tóm tắt luận án cu based organic frameworks as catalysts for c c and c n coupling reactions (tiếng anh)

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 PhD THESIS SUMMARY HO CHI MINH CITY 2015 The thesis was completed in University of Technology –VNU-HCM Advisor 1: Prof. Dr. Phan Thanh Son Nam Advisor 2: Dr. Le Thanh Dung Independent examiner 1: Prof. Dr. Dinh Thi Ngo Independent examiner 2: Assoc. Prof. Dr. Nguyen Thi Phuong Phong Examiner 1: Assoc. Prof. Dr. Nguyen Cuu Khoa Examiner 2: Assoc. Prof. Dr. Nguyen Thai Hoang Examiner 3: Assoc. Prof. Dr. Le Thi Hong Nhan The thesis will be defended before thesis committee at On……………………………………………………………………………… The thesis information can be looked at following libraries: - General Science Library Tp. HCM - Library of University of Technology – VNU-HCM Abstract Four highly porous Copper-based organic frameworks (Cu-MOFs) such as Cu 3 (BTC) 2 , Cu 2 (BDC) 2 (DABCO), Cu 2 (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 (H 2 -TPR) and nitrogen physisorption measurements. Three Cu-MOFs including Cu 3 (BTC) 2 , Cu 2 (BDC) 2 (DABCO), Cu 2 (BPDC) 2 (BPY) were used as heterogeneous catalysts for direct CC coupling reactions to synthesize propargylamines. Cu(BDC) was employed as heterogeneous catalyst for CN 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. INTRODUCTION Homogeneous transition metals are often employed as catalysts to promote the transformation of an organic compound in the liquid phase. However, difficulties in removing catalyst impurities in the final products narrow the application of homogeneous catalytic systems, especially in pharmaceutical industry. Metal-organic frameworks (MOFs) have recently attracted significant attention with advantages in replacing homogeneous catalysts in chemical process. Propargylamines and quinoxalines have emerged as important intermediates in the synthesis of numerous nitrogen-containing biologically active compounds as well as a variety of functional organic materials. Many transition-metal catalytic systems, both in homogeneous and heterogeneous catalysis, were applied for the preparation of propargylmines and quinoxalines via the C−C and C−N coupling reations. However, many of those processes suffered from one or more limitations such as harsh reaction conditions, low product yields, tedious work-up procedures, and the use of toxic metal salts as catalysts. Consequently, study for the high-effective, sustainable synthetic routes of proparylamines and quinoxalines is an unquestionable trend in near future. Among several popular MOFs, copper-based organic frameworks (Cu- MOFs) previously exhibited high activity in various organic reactions due to their unsaturated open copper metal sites. Especially, the Cu-MOFs including Cu 3 (BTC) 2 , Cu(BDC), Cu 2 (BDC) 2 (DABCO) and Cu 2 (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 Cu-MOFs have surface areas higher than 1000 m 2 /g (except for Cu(BDC)) and thermal stability of up to 300 °C or higher. Moreover, the largest pore apertures of Cu 2 (BDC) 2 (DABCO), Cu 3 (BTC) 2 and Cu 2 (BPDC) 2 (BPY) are in the range of 7.5 – 9.0 Å which can allow average size substrates to enter the pores and reach catalytic sites. However, to the best of our knowledge, the direct C–C and C–N coupling reactions for the synthesis of proparylamines and quinoxalines using these Cu- MOFs were not previously mentioned in the literature. The first purpose of this thesis is to synthesize Cu-MOFs including Cu 3 (BTC) 2 , Cu(BDC), Cu 2 (BDC) 2 (DABCO) and Cu 2 (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. CHAPTER 1 LITERATURE REVIEW: Cu 3 (BTC) 2 , Cu 2 (BDC) 2 (DABCO), Cu 2 (BPDC) 2 (BPY), Cu(BDC) AND C–C, C–N COUPLING REACTIONS 1.1 Introduction to metal-organic frameworks  In comparison with other porous materials, MOFs possess unique structures, in which the metal ions combine with organic linkers to form secondary building units (SBUs), which dictate the final topology of a whole framework. The combination of numerous kinds of linkers and metal ions can lead to considerable diversity of this material.  Many studies reported MOFs containing copper active sites as efficient heterogeneous catalysts.  Among organic linkers that are often used for Cu-MOFs synthesis, 1,4- benzenedicarboxylic acid (BDC), 1,3,5-benzenetricarboxylic acid (BTC) and 4,4’-biphenyldicarboxylic acid (BPDC) have advantages that they are commercial and relatively cheap. In another approach, MOFs can be constructed from mixed linkers to provide greater flexibility in terms of surface area, modifiable pore size and chemical environment. Linkers BDC and BPDC could be easily combined with pillar linkers such as 1,4-diazabicyclo [2.2.2]octane (DABCO) or 4,4’- bipyridine (BPY) to form rigid Cu-MOFs. Therefore, Cu-MOFs constructed from BDC, BTC or BPDC recently attracted great attention. 1.1 1.2 Cu 3 (BTC) 2 , Cu(BDC), Cu 2 (BDC) 2 (DABCO) and Cu 2 (BPDC) 2 (BPY)  Cu 3 (BTC) 2 , Cu(BDC), Cu 2 (BDC) 2 (DABCO) and Cu 2 (BPDC) 2 (BPY) constitute Cu-MOFs that contain common SBUs of two 5-coordinate copper cations bridged in a paddle wheel-type configuration (Fig. 1.4). Fig 1.4. Common coordination geometry of paddle wheel building units of Cu 3 (BTC) 2 , Cu 2 (BDC) 2 (DABCO), Cu 2 (BPDC) 2 (BPY), Cu(BDC) and their framework structures (L = Carboxylate linker, P = N-containing bidentate pillar linker and G = Guest molecule).  Cu 3 (BTC) 2 , Cu(BDC), Cu 2 (BDC) 2 (DABCO) and Cu 2 (BPDC) 2 (BPY) are synthesized by solvothermal methods. Their physicochemical properties are presented in Table 1.2: Table 1.2: Physicochemical properties of Cu 3 (BTC) 2 , Cu(BDC), Cu 2 (BDC) 2 (DABCO) and Cu 2 (BPDC) 2 (BPY) MOFs Decomposition temperature (°C) BET surface area (m 2 /g) Pore aperture (Å 2 ) Cu 3 (BTC) 2 300 1000-1450 8.0  9.0 Cu(BDC) 325 545-625 _ Cu 2 (BDC) 2 (DABCO) 300 1461 7.5  7.5 4.7  3.8 Cu 2 (BPDC) 2 (BPY) 320 1210 12.3  7.8 8.8  8.0  Cu 3 (BTC) 2 , Cu(BDC), Cu 2 (BDC) 2 (DABCO) and Cu 2 (BPDC) 2 (BPY) can be characterized by various techniques, such as single crystal X-ray diffraction (SC-XRD), powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), inductively coupled plasma mass spectrometry (ICP-MS), and gas physisorption measurement, etc. 1.3 C–C coupling reactions  Traditional routes to access propargylamines often suffer from disadvantages such as hard conditions, low yields, and limited reaction scopes.  Difficults in removing catalysts contaminated in final products narrow the application of homogeneous catalytic systems, especially in pharmaceutical industry.  Recently, the most attractive synthetic route is the use of Manich-type reaction, a three component procedure of terminal alkynes, formaldehyde, and secondary amines. However, the aldehyde-free, oxidative Manich reactions have not been previously reported under any catalysis. 1.4 C–N coupling reactions  Traditionally, quinoxalines have been prepared by the acid-catalyzed condensation of 1,2-aryldiamines with 1,2-diketone or 1,2-diketone alternatives, such as epoxides, α-bromoketones, and α-hydroxyketones.  