Luận án tiến sĩ công nghệ hóa hữu cơ application of mil 68 in fe3o bpdc3 mof 235

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 Cí1$1'&í2 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 CíN AND CíO BOND FORMING REACTIONS Major: Organic Chemical Technology Major code: 62520301 Independent examiner 1: Assoc. Nguyen Phuong Tung Independent examiner 2: Assoc. Hoang Thi Kim Dung Examiner 1: Assoc. Tran Ngoc Quyen Examiner 2: Assoc.

Nguyen Thi Le Thu Examiner 3: Assoc. Ton That Quang ADVISORS: 1. Phan Thanh Son Nam 2. 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 7Ï07Ҳ7/8Ұ1È1 /XұQiQQj\WUuQKEj\ SKѭѫQJSKiSWәQJKӧSÿһFWUѭQJKyDOêYjKRҥWWtQK[~FWiFFӫD YұWOLӋXNKXQJFѫNLPORҥL,QGLXP ,Q-MOF) là MIL-68 (In) YjYұWOLӋXNKXQJ FѫNLP VҳW )H-02) EDRJӗP)H3O(BPDC)3 và MOF-&iFYұWOLӋX02)Qj\ÿѭӧFVӱGөQJ OjPFKҩW[~FWiFGӏWKӇFKRFiFSKҧQӭQJKuQKWKjQKOLrQNӃW&í1Yj&í2ÿӇWәQJKӧS FiFKӧSFKҩW-nitro-3-arylimidazo[1,2-a]pyridine, 2,4-diarylpyridine và các Į-acyloxy ether. &KѭѫQJÿҫXWLrQFӫDOXұQiQQj\WUuQKEj\WәQJTXDQWjLOLӋXYӅFiFYұWOLӋX,Q-MOF và Fe-02)FөWKӇOjYұWOLӋX MIL-68(In), Fe3O(BPDC)3 và MOF-7әQJTXDQYӅFҩX WU~FWtQKFKҩWSKѭѫQJSKiSWәQJKӧSÿһFWtQKYjӭQJGөQJ[~FWiFFӫDFK~QJ1JRjL UDFKѭѫQJQj\FNJQJWәQJTXDQYӅFiFSKҧQӭQJKuQKOLrQNӃW&í1Yj&í2ÿӇWәQJKӧS các KӧS FKҩW 2-nitro-3-arylimidazo[1,2-a]pyridine, 2,4-diarylpyridine và Į-acyloxy ether.

