VIETNAM NATIONAL UNIVERSITY HOCHIMINH CITY HCM City University of Technology MINH-DUNG TRAN EFFICIENT AND REUSABLE Ni-BASED-METAL ORGANIC FRAMEWORK CATALYZED CARBOXYLATION OF HALIDES WITH CO2 Chuyên ngành: Kỹ thuật Hóa học Mã ngành: 60 52 03 01 Ho Chi Minh City, July , 2016 CÔNG TRÌNH ĐƯỢC HOÀN THÀNH TẠI TRƯỜNG ĐẠI HỌC BÁCH KHOA –ĐHQG -HCM Cán bộ hướng dẫn khoa học :. (Ghi rõ họ, tên, học hàm, học vị và chữ ký) Cán bộ chấm nhận xét 1 :. (Ghi rõ họ, tên, học hàm, học vị và chữ ký) Cán bộ chấm nhận xét 2 :. (Ghi rõ họ, tên, học hàm, học vị và chữ ký) Luận văn thạc sĩ được bảo vệ tại Trường Đại học Bách Khoa, ĐHQG Tp.
Thành phần Hội đồng đánh giá luận văn thạc sĩ gồm: (Ghi rõ họ, tên, học hàm, học vị của Hội đồng chấm bảo vệ luận văn thạc sĩ) 1. Xác nhận của Chủ tịch Hội đồng đánh giá LV và Trưởng Khoa quản lý chuyên ngành sau khi luận văn đã được sửa chữa (nếu có). CHỦ TỊCH HỘI ĐỒNG TRƯỞNG KHOA………… 3 ĐẠI HỌC QUỐC GIA TP.HCM CỘNG HÒA XÃ HỘI CHỦ NGHĨA VIỆT NAM TRƯỜNG ĐẠI HỌC BÁCH KHOA Độc lập - Tự do - Hạnh phúc NHIỆM VỤ LUẬN VĂN THẠC SĨ Họ tên học viên: Trần Minh Dũng MSHV: 13051165 Ngày, tháng, năm sinh: 18-11-1991 Nơi sinh: Tây Ninh Chuyên ngành: Kỹ Thuật Hóa Học Mã số : 60. TÊN ĐỀ TÀI: Efficient and reusable Ni-based-metal organic framework catalyzed carboxylation of halides with CO2 II.
NHIỆM VỤ VÀ NỘI DUNG: • Tổng hợp và khảo sát cấu trúc vật liệu MOF Ni2(BDC)2(DABCO) • Khảo sát tối ưu phản ứng carboxylation benzyl bromide III. NGÀY GIAO NHIỆM VỤ : (Ghi theo trong QĐ giao đề tài): 19/01/2015 IV. NGÀY HOÀN THÀNH NHIỆM VỤ: (Ghi theo trong QĐ giao đề tài): 17/06/2016 V. CÁN BỘ HƯỚNG DẪN (Ghi rõ học hàm, học vị, họ, tên) : TS.
Trương Vũ Thanh GS. Phan Thanh Sơn Nam Tp. CÁN BỘ HƯỚNG DẪN CHỦ NHIỆM BỘ MÔN ĐÀO TẠO (Họ tên và chữ ký) (Họ tên và chữ ký) TRƯỞNG KHOA….……… (Họ tên và chữ ký) 2 Acknowledgement A completed study would not be done without any assistance. Therefore, I conducted this research gratefully gives acknowledgement to their support and motivation during the time of doing this research as a requirement of completing Master of Science Thesis.
First of all, I would like to express my endless thanks and gratefulness to my supervisor Dr. Truong Vu Thanh, Prof. Phan Thanh Son Nam and Tran Duc Thien. Their kindly support and continuous advice went through the process of completion of my thesis.
Their encouragement and comments had significantly enriched and improved my work. Without their motivation and instructions, the thesis would have been impossible to be done effectively: So far, I would like to thanks to groups who took charge in the process of data collection and data entry for doing this research as a part of the project.I would like to state my thanks to Bach Khoa University where supported financial for the project and provided me scholarship to pursuing and completing my degree.My special thanks approve to my parents for their endless love, care and have most assistances and motivation me for the whole of my life. As last, my deeply thanks come to all my friends during time I study in Bach Khoa University. Ho Chi Minh City, July , 2016 Trần Minh Dũng 4 ABSTRACT The utilization of linker Benzen-1,4-dicarboxylic acid (H2BDC) and ligand 1,4- diazabicyclo(2.2) octane (DABCO) for the synthesis of Ni2(BDC)2(DABCO) was implemented by solvothermal method.
The structure of this materials were characterized by 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 Ni2(BDC)2(DABCO) was used as heterogeneous catalysts for the direct carboxylation of benzyl bromide with CO2. Several essential factors including solvent, temperature, catalyst amount, type of catalysts and the amount of reductant were investigated. In leaching test, the catalyst was facilely separated from the reaction by centrifugation.
