VIETNAM NATIONAL UNIVERSITY – HO CHI MINH CITY HO CHI MINH CITY UNIVERSITY OF TECHNOLOGY DANG HUYNH GIAO Cu-BASED ORGANIC FRAMEWORKS AS CATALYSTS FOR C–C AND C–N COUPLING REACTIONS PhD THESIS HO CHI MINH CITY 2015 VIETNAM NATIONAL UNIVERSITY – HO CHI MINH CITY HO CHI MINH CITY UNIVERSITY OF TECHNOLOGY DANG HUYNH GIAO Cu-BASED ORGANIC FRAMEWORKS AS CATALYSTS FOR C–C AND C–N COUPLING REACTIONS Major: Organic Chemical Technology Major code: 62527505 Independent examiner 1: Prof. Dinh Thi Ngo Independent examiner 2: Assoc. Nguyen Thi Phuong Phong Examiner 1: Assoc. Nguyen Cuu Khoa Examiner 2: Assoc.
Nguyen Thai Hoang Examiner 3: Assoc. Le Thi Hong Nhan 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 Dang Huynh Giao i THESIS SUMMARY This thesis describes the synthesis, characterization and catalytic applications of four copper-based metal-organic frameworks (Cu-MOFs) including Cu3(BTC)2, Cu2(BDC)2(DABCO), Cu2(BPDC)2(BPY) and Cu(BDC). These Cu-MOFs were used as heterogeneous catalysts for direct CC and CN coupling reactions to synthesize propargylamines and quinoxalines.
The first chapter of this thesis provides a literature review of Cu-MOFs. The review is limited in Cu3(BTC)2, Cu2(BDC)2(DABCO), Cu2(BPDC)2(BPY) and Cu(BDC). An overview of their structures, properties, synthesis, characterization methods and catalytic applications is described. In addition, the chapter also reviews CC and CN coupling reactions for the synthesis of propargylamines and quinoxalines.
The second chapter of this thesis discusses the synthesis and characterization of four Cu-MOFs including Cu3(BTC)2, Cu2(BDC)2(DABCO), Cu2(BPDC)2(BPY) and Cu(BDC). These Cu-MOFs were prepared by solvothermal methods and characterized by X-ray powder diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), inductively coupled plasma mass spectrometry (ICP-MS), hydrogen temperature-programmed reduction (H2-TPR) and nitrogen physisorption measurements. The third chapter of this thesis describes the evaluation of Cu-MOFs as heterogeneous catalysts for direct CC and CN coupling reactions. These Cu-MOFs were found to be highly catalytically active for direct CC and CN coupling reactions.
The Cu- MOF catalysts could be recovered and reused several times without a significant degradation in catalytic activity. To the best of our knowledge, these transformations using MOFs catalysts were not previously mentioned in the literature. ii ABSTRACT Four highly porous Copper-based organic frameworks (Cu-MOFs) such as Cu3(BTC)2, Cu2(BDC)2(DABCO), Cu2(BPDC)2(BPY) and Cu(BDC) were synthesized and characterized by X-ray powder diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), inductively coupled plasma mass spectrometry (ICP-MS), hydrogen temperature-programmed reduction (H2-TPR) and nitrogen physisorption measurements. Three Cu-MOFs including Cu3(BTC)2, Cu2(BDC)2(DABCO), Cu2(BPDC)2(BPY) were used as heterogeneous catalysts for direct CC coupling reactions to synthesize propargylamines.
Cu(BDC) was employed as heterogeneous catalyst for CN coupling reaction to synthesize quinoxalines. These catalytic systems offered practical approaches with high yields and selectivity. Additionally, broad functionality was shown to be compatible. The Cu-MOFs catalysts could be recovered and reused several times without significant degradation in catalytic activity.
To the best of our knowledge, these transformations using Cu-MOFs catalysts were not previously mentioned in the literature. iii 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 Dr.
Truong Vu Thanh and Assoc. Le Thi Hong Nhan for their insight and questions that have undoubtedly helped me progress to this point. I would like to thank Dr. Hiroyasu Furukawa 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 (Nguyen Kim Chung, Nguyen Thanh Tung, Nguyen Thai Anh, Le Khac Anh Ky, Nguyen Dang Khoa, Nguyen Van Chi, Nguyen Tran Vu, Le Thi Ngoc Hanh) for the stimulating discussions in Organic Chemistry Division. Additionally, I wish to acknowledge four undergraduate students (Dang Truong Thinh, Nguyen Thanh Duy, Nguyen Duy Thanh, Dong Anh Quoc) and graduated student (Vu Thi Hai Yen) for their helps during the time they studied in laboratory. I also thank to my colleagues in Chemical Engineering Department at CanTho University for their encouragement. Especially, I would like to thank Dr.