&KѭѫQJWKӭKDLFӫDOXұQiQQj\WUuQKEj\TXiWUuQKWKӵF QJKLӋPWәQJKӧSYұWOLӋXMIL- 68(In), Fe3O(BPDC)3 và MOF-235 và NKҧRViWFiFÿLӅXNLӋQWәQJKӧS FiFKӧSFKҩW- nitro-3-arylimidazo[1,2-a]pyridine, 2,4-diarylpyridine và Į-acyloxyether YӟLFiF[~FWiF MIL-68(In), Fe3O(BPDC)3 và MOF-WѭѫQJӭQJ. &KѭѫQJWKӭEDFӫDOXұQiQQj\WUuQKEj\NӃWTXҧYjWKҧROXұQYӅYұWOLӋX0,/-68(In), Fe3O(BPDC)3 và MOF-ÿmWәQJKӧSYjNKҧQăQJӭQJ GөQJFiFYұWOLӋX02)Qj\ tUrQFiFSKҧQӭQJhình thành OLrQNӃW&íN và Cí2&iF02)Qj\ÿѭӧFWәQJKӧS EҵQJ FiFSKѭѫQJSKiSQKLӋW dung môi và [iFÿӏQKFiFÿһFWUѭQJKRiOê EҵQJSKѭѫQJSKiS ÿR PXRD, SEM, TEM, TGA, FT-IRSKkQEӕNtFKWKѭӟFOӛ[ӕSYjÿRKҩSSKө YұWOêQLWѫ .ӃWTXҧWKX ÿѭӧFFKRWKҩ\Fác In-MOF và Fe-MOF Qj\FyKRҥWWtQK[~FWiFFDRFKRFiF SKҧQӭQJKuQKWKjQKOLrQNӃW&í1 và CíO và QKӳQJ [~FWiFQj\ÿѭӧF WKXKӗLYjWiLVӱ GөQJQKLӅXOҫQPjNK{QJEӏJLҧPÿiQJNӇKRҥWWtQK[~FWiF 7KHRKLӇXELӃWWӕWQKҩWFӫD chúng tôi, nKӳQJFKX\ӇQKRi này VӱGөQJFKҩW[~FWiF0,/-68(In), Fe3O(BPDC)3 and MOF-FKѭDÿѭӧFÿӅFұSWUѭӟFÿk\WURQJWjLOLӋX ii THESIS SUMMARY This thesis describes the synthesis, characterization and catalytic applications of indium- based 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 &í1and CíObond forming reactions to synthesize 2-nitro-3-aryl imidazo[1,2-a]pyridines, 2,4-diarylpyridines and Į-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 &í1and &í2 bond forming reactions for the synthesis of 2-nitro-3-aryl imidazo[1,2-a]pyridines, 2,4-diarylpyridines and Į- acyloxy ethers. The second chapter of this thesis presents the experimental process of synthesizing MIL- 68(In), Fe3O(BPDC)3 and MOF-235 and test catalytic activity of these MOFs on &í1 DQG&í2 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 &í1DQG&í2 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 CíN and &í2 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), iron- based 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 &í1 DQG &í2 forming reactions to synthesize 2-nitro-3- aryl imidazo[1,2-a]pyridines. Fe3O(BPDC)3 was employed as heterogeneous catalyst for CíN bond forming reactions to synthesize 2,4-diaryl pyridines. MOF-235 was utilized as heterogeneous catalyst for &í2 bond forming reactions to synthesize Į- acyloxy ethers.

These catalytic systems offered practical approaches with high yields and selectivity. Additionally, broad functionality was shown to be compatible. The In- MOF 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. 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. 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. 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. 1 CHAPTER 1 LITERATURE REVIEW OF MIL-68(In), Fe3O(BPDC)3, MOF-235 $1'&í1&í2%21')250,1*5($&7,216. 1 Metal-organic frameworks. 2 Synthesis and structure of MIL-68(In), MOF-235 and Fe3O(BPDC)3.

1 Synthesis and structure of MIL-68(In). 2 Synthesis and structure of MOF-235. 3 Synthesis and structure of Fe3O(BPDC)3. 3 Application of MIL-68 (In), MOF-235 and Fe3O(PBDC)3 in catalysis.

4 &í1DQG&í2ERQGIRUPing reactions .1 &í1ERQGIRUPDWLRQLQV\QWKHVLVRI-nitro-3-arylimidazo[1,2-a]pyridine derivatives .2 &í1ERQGIRUPDWLRQIRUV\QWKHVLVRIaryl substituted pyridines .3 &í2ERQGIRUPDWLRQIRUV\QWKHVLVRIĮ-acyloxy ethers .2 Synthesis of MIL-68(In), Fe3O(BPDC)3 and MOF-235 .1 Materials and instrumentation .3 Catalyitic studies of MIL-68(In), Fe3O(BPDC)3 DQG02)RQ&í1 DQG&í2ERQGIRUPLQJUHDFWLRQV. 1 Materials and instrumentation. 2 Catalytic studies of MIL- ,Q RQ&í1ERQGIRUPDWLRQUHDFWLRQ between 2-aminopyridines and nitroalkenes. 3 Catalytic studies of Fe3O(BPDC)3 RQ&í1ERQGIRUPDWLRQUHDFWLRQ between N,N-dialkylanilines with ketoxime carboxylates.