The catalyst recyclability was also specifically examined and the reaction could be reused several times without a significant degradation in catalytic activity. The products were confirmed by 1 H NMR and 13C NMR. To the best of our knowledge, there are no previous reports on carboxylation of halides using CO2 under MOFs catalysis. 5 LỜI CAM ĐOAN Tôi xin cam đoan rằng: Số liệu trong luận văn hoàn toàn do tôi thực hiện và chưa từng được sử dụng trong các bài báo, công trình nào khác.
Mọi sự giúp đỡ cho việc thực hiện luận văn này đã được cảm ơn và thông tin trích dẫn đều có nguồn gốc rõ ràng. Tác giả luận văn DECLARATION I assure that: The data in thesis completed by myseft and have not been used in the article or other works. All assistance for the implementation of this thesis was to thank and the information was used which clear origins. Author essay 6 LIST OF ABBREVIATIONS DMF: N,N-Dimethylformamide DMA: Dimethylacetamide GC: Gas chromatography ICP: Inductively coupled plasma NNP: N-Methyl-2-pyrrolidone NMR: Nuclear magnetic resonance XRPD: X-ray Powder Diffraction H2DBC: Bezene-1,4-dicarboxylic acid DABCO: 1,4-diazabicyclo(2.2) octane SEM: Scanning electron microscopy TEM: Transmission electron microscopy TGA: Thermogravimetric analysis ICP: Inductively coupled plasma EtOAc: Etyl acetat 7 List of Tables Table 2.1: List of chemicals needed for synthesizing Ni2(BDC)2(DABCO) .2 List of purification chemical .3 The different amount of phenylacetic acid used for the standard line graph.1 The effect of several type catalyst on reaction yield.2 The effect of the amount MgCl2 on yield reaction .3 The effect of different solvents on reaction conversion and yield.
54 8 List of Schemes Sheme 1.1: Synthesis of phenylacetic acids via Willgerodt-Kindler reaction [5] .2: The synthesis of phenylacetic acid in the carbonylation reaction [6] .3: The synthesis of phenylacetic acids under rhodium-catalyzed carbonylation conditions [7].4: Ni-Catalyzed Carboxylation of Alkyl Bromides [8] .5: Ni-catalyzed reductive carboxylation of Allyl Esters with CO2 [9] .6: Ni-Catalyzed Carboxylation of C(sp2) − and C(sp3)−O Bonds with CO2 [10].7: Ni-Catalyzed Carboxylation of alkyl halides with CO2 [11]. Ni-MOF carboxylation of benzyl halides .9: The hydrogenation with catalytic nickel nanoparticles embedded in MOF- 1 [44].10: The hydrogenation with Nickel nanoparticles supported on MOF-5 [45].11:The arylation of aldehydes with arylboronic acids using Ni(HBTC)(BPY) catalyst [46].12: The cross-coupling reaction of phenylacetylene and phenylboronic acids using the Ni2(BDC)2(DABCO) as catalyst [50].13: The direct heterocycle C–H arylation reactions between azoles and arylboronic acids using Ni2(BDC)2(DABCO) as a catalyst [51].14 Nickel-catalyzed double carboxylation of various internal alkynes .15 Synthesis of phenylacetic acids .16 Carboxylation of secondary and tertiary alkyl halides .18 Optimization of the Reaction Conditions .19 Nickel-catalyzed carboxylation of vinyl chlorides .1 Ni-MOF carboxylation of benzyl bromide. 37 9 List of Figures Figure 1.1: Significance of Phenylacetic Acids [2] .2: Structure of Plavix (Clopidogrel).3: Number of publications on MOFs over the past decade .4: General structure of MOFs [13].5: Some different MOFs’ structures.6: Aromatic dicarboxylates varying in length used as linkers [13] .7: Possible applications of MOFs in various areas [13] .8: The ability of MOF adsorption as compared to the traditional adsorption [35].9 : Gravimetric uptake curves of CH4, CO2, H2 and N2 on SIFSIX-3-Zn MOF [37].10 Examples of chemical fixation of CO2 [52].11 Ni-Based MetalOrganic Frameworks Containing Paddle-Wheel Type Inorganic Building Units via High-Throughput Methods.1: Structure simulation of Ni2(BDC)2(DABCO) [57] .1 X-ray powder diffractograms of MOF Ni2(BDC)2(DABCO).2 FT-IR spectra of Ni2(BDC)2(DABCO) .3 SEM micrograph of Ni2(BDC)2(DABCO).4 TEM micrograph of the Ni2(BDC)2(DABCO).5 TGA of Ni2(BDC)2(DABCO).6 Nitrogen adsorption/desorption isotherm of the Ni2(BDC)2(DABCO).7 Pore size distribution of the Ni2(BDC)2(DABCO).8 The standard line graph of phenyacetic acid .9 The effect of room temperature on conversion and GC yield.10 The reaction rate at 40OC .11 The reaction at 60oC .12 The effect of catalyst loading on carboxylation reaction conversion and yield.13 The effect of the amount of reductant on the reaction conversion and yield .14 Leaching test indicated no contribution from homogeneous catalysis of active species leaching into reaction solution .15 Comparing reusability of catalyst .16 XRD of the resused Ni2(BDC)2(DABCO). 1 LIST OF ABBREVIATIONS.
