VIETNAM NATIONAL UNIVERSITY – HOCHIMINH CITY UNIVERSITY OF TECHNOLOGY TRAN VAN THUAN COPPER – BASED METAL – ORGANIC FRAMEWORKS AS EFFICIENT AND RECYCLABLE CATALYSTS FOR THE OXIDATIVE AMINATION REACTIONS Major: Chemical technology Major code: 60 52 03 01 M. THESIS HO CHI MINH CITY, JANUARY 2015 The thesis was completed at Ho Chi Minh City University of Technology - Vietnam National University – Ho Chi Minh City. Truong Vu Thanh …………………………………… Independent opponent 1: Dr. Nguyen Quoc Thiet …………………………………… Independent opponent 2: Dr.
Phan Thi Hoang Anh …………………………………… Master thesis was defended at Ho Chi Minh City University of Technology – Vietnam National University – Ho Chi Minh City on January 14th, 2015 Member of the committee included: 1. Nguyen Ngoc Hanh 2. Phan Thi Hoang Anh 3. Nguyen Quoc Thiet 4.
Bui Tan Nghia 5. Ha Cam Anh Identification of the President’s committee and Dean of the faculty for several adjustments (if any)………………………………………………………………………………………. President’s committee Dean of the faculty of chemical engineering Assoc. Nguyen Ngoc Hanh Prof.
Phan Thanh Son Nam VIETNAM NATIONAL UNIVERSITY HCMC SOCIALIST REPUBLIC OF VIETNAM UNIVERSITY OF TECHNOLOGY Independence – Freedom – Happiness Ho Chi Minh City, January 28th, 2015 I. Personal information Full name: TRAN VAN THUAN Gender: Male Birthday: 20/12/1990 Major: Chemical technology Major code: 60 52 03 01 Student code: 12144423 II. Thesis title COPPER – BASED METAL – ORGANIC FRAMEWORKS AS EFFICIENT AND RECYCLABLE CATALYSTS FOR THE OXIDATIVE AMINATION REACTIONS III. Aim and objectives 1.
Characteristics of the Cu2(BDC)2(BPY) and Cu3(BTC)2 by various techniques including XRD, FT-IR, SEM, TEM, TGA, ICP and nitrogen physisorption measurement. Catalytic investigation of the Cu2(BDC)2(BPY) and Cu3(BTC)2 for the oxidative amination reactions. Started date: January 20th, 2014 V. Finished date: November 21st, 2014 VI.
Truong Vu Thanh The project was approved by the Department of Organic Chemical Engineering. Faculty of Chemical Organic Chem. Department Supervisor Engineering Prof. Truong Vu Thanh Phan Thanh Son Nam Le Thi Hong Nhan ACKNOWLEDGEMENTS I would like to express sincere gratitude to my supervisor, Dr.
Truong Vu Thanh for his constant advice, guidance, insight, and for sharing his extensive knowledge of chemistry. I am also grateful to all teaching staffs of the Organic Chemical Engineering Department for their valuable help. I would like to give my special thanks to Ms. Nguyen Thi Ngoc Hạnh, Mr.
Nguyen Kim Chung, Ms. Dang Huynh Giao, Mr. Nguyen Thai Anh, Mr. Nguyen Dang Khoa, Mr.
Nguyen Thanh Tung, Mr. Nguyen Tran Vu, Mr. Tran Hai Quan and Mr. Phan Vu Duc Ha and for their meaningful encouragement and help.
I wish to thank all of my friends and all students for their support during course of my study. Especially, I would like to express my sincere thankfulness to my family who are always standing by my side through the hardest times. Their unconditional love and support have always accompanied with every achievement in my life. Ho Chi Minh City, January 2015 Tran Van Thuan i ABSTRACT The utilization of both ligand 1,4-dicarboxylic acid and 4,4-bipyridine preparing for the Cu2(BDC)2(BPY) were implemented by solvothermal method.