4 Catalytic studies of MOF-235 RQ&í2ERQGIRUPDWLRQUHDFWLRQfor the direct esterification of carboxylic acids with C(sp3)íH bonds to form Į-acyloxy ethers. 46 RESULT AND DISCUSSION. 1 Characterization of MIL-68(In), MOF-235 and Fe3O(BPDC)3 .1 Characterization of MIL-68(In) .2 Characterization of MOF-235 .3 Characterization of Fe3O(BPDC)3. 2 Catalyitic studies of MIL-68(In), Fe3O(BPDC)3 DQG02)RQ&í1 DQG&í2ERQGIRUPLQJUHDFWLRQV .1 Catalytic studies of MIL-68(In) on CN bond formation reactions (1) .2 Catalytic studies of Fe3O(BPDC)3 on CN bond formation reactions (2) .3 Catalytic studies of MOF-235 on CO bond forming reaction (3) .103 CONCLUSION AND RECOMMENDATIONS.

1 Summary of current work. 2 Contributions of this thesis .125 LIST OF PUBLICATIONS .127 LIST OF OTHER PUBLICATIONS .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].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] .3 Potential polytopic organic acids as linkers in MOFs [6].4 Coordination geometries of transition metal ions [6] .5 Examples of SBUs from carboxylate MOFs. O, red; N, green; C, black [27] .6 The values in parentheses represent the pore volume (cm3.g-1) of these materials [29].7 Aspects of crystallization in synthesis of solid compounds [32].10 View of the structure of MIL-68(In) along the c axis [42] .11 View of a chain of InO4(OH)2 octahedra in MIL-68(In) [42] .12 The structures of MOF-235 (Fe, blue; O, red; Cl, teal; C, gray) [53] .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-and- stick and polyhedral representations of trigonal prismatic geometry (blue) and (b) ditopic links, 1,4-benzenedicarboxylate (BDC) [53] .14 The basic unit of MOF-235 in solvent (a) and activated (b) [53] .15 Organization of the two orthogonally interpenetrated trigonal bipyramidalbuilding units of of Fe3O(BPDC)3 [45].16 Proposed mechanisms for the Strecker reaction catalyzed by In-MOF [65] .17 Some biologically active heterocycles containing 3-aryl substituted imidazopyridines [86-88] .18 Selected bioactive agents containing the poly-arylated pyridine structure [95, 96].19 Selected examples of Į-acyloxy ethers [103] .1 X-ray powder diffractograms of the MIL-68(In).2 SEM and TEM micrograph of the MIL-68(In).3 TGA analysis of the MIL-68(In).4 Pore size distribution of the MIL-68(In).5 FT-IR spectrum of terephthalic acid (a), and the MIL-68(In) (b) .6 Nitrogen adsorption/desorption isotherm of the MIL-68(In).

