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: 60.01 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. Phan Thanh Son Nam for providing me an opportunity to do 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 do 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. iii LIST OF FIGURES.
v LIST OF TABLES. viii LIST OF SCHEMES. ix ABBREVIATIONS AND SYMBOLS. xi CHAPTER 1: LITERATURE REVIEWS.
Introduction to metal-organic frameworks. General methods for the synthesis of metal-organic frameworks. Applications of metal–organic frameworks. Copper-based metal-organic frameworks as heterogeneous catalyst.
9 CHAPTER 2: RESEARCH OF CATALYTIC ACTIVITY OF COPPER- BASED METAL-ORGANIC FRAMEWORK Cu-MOF-74 IN THE SYNTHESIS OF 1,4-BENZOTHIAZINE. The Cu-MOF-74 metal-organic framework. Structure and properties. Application in catalysis.
The 1,4-benzothiazines and conventional synthesis. Chemicals and instruments. Synthesis of Cu-MOF-74. Catalytic studies on the synthesis of 3-phenyl-4H-benzo[b][1,4]thiazine- 4-carbonitrile.
Results and discussions. Synthesis of Cu-MOF-74. Catalytic studies on the synthesis of 3-phenyl-4H-benzo[b][1,4]thiazine- 4-carbonitrile. 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.
The Cu2(OBA)2(BPY) metal-organic framework. Structure and Properties of Cu2(OBA)2(BPY). Applications of Cu2(OBA)2(BPY) in catalysis. The quinoline derivatives.
Synthesis route of quinoline derivatives. Materials and Instrumentations. Synthesis of Cu2(OBA)2(BPY) catalyst. The catalytic studies on the synthesis of phenyl(quinolin-3- yl)methanone.
Results and discussions. Synthesis and characterization of Cu2(OBA)2(BPY). The catalytic studies on the synthesis of phenyl(quinolin-3- yl)methanone. 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.
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. Structure of Cu-MOF-74 before and after activation. Antipsychotic and antihistaminic drugs from phenothiazines.
Powder X-ray diffraction patterns of Cu-MOF-74. FT-IR spectra of the Cu-MOF-74 and dihydroxyterephtalic acid. SEM and TEM micrographs of Cu-MOF-74. Isotherm linear plot of Cu-MOF-74.
Poresize distribution of Cu-MOF-74. TGA curve of the Cu-MOF-74. Yield of 3-phenyl-4H-benzo[b][1,4]thiazine-4-carbonitrile vs reaction time at different temperatures. Yield of 3-phenyl-4H-benzo[b][1,4]thiazine-4-carbonitrile vs time in different solvents.
Yield of 3-phenyl-4H-benzo[b][1,4]thiazine-4-carbonitrile vs time at different catalyst concentrations. Yield of 3-phenyl-4H-benzo[b][1,4]thiazine-4-carbonitrile vs time at different reactant molar ratios. Yield of 3-phenyl-4H-benzo[b][1,4]thiazine-4-carbonitrile vs time with different oxidants. Yield of 3-phenyl-4H-benzo[b][1,4]thiazine-4-carbonitrile vs time at different DTBP amounts.
Yield of 3-phenyl-4H-benzo[b][1,4]thiazine-4-carbonitrile vs time with different bases. Yield of 3-phenyl-4H-benzo[b][1,4]thiazine-4-carbonitrile vs time at different Cs2CO3 amounts. Leaching test showed that 3-phenyl-4H-benzo[b][1,4]thiazine-4- carbonitrile was not produced after the isolation of the catalyst. Yield of 3-phenyl-4H-benzo[b][1,4]thiazine-4-carbonitrile vs time with different homogeneous catalysts.
Yield of 3-phenyl-4H-benzo[b][1,4]thiazine-4-carbonitrile vs time with different heterogeneous catalysts. Catalyst reutilizing studies. FT-IR results of the new (a) and reutilized (b) catalyst. XRD results of the new (a) and reutilized (b) catalyst.
The structure of Cu(OBA)2BPY…………………………………. Biologically active molecules containing 3-substituted quinolones. X-ray powder diffractograms of the Cu2(OBA)2(BPY). FT-IR spectra of the Cu2(OBA)2(BPY), H2OBA, 4,4-bipyridine.