The Cu3(BTC)2 also was synthesized according to previous works. The structure of this materials were characterized using several various techniques, including X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), inductively coupled plasma (ICP) analysis, and nitrogen physisorption measurements. The Cu2(BDC)2(BPY) and Cu3(BTC)2 were used as heterogeneous catalysts for the oxidative amination reactions. Several essential factors including solvent, temperature, molar ratio, catalyst concentration and oxidant component were rigorously investigated in order to establish optimal circumstances of reaction.
In leaching test, the catalyst was facilely separated from the reaction by centrifugation. The catalyst recyclability was also specifically investigated and the reaction could be reused several times without a significant degradation in catalytic activity. Under optimal reaction, reactions scope with respect to coupling partners were also determined. The products were confirmed by GC- MS, 1H NMR and 13C NMR.
ii TABLE OF CONTENTS ACKNOWLEDGEMENTS. ii LIST OF ABBREVIATIONS. v LIST OF FIGURES .vi LIST OF TABLES .ix LIST OF SCHEMES. x CHAPTER 1: LITERATURE REVIEW.1 METAL – ORGANIC FRAMEWORKS .2 MOFs AS CATALYST FOR ORGANIC REACTION .1 MOFs with catalytically active metal nodes in the framework .2 Catalytic functionalization of organic framework linkers .4 MOF-encapsulated catalytically active guests .3 C – N OXIDATIVE COUPLING REACTION .1 Copper-catalyzed oxidative amidation of terminal alkynes .2 Copper-catalyzed C-N oxidative amination of C-H/N-H.
19 iii CHAPTER 2: EXPERIMENTAL SECTION .1 MATERIALS AND INSTRUMENTATION .2 SYNTHESIS OF THE METAL-ORGANIC FRAMEWORKS .2 Preparation of Cu2(BDC)2(BPY).3 Preparation of Cu3(BTC)2.1 Oxidative amindation of terminal alkynes between phenylacetylene and 2 – oxazolidone .2 The oxidative α-amination between propiophenone and morpholine .4 Formulate for reaction calculation .1 Formulate for calculating conversion of reaction .2 Formulate for calculating selectivity of reaction. 26 CHAPTER 3: RESULTS AND DISCUSSION. CATALYTIC INVESTIGATION OF THE Cu2(BCD)2(BPY) FOR THE OXIDATIVE AMINDATION OF TERMINAL ALKYNES .3 CATALYTIC INVESTIGATION OF THE Cu3(BTC)2 FOR THE C-N OXIDATIVE AMINATION OF C-H/N-H. 76 iv LIST OF ABBREVIATIONS DMF: N,N-Dimethylformamide DCM: Dichloromethane FT-IR: Fourier transform infrared GC: Gas chromatography GC-MS: Gas chromatography-mass spectrometry ICP-AES: Inductively coupled plasma atomic emission spectroscopy BDC: 1,4 – benzenedicarboxylic acid BTC: 1,3,5 – benzenetricarboxylic acid DABCO: 1,4-diazabicyclo[2.2]octane IRMOF: Iso-reticular metal-organic framework MIL: Materials of Institut Lavoisier MOF: Metal-organic framework SEM: Scanning electron microscopy TBHP: Tert-butyl hydroperoxide TEM: Transmission electron microscopy TGA: Thermogravimetric analysis TON: Turnover number TOF: Turnover frequency BPY: 4,4’ – bipyridine DBU: 1,8-Diazabicycloundec-7-ene H2BTEC: 1,4-benzenedicarboxylic acid 4-BTAPA: 1,3,5-benzene tricarboxylic acid tris[N-(4-pyridyl)amide v LIST OF FIGURES Page Content 2 Figure 1.1 (a) The Re6Se8(CN)6 unit and (b) the same abstracted as an octahedral SBU 2 Figure 1.3 SBUs with (from top) eight, eight, and 12 points of extension 3 Figure 1.4 Examples of tetratopic linkers: (a and b) tetrahedral and (c) square.5 Different modes of interpenetration for 1D nets: (a) 1D → 1D parallel (b) 1D → 2D parallel and (c) 1D → 3D inclined interpenetration 4 Figure 1.6 (a) Heterochiral and (b) homochiral interpenetration of two 3D nets.7 Crystal structure of MOF-210, DOI: 10.8 Structural representations of the different forms of [Zn2(2,5-BME- BDC)2(DABCO)] n along the crystal ographic c-axis.9 Schematic view of the formation of a Bio-MOF (Bio-MIL-1) built up from bioactive linker and its delivery.
