The presence of water and solvent can also be observed The coordination mode between metal and carboxylate can be determined The FT-IR spectra of Cu3 (BTC)2, Cu( BDC), Cu2 (BDC)2(DABCO)... The results indicated that the reaction using Cu( BDC) as catalyst gave the same excellent yield of product compared to ultilizing Cu3 (BTC)2, and remarkably higher yield than cases applying Cu- MOFs such as Cu( pymo)2 and Cu( im)2 or homogeneous catalysts including CuI and Cu( OAc) 2 Therefore, the Cu( BDC) with open active sites is a greatly potential heterogeneous catalyst for several organic syntheses 24... 1,4-diazabicyclo [2.2.2]octane (DABCO) or 4,4’-bipyridine (BPY) to form rigid Cu- MOFs [43-47] Therefore, Cu- MOFs constructed from BDC, BTC or BPDC recently attracted great attention In this chapter, literature review of structure, physicochemical properties, synthesis methods, characterization, and catalytic applications of four Cu- MOFs including Cu3 (BTC)2 , Cu( BDC), Cu2 (BDC)2(DABCO) and Cu2 (BPDC)2(BPY) has... coordination geometry of paddle wheel building units of Cu3 (BTC)2, Cu2 (BDC)2 (DABCO), Cu2 (BPDC)2(BPY), Cu( BDC) and their framework structures (L = Carboxylate linker, P = N- containing bidentate pillar linker and G = Guest molecule) [44-47] As shown in Figure 1.4, in these frameworks carboxylates act as grid-forming ligands In the case of Cu3 (BTC)2 and Cu( BDC), each copper completes its pseudooctohedral... and bond distances within the paddle-wheel fragment are comparable for all of four Cu- MOFs (Cu Cu = 2.627– 2.628 Å, Cu OCO = 1.952–2.001 Å, Cu G = 2.165 Å and Cu P = 2.101–2.103 Å) As Cu3 (BTC)2 was constructed from the tritopic ligand BTC and Cu2 (BDC)2(DABCO), Cu2 (BPDC)2(BPY) were constructed from two different types of ligand, the framework structures of these Cu- MOFs are three dimention Whereas Cu( BDC) ... Cu(BDC) AND C-C, C-N COUPLING REACTIONS 1.1 Introduction to metal -organic frameworks There are a variety of porous materials have been increasingly studied such as nanotubes [1], mesoporous silicas... Cu2(BDC)2(DABCO) and Cu2(BPDC)2(BPY) The second objective is to study their use as heterogeneous catalysts for the direct C–C and C–N coupling reactions to form proparylamines and quinoxalines... Cu(NO3)2 3H2O and H2 BDC was dissolved in DMF and then heated at 110 o C in an isothermal oven for 36 hours to form a blue powder The BET surface areas of 625 m2/g and Langmuir surface areas of m2