TGA analysis of the Cu2(OBA)2(BPY). Pore size distribution of the fresh Cu2(OBA)2(BPY). Nitrogen adsorption/desorption isotherm of the Cu2(OBA)2(BPY). Adsorption data are shown as closed circles and desorption data as open circles.
Effect of temperature on reaction yield. Effect of different solvents on reaction yield. Effect of amount of DMF on the reaction yield. Effect of the 2-aminobenzyl alcohol : propiophenone molar ratio on the reaction yield.
Effect of catalyst amount on the reaction yield. Effect of time on the reaction yield. Effect of different oxidants on the reaction yield. Effect of oxidant amount on the reaction yield.
Effect of different ligands on the reaction yield. Effect of pyridine amount on reaction yield. Effect of different heterogeneous catalysts on the reaction. Effect of different homogeneous catalysts on the reaction.
Catalyst recycling studies. X-ray powder diffractograms of the fresh (a) and reused (b) Cu2(OBA)2(BPY) catalyst. FT-IR spectra of the fresh (red) and reused (black) Cu2(OBA)2(BPY) catalyst. Yields of phenyl(quinolin-3-yl)methanone in the presence of ascorbic acid.
85 vii LIST OF TABLES Table 2. Some physical properties of synthesised Cu-MOF-74 compared with the literatures. The synthesis of benzo[1,4]thiazines from 2-aminobenzothiazoles and terminal alkynes utilizing Cu-MOF-74 catalyst. List of the utilized substances and their providers……………………… 57 Table 3.
Table Synthesis of 3-aroylquinolines via Cu2(OBA)2(BPY)-catalyzed one- pot domino reactions. 86 viii LIST OF SCHEMES Scheme 1. The cycloaddition of benzyl azide and phenylacetylene using Cu- MOFs. Ring-opening of styrene oxide with methanol using metal–organic framework Cu(bpy)(H2O)2(BF4)2(bpy).
The aza-Michael reaction using the MOF-199 catalyst. The Cu2(BDC)2(BPY) was used as catalyst for the reaction of phenylacetylene with 2-oxazolidinone. The Suzuki coupling reaction using Pd@CuBDC. The aerobic cross-coupling of aromatic amines and phenyl boronic acid (Chan–Lam coupling) through Cu2(BDC)2(BPY)–MOF.
The ring expansion reaction of 2-aminobenzothiazole with phenylacetylene utilizing Cu–MOF-74 catalyst. Knoevenagel condensations (top) and Michael additions (bottom) using MOF-74……………………………………………………………………………. Simplified reaction scheme for the acylation of anisole with acetyl chloride using Cu-MOF-74 as catalyst. Amidation of alkanes by amides catalyzed by Cu-MOF-74.
Derivable antimicrobial compounds from 3-phenyl-4H- benzo[b][1,4]thiazine-4-carbonitrile. The exploration of 3-phenyl-4H-benzo[b][1,4]thiazine-4-carbonitrile synthesis. The synthesis 3-phenyl-4H-benzo[b][1,4]thiazine-4-carbonitrile found by Qiu and co-workers. The three-component tandem cyclization to synthesis 1,4-benzothiazines.
Microwave-assisted synthesis of 3-phenyl-4H-benzo[b][1,4]thiazine-4- carbonitrile. Synthesis of Cu-MOF-74. The ring expansion reaction of 2-aminobenzothiazole with phenylacetylene utilizing Cu-MOF-74 catalyst. Proposed reaction pathway.
Reaction of benzothiazole with iodobenzene………………………… 48 Scheme 3. The direct C–S coupling reaction utilizing Cu2(OBA)2(BPY) catalyst (a), and the hydrolysis step to form β-ketosulfone (b). One-pot phosphine-catalyzed syntheses of quinolones. Synthesis of quinoline-based lead agonist and its derivatives.