Although the contamination of the desired products with transition metals or other solids would be minimized under heterogeneous catalysts conditions, developing an efficient heterogeneous catalyst system for the quinoxaline synthesis still remains to be explored. 1.2 1.5 Aim and objectives  Propargylamines and quinoxalines are frequently found as the versatile intermediates for the synthesis of many nitrogen-containing biologically active compounds.  Cu 3 (BTC) 2 , Cu 2 (BDC) 2 (DABCO), Cu 2 (BPDC) 2 (BPY) and Cu(BDC) have many advantages for suitable catalytic applications.  To the best of our knowledge, the direct C–C and C–N coupling reactions for synthesizing proparylamines and quinoxalines using these Cu-MOFs were not previously mentioned in the literature.  The main aim of this dissertation is using Cu 3 (BTC) 2 , Cu 2 (BDC) 2 (DABCO), Cu 2 (BPDC) 2 (BPY) and Cu(BDC) as catalysts for the synthesis of proparylamines and quinoxalines: i) Synthesis and characterization of the Cu-MOFs including Cu 3 (BTC) 2 , Cu 2 (BDC) 2 (DABCO), Cu 2 (BPDC) 2 (BPY) and Cu(BDC); ii)Catalytic studies of Cu 3 (BTC) 2 , Cu 2 (BDC) 2 (DABCO), Cu 2 (BPDC) 2 (BPY) on C–C coupling reactions between amine compounds and terminal alkynes, catalytic studies of Cu(BDC) on C–N coupling reaction between α-hydroxyacetophenone and o- phenylenediamine. CHAPTER 2 SYNTHESIS AND CHARACTERIZATION OF Cu 3 (BTC) 2 , Cu 2 (BDC) 2 (DABCO), Cu 2 (BPDC) 2 (BPY), Cu(BDC) 2.1 Introduction In this chapter, the synthesis, characterization methods, physicochemical properties of Cu 3 (BTC) 2 , Cu 2 (BDC) 2 (DABCO), Cu 2 (BPDC) 2 (BPY) and Cu(BDC) were studied. 2.2 Experimental  Cu 3 (BTC) 2 , Cu 2 (BDC) 2 (DABCO), Cu 2 (BPDC) 2 (BPY) and Cu(BDC) were synthesized by solvothermal methods.  They were charactized by different techniques such as PXRD, FT-IR, SEM, TEM, TGA, ICP-MS and nitrogen physisorption measurement. 2.3 Results and discussions 2.3.1 Synthesis and characterization of Cu 3 (BTC) 2  The synthesis yield was approximately 85% based on H 3 BTC.  The copper content in the Cu 3 (BTC) 2 was 29% (ICP-MS).  The BET surface areas of Cu 3 (BTC) 2 were achieved approximately 1799 m 2 /g, the Langmuir surface areas were achieved approximately 2007 m 2 /g.  The thermal stability of Cu 3 (BTC) 2 is over 300 o C (TGA).  The PXRD pattern of the synthesized Cu 3 (BTC) 2 was similar to the simulated pattern previously reported in the literature (Figure 2.2).  The SEM micrograph indicated Cu 3 (BTC) 2 exhibited a cubic octahedral morphology (Fig. 2.4). [...]... Conclusion The four Cu- MOFs such as Cu3 (BTC)2 , Cu2 (BDC)2 (DABCO), Cu2 (BPDC)2 (BPY) and Cu( BDC) were successfully synthesized and characterized by PXRD, FT-IR, TGA, H2 TPR, ICP-MS and nitrogen physisorption measurements CHAPTER 3 CATALYTIC STUDIES OF Cu3 (BTC)2 , Cu2 (BDC)2 (DABCO), Cu2 (BPDC)2 (BPY), Cu( BDC) ON C C AND C N COUPLING REACTIONS 3.1 Introduction  Cu3 (BTC)2 , Cu2 (BDC)2 (DABCO), Cu2 ... 