Luong Huynh Vu Thanh about help me download the scientific papers I could not download in Viet Nam. My deepest gratitude to my family: my parents, my oldest sister Dang Huynh Thu, my older sister Dang Huynh Nhu, my younger brother Dang Quoc Dung and my youngest sister Dang Huynh Anh. The support and love from my family is of inestimable value. iv TABLE OF CONTENTS TABLE OF CONTENTS.
v LIST OF FIGURES .vii LIST OF SCHEMES. xi LIST OF TABLES.xiii LIST OF ABBREVIATION. 1 CHAPTER 1 LITERATURE REVIEW: Cu3(BTC)2, Cu2(BDC)2(DABCO), Cu2(BPDC)2(BPY), Cu(BDC) AND CC, CN COUPLING REACTIONS .1 Introduction to metal-organic frameworks .1 Structures and properties of Cu3(BTC)2, Cu(BDC), Cu2(BDC)2(DABCO) and Cu2(BPDC)2(BPY) .2 Synthesis of Cu3(BTC)2, Cu(BDC), Cu2(BDC)2(DABCO) and Cu2(BPDC)2(BPY) .3 Characterization of Cu3(BTC)2, Cu(BDC), Cu2(BDC)2(DABCO) and Cu2(BPDC)2(BPY) .4 Catalytic activities of Cu3(BTC)2, Cu(BDC), Cu2(BDC)2(DABCO) and Cu2(BPDC)2(BPY) .3 CC cross coupling reactions .4 CN cross coupling reactions .5 Aims and objectives. 36 CHAPTER 2 SYNTHESIS AND CHARACTERIZATION OF Cu3(BTC)2, Cu2(BDC)2(DABCO), Cu2(BPDC)2(BPY), AND Cu(BDC) .1 Materials and instrumentation .2 Synthesis of Cu3(BTC)2 .3 Synthesis of Cu2(BDC)2(DABCO) .4 Synthesis of Cu2(BPDC)2(BPY) .5 Synthesis of Cu(BDC) .3 Results and discussions .1 Synthesis and characterization of Cu3(BTC)2 .2 Synthesis and characterization of Cu2(BDC)2(DABCO) .3 Synthesis and characterization of Cu2(BPDC)2(BPY) .4 Synthesis and characterization of Cu(BDC).
63 CHAPTER 3 CATALYTIC STUDIES OF Cu3(BTC)2, Cu2(BDC)2(DABCO), Cu2(BPDC)2(BPY) AND Cu(BDC) ON CC AND CN COUPLING REACTIONS65 3.1 Materials and instrumentation .2 Catalytic studies on CC, CN cross coupling reactions .3 Results and discussions .1 Catalytic studies of Cu3(BTC)2 on CC cross coupling reaction (1) .2 Catalytic studies of Cu2(BDC)2(DABCO) on CC cross coupling reaction (2) .3 Catalytic studies of Cu2(BPDC)2(BPY) on CC cross coupling reaction (3) .4 Catalytic studies of Cu(BDC) on CN cross coupling reaction (4) .1 Summary of current work.2 Contributions of this thesis. 116 LIST OF PUBLICATIONS. 132 vi LIST OF FIGURES Figure 1. The 3D structures of representative MOFs [7].
Development of MOF fields in comparison to the MOF catalysis in the last ten years (SciFinder until Jan 15, 2014) [25]. Cu-MOFs (M=Cu, L=carboxylate) contain open metal sites that enable the reactivity of organic compounds in organic transformations. 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]. Reversible crystalline phase transformation of Cu(BDC) from the lamellar to the compact structure upon desorption/adsorption of DMF [40].
X-Ray structure of the doubly interpenetrating pillared-grid framework Cu2(BPDC)2(BPY) [45]. Pore apertures of Cu2(BDC)2(DABCO) [48]. Solvothermal synthesis of MOFs [10]. PXRD patterns of Cu3(BTC)2, Cu(BDC), Cu2(BDC)2(DABCO) and Cu2(BPDC)2(BPY) [45-47, 52].
In situ PXRD patterns of Cu(BDC) [10]. SEM images of Cu3(BTC)2, Cu(BDC), Cu2(BDC)2(DABCO) and Cu2(BPDC)2(BPY) [10, 33, 35, 37]. TGA of Cu3(BTC)2, Cu(BDC), Cu2(BDC)2(DABCO) and Cu2(BPDC)2(BPY) [33, 35-37]. FT-IR spectra of Cu3(BTC)2, Cu(BDC), Cu2(BDC)2(DABCO) and Cu2(BPDC)2(BPY) [33, 35-37].
Structure of Cu3(BTC)2 (a) [46], Cu(BDC) (b) [44], Cu2(BDC)2(DABCO) [117] and Cu2(BPDC)2BPY [45]. X-ray powder diffractograms of the synthesized Cu3(BTC)2. FT-IR spectra of the Cu3(BTC)2 (a) and 1,3,5-benzenetricarboxylic acid (b). SEM micrograph of the Cu3(BTC)2.
TEM micrograph of the Cu3(BTC)2. TGA analysis of the Cu3(BTC)2. H2-TPR profile of the Cu3(BTC)2. X-ray powder diffractograms of the synthesized Cu2(BDC)2(DABCO).
SEM micrograph of the Cu2(BDC)2(DABCO). TEM micrograph of the Cu2(BDC)2(DABCO). FT-IR spectra of 1,4-benzenedicarboxylic acid (a), diazabicyclo[2. TGA analysis of the Cu2(BDC)2(DABCO).
