Luận án TS: Nanoparticles CuFe2O4, Fe2O3 xúc tác ghép C-N (Nguyễn Thị Kim Oanh)

VIETNAM NATIONAL UNIVERSITY – HO CHI MINH CITY HO CHI MINH CITY UNIVERSITY OF TECHNOLOGY NGUYEN THI KIM OANH CuFe2O4 AND Fe2O3 SUPERPARAMAGNETIC NANOPARTICLES AS CATALYSTS FOR SOME C-N CROSS- COUPLING REACTIONS PhD THESIS HO CHI MINH CITY - 2021 VIETNAM NATIONAL UNIVERSITY – HO CHI MINH CITY HO CHI MINH CITY UNIVERSITY OF TECHNOLOGY NGUYEN THI KIM OANH CuFe2O4 AND Fe2O3 SUPERPARAMAGNETIC NANOPARTICLES AS CATCALYSTS FOR SOME C-N CROSS-COUPLING REACTIONS Major: Chemical Engineering Code: 9520301 Independent examiner: Assoc. Hoang Thi Kim Dung Independent examiner: Assoc. Tran Hoang Phuong Examiner: Assoc. Tran Ngoc Quyen Examiner: Assoc.

Nguyen Phuong Tung Examiner: Assoc. Nguyen Quang Long Advisor: Prof. Phan Thanh Son Nam PLEDGE I assure that this is my own research. The research results and conclusions in this thesis are honest, and do not reproduce from any source and in any form.

References to sources (if any) have been cited and the source of reference is properly regulated. PhD Candidate Signature Nguyen Thi Kim Oanh i ABSTRACT Superparamagnetic nanoparticles (NPs) have attracted attention as catalyst supports, because of their response to an applied magnetic field. Magnetic separation has emerged as a robust, highly efficient and rapid catalyst separation tool with many advantages compared to other catalyst isolation techniques such as liquid-liquid extraction, chromatography, filtration or centrifugation. The superparamagnetic nanoparticle materials had highly catalytic activity in many organic reactions because they contain open-type centers.

Specifically, two superparamagnetic nanoparticle materials include CuFe2O4 and Fe2O3 were synthesized by simple methods, having many outstanding advantages suitable for catalytic applications. Moreover, these superparamagnetic nanoparticle materials were commercial materials and could be obtained at low cost. Two materials, including CuFe2O4 and Fe2O3 were used as heterogeneous catalysts for C–N cross-coupling reactions to synthesize compounds such as triphenylamines, 3- phenylquinoxalin-2(1H)-one and phenyl(2-phenylimidazo[1,2-a]pyrimidin-3- yl)methanone substances. The result of the reaction between benzoxazole: iodobenzene (1: 3) produced triphenylamine with a conversion rate of nearly 95% after 2 hours at 140 C in diethylene glycol solvent, 2.5 equivalent Cs2CO3 using 10 mol% catalyst of CuFe2O4 in the argon gas.

Fe2O3 material was used as a catalyst for the 3- phenylquinoxalin-2(1H)-one compound from 2-oxo-2-phenylacetic acid (0.25 mmol) and benzene-1,2-diamine (0. The results achieved a conversion of about 82% after 24 hours at 100 °C in a mixture of solvent C6H5Cl/H2O (1.5) (v / v), using 10 mol% catalyst of Fe2O3. In addition, CuFe2O4 was also used for phenyl(2- phenylimidazo[1,2-a] pyrimidin-3-yl)methanone from trans-chalcone (0.3 mmol) and 2-aminopyrimidine (0. The results achieved a conversion of about 84% after 7 hours at 140 °C in 1,4-dioxane solvent, two equivalents of iodine using 10 mol% catalyst of CuFe2O4 in oxygen atmosphere.