95% was achieved with accepted NMR purity 3.4 Conclusion  Cu3 (BTC)2 , Cu2 (BDC)2 (DABCO), Cu2 (BDC)2 (BPY) were used as heterogeneous catalysts for direct C C coupling reactions to form propargylamines, Cu( BDC) was employed as heterogeneous catalyst for direct C N coupling reaction to get quinoxalines  The direct C C, C N coupling transformations of reaction 1, 2, 3 and 4 could only proceed in the... confirmed by 1 H NMR and 13 C NMR 3.3 Results and discussions 3.3.1 Catalytic studies of Cu3 (BTC)2 on C C coupling reaction (1) Scheme 3.3 The direct oxidative C- C coupling reaction between N, Ndimethylaniline and phenylacetylene using Cu3 (BTC)2 as catalyst  All optimized synthetic conditions of reaction 1 between N, Ndimethylaniline and phenylacetylene are summaried in Table 3.2 Reaction conditions Temperature... the Cu( BDC) was employed as a heterogeneous catalyst for the oxidative cyclization reaction between αhydroxyacetophenone and phenylenediamine derivatives (reaction 4)  Cu3 (BTC)2 , Cu2 (BDC)2 (DABCO), Cu2 (BPDC)2 (BPY) and Cu( BDC) showed high catalytic activities for those C C and C N coupling reactions and the optimal conditions of these reaction have been found  These Cu- MOFs can be reused and recycled... Experimental Catalytic studies of Cu3 (BTC)2 on C C coupling reaction from N, Ndimethylanilines and terminal alkynes (reaction 1); Catalytic studies of Cu2 (BDC)2 (DABCO) on C C coupling reaction from N- methylanilines and terminal alkynes (reaction 2); Catalytic studies of Cu2 (BPDC)2 (BPY) on C C coupling reaction from Tetrahydroisoquinoline, benzaldehydes and terminal alkynes (reaction 3); Catalytic studies... Cu- MOFs as catalysts for direct C C and C N coupling reactions to synthesize propargylamines and quinoxalines These compounds are found as the versatile intermediates for the synthesis of many nitrogen-containing biologically active compounds Herein, the following are the main research contributions of this thesis  Cu3 (BTC)2 , Cu2 (BDC)2 (DABCO), Cu2 (BPDC)2 (BPY) and Cu( BDC) were synthesized successfully... direct C C coupling reaction via C H functionalization between Nmethylaniline and phenylacetylene (reaction 2) Tert-butyl hydroperoxide also served as the methylating reagent in the transformation, and N- methyl -N- (3-phenylprop-2-ynyl)benzenamine but not N- (3-phenylprop-2-ynyl)benzenamine was produced as the principal product The direct C- C coupling reaction could proceed to 95 % conversion with a selectivity...  The Cu3 (BTC)2 was used as a heterogeneous catalyst for the direct oxidative C C coupling reaction via C H functionalization between N, N-dimethylanilines and terminal alkynes (reaction 1) The direct C C coupling transformation could proceed to 96 % conversion after 180 min in the presence of 5 mol% Cu3 (BTC)2 catalyst at 120 o C  The Cu2 (BDC)2 (DABCO) was used as a heterogeneous catalyst for the... Run 7 8 9 10 Figure 3.12 Catalytic recycling studies  Leaching test indicated no contribution from homogeneous catalysis of active species leaching into reaction solution (Fig 3.9)  The Cu3 (BTC)2 catalyst could be recovered and reused ten times in the direct C- C coupling reaction between N, N-dimethylaniline and phenylacetylene without a significant degradation in catalytic activity Indeed, a conversion... Thanh Dung, Dang Huynh Giao, Nguyen Tran Thanh Tai, Le Dang Phuong Thao, “New linkers containing alkyne and amine functionalities as precursors for the construction of new functionalized MOFs: synthesis and characterization”, Journal of Chemistry, 51 (2AB) (2013), 302-307 7 Le Thanh Dung, Dang Huynh Giao, Cao Tuyet Van, “Carboxylate ligands containing pyridinium groups- versitile linkers in construction . 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. Cu 2 (BPDC) 2 (BPY) were used as heterogeneous catalysts for direct CC coupling reactions to synthesize propargylamines. Cu(BDC) was employed as heterogeneous catalyst for CN coupling reaction to. Cu 2 (BDC) 2 (DABCO) and Cu 2 (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.