Here the bioactive linker is nicotinic acid. Iron, oxygen, nitrogen, and carbon atoms are in orange, red, gray, and black, respectively. Metal octahedra, oxygen and carbon atoms are in orange, red, and black, respectively.11 Schematic representation of the synthesis of POST – 1.12 The diamond – like 3D network of Cd(QA)2; selective sorption in favor of S-alcohol.13 Fluctuation of reagent and product concentration of the Cu3(BTC)2- catalyzed cyanosilylation of benzaldehyde (in pentane, 40 oC). Ligand employed in POST-1 synthesis (left) and transesterification of 2,4-dinitrophenylacetate with alcohol in CCl4 at 27 oC in the presence of POST-1 (right) 16 Figure 1.15 Cyclohexane catalytic oxidation catalyzed by Mn-metalated porphyrin encapsulated in rho-ZMOF.17 Farnesyl tethered ynamide based on C-N coupling reaction.18 A model of C-N coupling reaction between phenylacetylene and 2- oxazolidinone using copper catalyst 19 Figure 1.19 Common pharmacophore in medicinal agents toward α-amino carbonyls.1 X-ray powder diffractograms of the Cu2(BDC)2(BPY) 29 Figure 3.2 FT-IR spectra of the Cu2(BDC)2(PBY) (a); 1,4 – benzenedicarboxylic acid (b) and 4,4’-bipyridine (c).3 Nitrogen adsorption/desorption isotherm of the Cu2(BDC)2(BPY).
Adsorption data is shown as closed circles and desorption data as vertical bars.4 Pore size distribution of the Cu2(BDC)2(BPY) 31 Figure 3.5 TGA analysis of the Cu2(BDC)2(BPY) 32 Figure 3.6 SEM micrograph of the Cu2(BDC)2(BPY) 32 Figure 3.7 TEM micrograph of the Cu2(BDC)2(BPY) 33 Figure 3.8 XRD diffraction of Cu3(BTC)2 after 24 h heating (a) and after activating under vacuum pressure (b) 34 Figure 3.9 FT-IR spectra of the Cu3(BTC)2 (a) 1,3,5-benzenetricarboxylic acid (b) 34 Figure 3.10 Nitrogen adsorption/ desorption isotherm of the Cu3(BTC)2. Adsorption data is shown as closed circles and desorption data as vertical bars.11 Pore size distribution of the Cu3(BTC)2.12 TGA analysis of the Cu3(BTC)2 35 Figure 3.13 SEM micrograph of the Cu3(BTC)2.14 TEM micrograph of the Cu3(BTC)2.15 Effect of catalyst loading on reaction conversion (a) and selectivity (b) 41 Figure 3.16 Effect of reagent ratio on reaction conversion (a) and selectivity (b) 44 Figure 3.17 Leaching test with catalyst removal after first 40 minutes 45 Figure 3.18 Catalyst recycling studies.19 FT-IR spectra of the fresh (a) and reused (b) Cu2(BDC)2(BPY) catalyst.20 X-ray powder diffractograms of the fresh (a) and reused (b) Cu2(BDC)2(BPY) 51 Figure 3.21 Impact of the content of salt KBr on conversion 52 Figure 3.22 Impact of reagent molar ratio on conversion 53 Figure 3.23 Impact of the catalyst concentration on conversion 56 Figure 3.24 Leaching test with catalyst removal after 2 hours 57 Figure 3.25 Catalyst recycling studies 58 Figure 3.26 FT-IR spectra of the fresh Cu3(BTC)2 (a) and first reused (b) 58 Figure 3.27 PXRD spectra of the fresh Cu3(BTC)2 (a) and first reused (b) viii LIST OF TABLES Page Content 14 Table 1.1 Knoevenagel condensation reaction of benzlaldehyde with substrates, catalyzed by [Cd(4-BTAPA)2(NO3)2].1 List of common chemicals for experience 37 Table 3.1 Optimization of reaction conditions with respect to solvent and base 39 Table 3.2 Effect of oxidant 40 Table 3.3 Effect of other