These catalysts provided high efficiency and selectivity. In addition, the function of the catalysts has also been demonstrated. The superparamagnetic nanoparticle catalysts could be recovered and reused many iii times without any significant reduction in catalytic activity. To our knowledge, these transformations using superparamagnetic nanoparticle catalysts have not been studied before.

iv TÓM TẮT LUẬN ÁN Vật liệu nano siêu thuận từ đã thu hút sự chú ý của các nhà khoa học với vai trò là chất xúc tác hỗ trợ. Sự tách từ tính ngày càng được chú ý như một phương pháp tách xúc tác, hiệu quả cao và nhanh chóng với nhiều ưu điểm hơn so với việc phân lập xúc tác bằng cách truyền thống như chiết lỏng-lỏng, sắc ký, lọc hoặc ly tâm. Vật liệu này thể hiện hoạt tính xúc tác cao trong nhiều phản ứng hữu cơ vì chúng chứa các tâm kim loại mở. Đặc biệt hai vật liệu gồm CuFe2O4 và Fe2O3 được tổng hợp bằng phương pháp đơn giản, có nhiều ưu điểm vượt trội phù hợp trong ứng dụng xúc tác.

Hơn nữa, các vật liệu nano siêu thuận từ này đã được thương mại hóa và giá thành tương đối thấp. Cả hai vật liệu CuFe2O4 và Fe2O3 được sử dụng làm xúc tác dị thể cho phản ứng ghép đôi C–N trong quá trình tổng hợp các hợp chất hữu cơ như triphenylamine, 3- phenylquinoxalin-2(1h)-one và phenyl(2-phenylimidazo[1,2-a]pyrimidin-3- yl)methanone. Kết quả thực hiện phản ứng giữa benzoxazole : iodobenzene (1 : 3) tạo ra triphenylamine đạt hiệu suất gần 95% sau 2 giờ ở 140 C trong dung môi diethylene glycol, 2.5 đương lượng Cs2CO3 sử dụng 10 mol% CuFe2O4 trong môi trường khí argon. Vật liệu Fe2O3 được sử dụng làm xúc tác cho phản ứng tổng hợp 3- phenylquinoxalin-2(1h)-one từ 2-oxo-2-phenylacetic acid (0.25 mmol) và benzene- 1,2-diamine (0.

Kết quả thực hiện phản ứng đạt hiệu suất khoảng 82% sau 24 giờ ở 100 C trong hỗn hợp dung môi C6H5Cl/H2O (1.5) (v/v), sử dụng 10 mol% xúc tác Fe2O3. Ngoài ra, vật liệu CuFe2O4 cũng được sử dụng cho phản ứng tổng hợp phenyl(2-phenylimidazo[1,2-a]pyrimidin-3-yl)methanone từ trans-chalcone (0.3 mmol) và 2-aminopyrimidine (0. Kết quả thực hiện phản ứng đạt hiệu suất khoảng 84% sau 7 giờ ở 140 C trong dung môi 1,4-dioxane, hai đương lượng iodine sử dụng 10 mol% xúc tác CuFe2O4 trong môi trường khí oxi. Các xúc tác này cho hiệu suất và độ chọn lọc cao.

Ngoài ra, chức năng của các xúc tác cũng đã được chứng minh. Các xúc tác nano siêu thuận từ có thể thu hồi và tái sử dụng nhiều lần mà hoạt tính xúc tác giảm không đáng kể. Theo hiểu biết của chúng tôi, những phản ứng trên sử dụng các xúc tác CuFe2O4 và Fe2O3 chưa từng được nghiên cứu trước đây. iii ACKNOWLEDGEMENTS I would like to express our special appreciation and deep regards to my mentor, Prof.

Phan Thanh Son Nam, who guided me throughout the process of implementing this thesis. I have learned from him a lot of professional knowledge and through his guidance I have also learned how to approach and solve other scientific problems. I feel so precious when I have the opportunity to receive his guidance. Next, I would like to offer our sincere thank you to Assoc.