6 CHAPTER 1: LITERATURE REVIEW.1 The Synthesis of Phenyacetic Acids.1 The importance of phenylacetic acids .2 Conventional synthesis of phenylacetic acids .3 Metal- Organic Frameworks. Synthetic methods of MOFs .5 Application of MOFs .4 Potential of Nickel- MOFs in Catalysis.5 Nickel-catalyzed carboxylation of Aromatic Compounds with Carbon Dioxide .6 The Metal –Organic Framework Ni2(BDC)2(DABCO) .1 The Metal-Organic Framework Ni2(BDC)2(DABCO) .1 Materials and instrumentation .2 Synthesis of Ni2(BDC)2(DABCO) .2 The Direct Carboxylation of Akyl Halide with CO2 .1 Materials and instrumentation .3 Leaching test and the reusability of catalyst:. 39 CHAPTER III: RESULTS AND DISCUSSION .1 Characterization of Ni2(BDC)2(DABCO) .1 XRD result of Ni2(BDC)2(DABCO) .2 FT-IR results of Ni2(BDC)2(DABCO) .3 SEM and TEM results of Ni2(BDC)2(DABCO) .4 TGA results of Ni2(BDC)2(DABCO) .5 Nitrogen physisorption measurements of Ni2(BDC)2(DABCO).6 ICP result of Ni2(BDC)2(DABCO).2 The Carboxylation of Benzylbromide with CO2 .1 The standard line graph of phenyacetic acid .2 The influence of temperature.3 The influence of catalyst loading .4 The influence of several kind of catalyst .5 The influence of the amount of reductant .6 The influence of the amount of additive material .7 The influence solvent .8 The leaching test study .9 The catalyst recycling. 56 CHAPTER IV:CONCLUSION.
64 13 CHAPTER 1: LITERATURE REVIEW 1.1 The Synthesis of Phenyacetic Acids 1.1 The importance of phenylacetic acids Phenylacetic acid is one of the most important organic chemical materials, widely used in the field of medicine, pesticide, aromatizer and so on. In more details, the interest in these compounds arises from the fact that a large number of complex molecules such as vancomycin, carbenicillin, ibuprofen, diclofenac, lyrica or lipitor, among many other displayed significant biological activities [1]. Especially, lipitor is ranked the first in the top 200 pharmaceutical Products by Worldwide Sales in 2009 [2].1: Significance of Phenylacetic Acids [2] Besides, phenylacetic acids are used as intermediates in synthesis of some outstanding drugs, for instance, Plavix is a potent anti- platelet drug launched in 1997 by Sanofi- Synthelabo [3,4].2: Structure of Plavix (Clopidogrel) 1.2 Conventional synthesis of phenylacetic acids According to M. Mujahid Alam and his partners’ study, phenylacetic acids were synthesized by Willgerodt-Kindler reaction under PTC (Phase Transfer Catalytic) condition [5].1: Synthesis of phenylacetic acids via Willgerodt-Kindler reaction [5] Other studies concentrated on the carbonylation of alkyl halides.
For example, ZuminQiu and co-workers set a carbonylation reaction under milder condition.2: The synthesis of phenylacetic acid in the carbonylation reaction [6] Furthermore, the direct formation of carboxylic acids under a rhodium catalyst was studied in Department of medicinal chemistry in Canada by Andre´ Giroux and co-workers [7].3: The synthesis of phenylacetic acids under rhodium-catalyzed carbonylation conditions [7]. However, the studies above still presented various limitations such as long reaction times, hazardous reaction conditions and difficulty in product isolation and purification. Therefore, there was an intense demand to develop a new and efficient method for the synthesis of biologically active phenylacetic acids under mild and ecofriendly reaction conditions. As a result, a series of studies of carboxylation using CO2 as an inexpensive and environmental-friendly chemical reagent has published by Ruben Martin .4: Ni-Catalyzed Carboxylation of Alkyl Bromides [8] Scheme 1.5: Ni-catalyzed reductive carboxylation of Allyl Esters with CO2 [9] Scheme 1.6: Ni-Catalyzed Carboxylation of C(sp2) − and C(sp3)−O Bonds with CO2 [10] 1.2 Our approach The carboxylation of alkyl halides with CO2 under homogeneous catalyst In 2003, Ruben Martin and his colleagues showed their experiments on Ni- catalyzed direct carboxylation of benzyl halides with CO2.
This research illustrated the development of a user-friendly and operationally simple catalytic protocol without sensitive and expensive metal complexes [11].