components in air to reaction efficiency 43 Table 3.4 Reactivity of other catalysts 47 Table 3.5 Comparative summary: Role of Bipyridine ligand 48 Table 3.6 Reactions scope with respect to coupling partners 54 Table 3.7 Optimization of reaction conditions with respect to solvent 59 Table 3.8 Reactivity of other catalysts 60 Table 3.9 Reactions scope with respect to coupling partners ix LIST OF SCHEMES Page Content 12 Scheme 1.1 Cyanosilylation of benzaldehyde.2 Isomerization of a-pineneoxide to campholenic aldehyde 14 Scheme 1.3 Proposed mechanism for the formation of the epoxide using [Cu(H2BTEC)(BPY)] as heterogeneous catalyst 17 Scheme 1.4 Copper-catalyzed pathways for ynamine synthesis 18 Scheme 1.5 Procedures and issues summary forming C-N bond in comparison 19 Scheme 1.6 Proposed mechanism for copper-catalyzed oxidative coupling terminal alkyne and nitrogen nucleophiles 20 Scheme 1.7 Traditional strategy via many protocols between nucleophilic enolate and electrophilic amine 20 Scheme 1.8 Procedures and issues summary forming C-N bond in comparison 21 Scheme 1.9 Proposed mechanism for Cu(II)-Catalyzed Carbonyl−Amine Coupling x Chapter 1 Literature Review CHAPTER 1: LITERATURE REVIEW 1.1 METAL – ORGANIC FRAMEWORKS 1.1 General background Over the several decades, the study of porous solid materials has been arousing great attention from researches of various fields, including chemistry, physics and material science.1 From the first ideal about coordination network having a chemical formula of Ni(CN)2(NH3).C6H6 discovered by Hofmann and Küspert in 1897,2 the porous structures have illustrated with a vast number of applications in various fields such as adsorption, separation and purification as well as catalysis.3 Because of numerous features concerning about high stability and porosity, the exploration of advanced porous materials for such applications is therefore an interesting subject of scientific research. Metal – Organic Frameworks (MOFs) emerged as a new class of porous solid materials, as well as, have unprecedentedly evolved into a potential research field.4,5 Although the first reports on MOFs began from the late 1950s,6 Robson and co-workers,7 followed by Kitagawa et al.8 also discovered many innovative structures, there was no evidence that both official definitions and considerable characteristics were indicated. At the beginning 1990s, Yaghi and co-workers 9, and then Ferey et al.10 much contributed toward boost in applicable extent.
Thus, new terms of Materials Institute Lavoisier (MILs), Secondary Building Units (SBUs), Meso–Porous Metal–Organic Framework (meso – MOF) and Pore size were integrally described. 11 Moreover, several MOFs are nowadays industrially prepared and marked by BASF, such as ZIF-9 (Zeolite Imidazolate Frameworks, BASOLITETM Z2100) and Cu3(BTC)2 (HKUST-1, MOF-199, BASOLITETM C300). Some also commercially available through Aldrich.12 In addition, reticular chemistry forms and predetermines thousands of structure in proportion to topology in which unit is repeated and held together by strong bonds.13 This is also one of the most highlighting and advanced features in comparison with traditional materials. THESIS Page | 1 Chapter 1 Literature Review 1.