Pham Thanh Quan, Dr. Phan Thi Hoang Anh, Dr. Nguyen Thanh Tung and the staff of lecturers of Organic Engineering, Faculty of Chemical Engineering, Ho Chi Minh City University of Technology have made sincere suggestions and created many favorable conditions for me to complete this thesis. Last time I had the opportunity to learn and exchange professional knowledge with the staffs in Manar laboratory (MSc.

Nguyen Kim Chung, MSc. Nguyen Thai Anh, Đang Van Ha, Ha Quang Hiep, Pham Huy Hoang). Master's students (Ha Trong Pha, Phan Thi Phuong) and some students (Truong Kim Nhu, Phan Le Tuan Anh, Huynh Dang Khoa) helped me a lot during my time at the lab. Last but not least, I would like to express my special thanks to my families.

Words cannot express how grateful I are to my parents for all of the sacrifices that they have made on my behalf. Their constant encouragement is my most important strength to finish this research work. iv TABLE OF CONTENT LIST OF FIGURES. ix LIST OF SCHEMES .xii LIST OF TABLES.

xviii CHAPTER 1 OVERVIEW. Green and sustainable catalysis. Homogeneous and heterogeneous catalysis. Nanocatalyst and magnetic nanoparticles.

Ferrite nanoparticles and copper ferrite nanoparticles. Ferrite nanoparticles catalyst. Copper ferrite nanoparticles catalyst. Application of superparamagnetic nanoparticles in catalyst.

C-N cross-coupling reactions. C-N cross-coupling reaction synthesizes triphenylamines. C–N cross-coupling reactions synthesize Quinoxalin-2-ones. C-N cross-coupling reactions synthesize aroylimidazo[1,2- a]pyrimidines/aroylimidazo[1,2-a]pyridines.

Necessity – Novelty of thesis. The necessity of the thesis. The novelty of the thesis. Aim and objective.

36 CHAPTER 2 RESEARCH METHODS. Materials and instrumentation. Formulate for calculating yield and isolated yield. The catalytic activity investigation of nano CuFe2O4 for synthesis reaction of triphenylamine (TPAs).

The catalytic activity investigation of nanostructured Fe2O3 material for synthesis reaction of quinoxalin-2-ones. The catalytic activity investigation of nanostructured CuFe2O4 material for synthesis reaction of phenyl(2-phenylimidazo[1,2-a]pyrimidin-3-yl)methanone. 41 CHAPTER 3 RESULTS AND DISCUSSION. Characteristic structure of materials.

Nanostructured CuFe2O4 material. Nanostructured Fe2O3 material. The catalytic activity investigation for C–N cross-coupling reactions. The catalytic activity investigation of CuFe2O4 for synthesis reaction of triphenylamine (TPAs).

Effect of different catalysts on the conversion reaction. Effect of different solvents on reaction conversion. Effect of different bases and base amounts on reaction conversion. Effects of reactant concentrations and reactants molar ratio on reaction conversion 53 3.

Effect of catalyst concentrations on reaction conversion. Effect of homogenous catalysts and heterogeneous catalysts on reaction conversion 58 3. The mechanism proposal of reaction. Catalyst recycling and reusing.

Effect of TPAs derivatives on reaction conversion. The catalytic activity investigation of Fe2O3 for synthesis reaction of quinoxalin-2-ones. Effect of different temperatures on the conversion reaction. Effect of reactant molar ratios on the conversion reaction.

Effect of solvent volume ratios on the conversion reaction. Effect of catalyst amount on the conversion reaction. Effect of solvent types on the conversion reaction. Effect of different catalysts on the conversion reaction.

The mechanism proposal of reaction. Effect of catalyst loading on reaction conversion. Catalyst recycling and reusing. Effect of quinoxalin-2(1H)-one derivative on reaction conversion.

The catalytic activity investigation of the nano CuFe2O4 for synthesis reaction of phenyl(2-phenylimidazo[1,2-a]pyrimidin-3-yl)methanone. Effect of different temperatures on the conversion reaction. Effect of different catalytic amounts on reaction conversion. Effect of different ratios of the reactant on reaction conversion.