Strategy for the synthesis of 1,2-dihydroquinolines, quinolines and benzo[b]azepine derivatives. Synthesis quinolines through modified Friedländer approach involving SNAr/reduction/annulation cascade in one-pot in the presence of CuSO4-D- glucose. Synthesis of 4-substituted 3-aroyl quinolines from o-aminoaryl ketones and enaminones. Designation on 3-acylquinoline synthesis via enaminone C=C bond.
Transition-metal-free synthesis of 3-ketoquinolines. Synthesis of 3-acylquinolines through Cu-catalyzed double C(sp3)–H bond functionalization of saturated ketones. The cyclization of 2-aminobenzyl alcohol and propiophenone utilizing Cu2(OBA)2(BPY) as a heterogeneous catalyst. Synthetic scheme for self-assembling the light green crystal of Cu2(OBA)2(BPY).
Proposed reaction mechanism. 85 x ABBREVIATIONS AND SYMBOLS BDC 1,4-benzenedicarboxylate BPDC 4,4’-biphenyldicarboxylate BTC 1,3,5-benzenetricarboxylate CSD Cambridge Structural Database DABCO 1,4-diazabicyclo[2.2]octane DCB 1,2-dichlorobenzene DMAc N,N-dimethylacetamide DMF N,N-dimethylformamide DMSO dimethylsulfoxide DTBP di-tert-butyl peroxide FT-IR Fourier Transform Infrared GC Gas Chromatography GC-MS Gas Chromatography – Mass Spectrometry HKUST Hong Kong University of Science and Technology MDR Multidrug-resistance MIL Matériaux de l′Institut Lavoisier MOFs Metal-Organic Frameworks NMP N-methyl-2-pyrrolidone NMR Nuclear Magnetic Resonance XRD X-ray Diffraction rt Room temperature SBUs Secondary Building Units SEM Scanning Electron Microscopy TBHP tert-butyl hydroperoxide xi TEAB tetraethylammonium bromide TEM Transmission Electron Microscopy TEMPO 2,2,6,6-Tetramethyl-1-piperidinyloxy TGA Thermogravimetric TMEDA Tetramethylethylenediamine xii CHAPTER 1: LITERATURE REVIEWS 1. Introduction to metal-organic frameworks 1. General introduction Metal-organic frameworks (MOFs) have received much attention in recent years especially as newly developed porous coordination polymers, have emerged as a new family of crystalline materials composed of organic linkers that connect metal ions or metal clusters to produce one-, two-, or three-dimensional networks [1].
Flexibility or the rigidity of the frameworks is greatly affected by the choice of organic linker in the structure [2]. Furthermore, the tendency of metal ions can make different coordination numbers of metal, which can influence the geometric configuration of MOF structures [3]. The abundant structures of MOFs (1D, 2D and 3D) are reported in the Cambridge Structural Database (CSD) (Figure 1. Growth of the Cambridge structural database (CSD) from 1972 to 2016, the red bar shows structures added annually.
MOFs are constructed by joining secondary building units (SBUs) with organic linkers, using strong bonds to create open crystalline frameworks with permanent porosity. 2 The great diversity of metal SBUs and organic linkers have led to thousands of MOFs being synthesized and studied. These metal-containing SBUs are essential to the design of directionality for the construction of MOFs and to the achievement of robust frameworks. The organic units are ditopic or polytopic organic carboxylates (and other similar negatively charged molecules) [4].
Longer organic linkers provide larger storage space and a greater number of adsorption sites within a given material. Containing both organic linkers and metal ions in the frameworks, MOFs possess several interesting properties, such as well-defined structures, high surface areas, high porosity, structural diversity, the ability to tune the pore size, and the possibility to modify the surface hydrophobicity/ hydrophilicity [5]. These unique properties have paved the way for MOFs research to grow substantially, and applications are being considered in many areas including gas storage [6, 7], separation [8], catalysis [9] and carbon capture as well as biomolecule encapsulation [10], drug delivery [11], and imaging [12]. General methods for the synthesis of metal-organic frameworks Figure 1.
Structural model of MOF (top row) and the representative SBUs (middle row), as well as ligands (down row). 3 MOFs are typically synthesized by combining metal salts clusters as connectors and organic ligands as linkers (Figure 1. The characteristics of the ligand (bond angles, ligand length, bulkiness, chirality, etc.