H2-TPR profile of the Cu2(BDC)2(DABCO). X-ray powder diffractograms of the synthesized Cu2(BPDC)2(BPY). TGA of the Cu2(BPDC)2(BPY). SEM micrograph of the Cu2(BPDC)2(BPY).
TEM micrograph of the Cu2(BPDC)2(BPY). FT-IR spectra of 4,4’-Biphenyldicarboxylic acid (a), 4,4’-Bipyridine (b) and the Cu2(BPDC)2(BPY) (c). H2-TPR profile of the Cu2(BPDC)2(BPY). X-ray powder diffractograms of the synthesized Cu(BDC).
TGA of the Cu(BDC). SEM micrograph of the Cu(BDC). TEM micrograph of the Cu(BDC). FT-IR spectra of 1,4-benzenedicarboxylic acid (a) and the Cu(BDC) (b)62 Figure 2.
H2-TPR profile of the Cu(BDC). Effect of temperature on reaction conversions. Effect of catalyst amount on reaction conversions. Effect of phenylacetylene: N,N-dimethylaniline molar ratio on reaction conversions.
Effect of oxidant on reaction conversions. Effect of oxidant concentration on reaction conversions. The selectivity of reaction with different oxidant concentrations on reaction conversions. Effect of different solvents on reaction conversions.
The selectivity of reaction with different solvents on reaction conversions. Leaching test indicated no contribution from homogeneous catalysis of active species leaching into reaction solution. Different Cu-MOFs catalysts for the direct CC coupling reactions. Catalyst recycling studies.
FT-IR spectra of the fresh (a) and reused (b) Cu3(BTC)2 catalyst. X-ray powder diffractograms of the fresh (a) and reused (b) Cu3(BTC)2 catalyst. Effect of temperature on reaction conversions. Effect of catalyst amount on reaction conversions.
Effect of phenylacetylene: N-methylaniline molar ratio on reaction conversions. Effect of oxidant on reaction conversions. Effect of oxidant concentration on reaction conversions. The selectivity of reaction with different oxidant concentrations on reaction conversions.
Effect of different solvents on reaction conversions. The selectivity of reaction with different solvents on reaction conversions. Leaching test indicated no contribution from homogeneous catalysis of active species leaching into reaction solution. Different Cu-MOFs catalysts for the direct C-C coupling reactions.
Catalyst recycling studies: Reaction conversion (a) and selectivity of reaction (b). FT-IR spectra of the fresh (a) and reused (b) Cu2(BDC)2(DABCO) catalyst. X-ray powder diffactograms of the fresh (a) and reused (b) Cu2(DABCO)2(DABCO). Effect phenylacetylene:benzaldehyde: tetrahydroisoquinoline molar ratio ratio on reaction conversions.
Effect of temperature on reaction conversions. Effect of catalyst amount on reaction conversions. Effect of different solvents on reaction conversions. Different copper salts as catalyst for the C1-alkynylation reaction of tetrahydroisoquinoline.
Different MOFs as catalyst for the C1-alkynylation reaction of tetrahydroisoquinoline. Effect of catalyst poison on reaction conversion. Adding product to the reaction mixture. Leaching test indicated no contribution from homogeneous catalysis of active species leaching into reaction solution.
Catalyst recycling studies. FT-IR spectra of the fresh (a) and reused (b) Cu2(BPDC)2(BPY) catalyst. X-ray diffractograms of the fresh (a) and reused (b) Cu2(BPDC)2(BPY) catalyst. Effect of different derivative benzaldehydes on reaction conversions.
Effect of different derivative phenylacetylenes on reaction conversions. Effect of temperature on reaction conversions. Effect of catalyst amount on reaction conversions. Effect of α-hydroxyacetophenone : phenylenediamine molar ratio on reaction conversions.
Effect of different solvents on reaction conversions. Leaching test indicated no contribution from homogeneous catalysis of active species leaching into reaction solution. Effect of catalyst poison on reaction conversion. Different catalyst for the quinoxaline synthesis reaction.
Effect argon on reaction conversion. Catalyst recycling studies. FT-IR spectra of the fresh (a) and reused (b) Cu(BDC) catalyst. X-ray powder diffractograms of the fresh (a) and reused (b) Cu(BDC) catalyst.
The reaction between α-hydroxyacetophenone and different 1,2- aryldiamines. 111 x LIST OF SCHEMES Scheme 1. Solvothermal synthesis of Cu3(BTC)2, Cu2(BDC)2(DABCO), Cu2(BPDC)2(BPY) and Cu(BDC) [44-47]. The reaction of various aldehydes with methanol using the Cu3(BTC)2 as catalyst [64].
The oxidation of the benzylic compounds with t-butylhydroperoxide using the Cu3(BTC)2 as catalyst [66]. The 1,3-dipolar cycloaddition reaction catalyzed by various Cu- MOFs catalysts [41]. The modified Friedländer reaction using the Cu(BDC) as catatalyst [37].