Effect of iodine amount on reaction conversion. Effect of solvent types on reaction conversion. The effect of homogeneous and heterogeneous catalysts on reaction conversion 100 3. The mechanism proposal of reaction.

Effect of catalyst loading on reaction conversion. Catalyst recycling and reusing. Effect of aroylimidazo[1,2-a]pyrimidines and aroylimidazo[1,2- a]pyridines derivatives on reaction conversion. Contribution of the thesis.

120 LIST OF PUBLICATIONS. 142 vii LIST OF FIGURES Figure 1.1: Schematic illustrating the arrangements of magnetic dipoles for five different types of materials in the absence or presence of an external magnetic field (H) [29].2: Schematic illustrating the dependence of magnetic coercivity on particle size. In the single-domain regime, the coercivity can follow either the solid curve for noninteracting particles or the dashed line for particles that have coupling between them. The coercivity falls to zero for superparamagnetic colloidal particles [29].3: Crystallographic unit cell of different iron oxides: (a) α-Fe2O3, (b) γ-Fe2O3, (c) Fe3O4 and (d) FeO [36] .4: Magnetic separation of copper ferrite NPs [49].5: Structure of CuFe2O4 [67] .6: Structure of TPAs .7: Structure of Quinoxalin-2(1H)-ones .8: Structures of some imidazo[1,2-a]pyridine drugs and drug candidates [142] .9: Biologically active 3-aroylimidazo[1,2-a]pyridine derivatives [142] .1: Copper-oxide-based nano-catalyst dispersed in DMSO reactive solvent (left) and after being applied to an external magnetic field (right) .2: Screening solid catalysts for the ring-opening reaction .3: Yields of 2-(diphenylamino)phenol versus solvents .4: Yields of 2-(diphenylamino)phenol versus bases .5: Yields of 2-(diphenylamino)phenol versus base amount .6: Yields of 2-(diphenylamino)phenol versus benzoxazole concentration .7: Yields of 2-(diphenylamino)phenol versus reactant molar ratios .8: Yields of 2-(diphenylamino)phenol versus catalyst concentration .9: Yields of 2-(diphenylamino)phenol versus temperatures .10: Leaching assessment verified that 2-(diphenylamino)phenol was not generated in the absence of CuFe2O4 superparamagnetic nanoparticles .11: Yields of 2-(diphenylamino)phenol using the CuFe2O4 nanocatalyst versus some homogeneous catalysts .12: Yields of 2-(diphenylamino)phenol versus heterogeneous catalyst .13: Catalyst reutilizing investigation .14: XRD results of the fresh (a) and reutilized (b) catalyst .15: TEM micrograph of the recovery catalyst .16: Yield of 3-phenylquinoxalin-2(1H)-one versus temperature.17: Yield of 3-phenylquinoxalin-2(1H)-one versus 2-oxo-2-phenylacetic acid:benzene-1,2-diamine molar ratio.18: Yield of 3-phenylquinoxalin-2(1H)-one versus MeCN: H2O volume ratio.19: Yield of 3-phenylquinoxalin-2(1H)-one versus catalyst amount.20: Yield of 3-phenylquinoxalin-2(1H)-one versus the solvent system.21: Yield (a) and selectivity (b) of 3-phenylquinoxalin-2(1H)-one versus heterogeneous catalysts.22: Yield (a) and selectivity (b) of 3-phenylquinoxalin-2(1H)-one using the Fe2O3 nanocatalyst versus homogeneous catalysts.23: Leaching experiment verified that the transformation proceeded under heterogeneous catalysis.24: Catalyst reutilizing studies: Yield (a), and selectivity to 3- phenylquinoxalin-2(1H)-one (b).25: XRD analysis of the new (a) and reutilized (b) catalyst.