Adsorption data are shown as closed circles and desorption data as open circles .7 X-ray powder diffractograms of the MOF-235 .8 SEM and TEM micrograph of the MOF-235, respectively .9 TGA analysis of the MOF-235 .10 Pore size distribution of the MOF-235 .11 FT-IR spectrum of 1,4-benzenedicarboxylic acid (a), and MOF-235 (b) .12 Nitrogen adsorption/desorption isotherm of the MOF-235. Adsorption data are shown as closed circles and desorption data as open circles.13 Powder X-ray diffractograms of the Fe3O(BPDC)3.14 SEM and TEM micrograph of the Fe3O(BPDC)3 .15 TGA analysis of the Fe3O(BPDC)3 .16 FT-IR spectrum of ¶-biphenyldicarboxylic acid (a), and the Fe3O(BPDC)3(b).17 Pore size distribution of the Fe3O(BPDC)3.18 Nitrogen adsorption/desorption isotherm of the Fe3O(BPDC)3. Adsorption data are shown as closed triangles and desorption data as open triangles .19 Yields of 2-nitro-3-phenylimidazo[1,2-a]pyridine at varied temperatures64 Figure 3.20 Yields of 2-nitro-3-phenylimidazo[1,2-a]pyridine at various catalyst amounts .21 Yields of 2-nitro-3-phenylimidazo[1,2-a]pyridine with diverse reactant mole proportions .22 Yields of 2-nitro-3-phenylimidazo[1,2-a]pyridine in miscellaneous solvents.23 Yields of 2-nitro-3-phenylimidazo[1,2-a]pyridine with different co- catalysts .24 Yields of 2-nitro-3-phenylimidazo[1,2-a]pyridine at varied co-catalyst quantities .25 Yields of 2-nitro-3-phenylimidazo[1,2-a]pyridine at diverse 2- aminopyridine concentrations .26 Leaching assessment showed that 2-nitro-3-phenylimidazo[1,2-a]pyridine was not generated in the absence of the solid catalyst .27 Yields of 2-nitro-3-phenylimidazo[1,2-a]pyridine with miscellaneous homogeneous catalysts .28 Yields of 2-nitro-3-phenylimidazo[1,2-a]pyridine with miscellaneous MOF-based catalysts .29 TEMPO test showing that the reaction could not proceed in the presence ix of radical trapping reagent.30 Argon test indicating that the reaction could proceed in dichloroethane under argon.31 Argon test indicating that yield was adjusted by the amount of dichloroethane .33 X-ray powder diffractograms of the new (a) and recovered (b) catalyst .34 FT-IR spectrum of the new (a) and recovered (b) catalyst .35 Yield of 2,4-diphenylpyridine vs temperature .36 Yield of 2,4-diphenylpyridine vs reactant molar ratio.37 Yield of 2,4-diphenylpyridine vs solvent.38 Yield of 2,4-diphenylpyridine vs oxidant .39 Yield of 2,4-diphenylpyridine vs oxidant amount .40 Yield of 2,4-diphenylpyridine vs catalyst quantity .41 Leaching test verified that 2,4-diphenylpyridine was not generated in the absence of the iron-organic framework catalyst.42 Yield of 2,4-diphenylpyridine vs heterogeneous catalysts .43 Yield of 2,4-diphenylpyridine vs homogeneous catalysts .44 Yield of 2,4-diphenylpyridine in the presence of radical scavengers .45 Catalyst recycling studies.46 FT-IR spectrum of the fresh (a) and recovered (b) catalyst .47 X-ray powder diffractograms of the fresh (a) and recovered (b) catalyst .48 Conversion and selectivity vs reaction time .49 Yields of 1,4-dioxan-2-yl 4-methoxybenzoate vs temperature .50 Yields of 1,4-dioxan-2-yl 4-methoxybenzoate vs catalyst concentration 105 Figure 3.51Yields of 1,4-dioxan-2-yl 4-methoxybenzoate vs 4-methoxybenzoic acid:1,4-dioxane molar ratio .52 Yields of 1,4-dioxan-2-yl 4-methoxybenzoate vs oxidant.53 Yields of 1,4-dioxan-2-yl 4-methoxybenzoate vs oxidant quantity .54 Yields of 1,4-dioxan-2-yl 4-methoxybenzoate vs homogeneous catalysts .55 Yields of 1,4-dioxan-2-yl 4-methoxybenzoate vs heterogeneous catalysts .56 Leaching experiment revealed that 1,4-dioxan-2-yl 4-methoxybenzoate was not generated in the absence of the solid catalyst .57 Yield of 1,4-dioxan-2-yl 4-methoxybenzoate in the presence of pyridine .58 Yield of 1,4-dioxan-2-yl 4-methoxybenzoate under air and under argon112 Figure 3.59 Catalyst recycling investigation for the direct esterification of 4- methoxybenzoic acid with 1,4-dioxane.60 XRD results of the new (a) and reutilized (b) catalysts .61 FT-IR results of the new (a) and reutilized (b) catalysts .114 xi LIST OF SCHEMES Scheme 1.1 The synthesis of 4-(1,3-diphenylprop-2-ynyl)morpholine via C±H bond activation using the MIL-68(In) catalyst [68] .