Cufe2o4 and fe2o3 superparamagnetic nanoparticles as catalysts for some c n crosscoupling reactions

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 CROSSCOUPLING 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 Prof Dr Hoang Thi Kim Dung Independent examiner: Assoc Prof Dr Tran Hoang Phuong Examiner: Assoc Prof Dr Tran Ngoc Quyen Examiner: Assoc Prof Dr Nguyen Phuong Tung Examiner: Assoc Prof Dr Nguyen Quang Long Advisor: Prof Dr Phan Thanh Son Nam PLEDGE I assure that this is my own research The research results and conclusions in this thesis are honest, and 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, 3phenylquinoxalin-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 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 3phenylquinoxalin-2(1H)-one compound from 2-oxo-2-phenylacetic acid (0.25 mmol) and benzene-1,2-diamine (0.375 mmol) The results achieved a conversion of about 82% after 24 hours at 100 °C in a mixture of solvent C6H5Cl/H2O (1.5 / 0.5) (v / v), using 10 mol% catalyst of Fe2O3 In addition, CuFe2O4 was also used for phenyl(2phenylimidazo[1,2-a] pyrimidin-3-yl)methanone from trans-chalcone (0.3 mmol) and 2-aminopyrimidine (0.2 mmol) The results achieved a conversion of about 84% after 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 T T LU N ÁN V t li u nano siêu thu n t thu hút s ý c a nhà khoa h c v i vai trò ch t xúc tác h tr S tách t tính ngày đ c ý nh m t ph ng pháp tách xúc tác, hi u qu cao nhanh chóng v i nhi u u m h n so v i vi c phân l p xúc tác b ng cách truy n th ng nh chi t l ng-l ng, s c ký, l c ho c ly tâm V t li u th hi n ho t tính xúc tác cao nhi u ph n ng h u c chúng ch a tâm kim lo i m c bi t hai v t li u g m CuFe2O4 Fe2O3 đ đ n gi n, có nhi u u m v c t ng h p b ng ph ng pháp t tr i phù h p ng d ng xúc tác H n n a, v t li u nano siêu thu n t đ c th ng m i hóa giá thành t C hai v t li u CuFe2O4 Fe2O3 đ c s d ng làm xúc tác d th cho ph n ng ghép đôi C–N trình t ng h p h p ch t h u c phenylquinoxalin-2(1h)-one nh ng đ i th p triphenylamine, 3- phenyl(2-phenylimidazo[1,2-a]pyrimidin-3- yl)methanone K t qu th c hi n ph n ng gi a benzoxazole : iodobenzene (1 : γ) t o triphenylamine đ t hi u su t g n 95% sau β gi glycol, β.5 đ ng l 140 C dung môi diethylene ng Cs2CO3 s d ng 10 mol% CuFe2O4 môi tr argon V t li u Fe2O3 đ c s phenylquinoxalin-2(1h)-one t d ng làm xúc tác cho ph n ng khí ng t ng h p 3- β-oxo-2-phenylacetic acid (0.25 mmol) benzene- 1,2-diamine (0.γ75 mmol) K t qu th c hi n ph n ng đ t hi u su t kho ng 8β% sau β4 gi 100 C h n h p dung môi C6H5Cl/H2O (1.5/0.5) (v/v), s d ng 10 mol% xúc tác Fe2O3 Ngoài ra, v t li u CuFe2O4 c ng đ c s d ng cho ph n ng t ng h p phenyl(2-phenylimidazo[1,2-a]pyrimidin-3-yl)methanone t trans-chalcone (0.3 mmol) 2-aminopyrimidine (0.β mmol) K t qu th c hi n ph n ng đ t hi u su t kho ng 84% sau gi 140 C dung môi 1,4-dioxane, hai đ iodine s d ng 10 mol% xúc tác CuFe2O4 mơi tr ng l ng ng khí oxi Các xúc tác cho hi u su t đ ch n l c cao Ngoài ra, ch c n ng c a xúc tác c ng đ c ch ng minh Các xúc tác nano siêu thu n t có th thu h i tái s d ng nhi u l n mà ho t tính xúc tác gi m không đáng k Theo hi u bi t c a chúng tôi, nh ng ph n ng s d ng xúc tác CuFe2O4 Fe2O3 ch a t ng đ iii c nghiên c u tr c ACKNOWLEDGEMENTS I would like to express our special appreciation and deep regards to my mentor, Prof Dr 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 Prof Dr 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 (εSc Nguyen Kim Chung, εSc Nguyen Thai Anh, ang 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 xv ABBREVIATIONS xvi PREFACE xviii CHAPTER OVERVIEW 1.1 Catalytic overview 1.1.1 Catalysis 1.1.2 Green and sustainable catalysis 1.1.3 Homogeneous and heterogeneous catalysis 1.1.4 Nanocatalyst and magnetic nanoparticles 1.2 Ferrite nanoparticles and copper ferrite nanoparticles 1.2.1 Ferrite nanoparticles catalyst 1.2.2 Copper ferrite nanoparticles catalyst 10 1.2.3 Application of superparamagnetic nanoparticles in catalyst 13 1.3 C-N cross-coupling reactions 23 1.3.1 C-N cross-coupling reaction synthesizes triphenylamines 24 1.3.2 C–N cross-coupling reactions synthesize Quinoxalin-2-ones 29 1.3.3 C-N cross-coupling reactions synthesize aroylimidazo[1,2a]pyrimidines/aroylimidazo[1,2-a]pyridines 31 1.4 Necessity – Novelty of thesis 35 1.4.1 The necessity of the thesis 35 1.4.2 The novelty of the thesis 35 1.5 Aim and objective 36 CHAPTER RESEARCH METHODS 38 2.1 Materials and instrumentation 38 2.2 Formulate for calculating yield and isolated yield 39 2.3 The catalytic activity investigation of nano CuFe2O4 for synthesis reaction of triphenylamine (TPAs) 40 2.4 The catalytic activity investigation of nanostructured Fe2O3 material for synthesis reaction of quinoxalin-2-ones 41 2.5 The catalytic activity investigation of nanostructured CuFe2O4 material for synthesis reaction of phenyl(2-phenylimidazo[1,2-a]pyrimidin-3-yl)methanone 41 CHAPTER RESULTS AND DISCUSSION 43 3.1 Characteristic structure of materials 43 v 3.1.1 Nanostructured CuFe2O4 material 43 3.1.2 Nanostructured Fe2O3 material 45 3.2 The catalytic activity investigation for C–N cross-coupling reactions 46 3.2.1 The catalytic activity investigation of CuFe2O4 for synthesis reaction of triphenylamine (TPAs) 47 3.2.1.1 Effect of different catalysts on the conversion reaction 47 3.2.1.2 Effect of different solvents on reaction conversion 48 3.2.1.3 Effect of different bases and base amounts on reaction conversion 50 3.2.1.4 Effects of reactant concentrations and reactants molar ratio on reaction conversion 53 3.2.1.5 Effect of catalyst concentrations on reaction conversion 55 3.2.1.8 Effect of homogenous catalysts and heterogeneous catalysts on reaction conversion 58 3.2.1.9 The mechanism proposal of reaction 60 3.2.1.10 Catalyst recycling and reusing 62 3.2.1.11 Effect of TPAs derivatives on reaction conversion 65 3.2.2 The catalytic activity investigation of Fe2O3 for synthesis reaction of quinoxalin-2-ones 74 3.2.2.1 Effect of different temperatures on the conversion reaction 74 3.2.2.2 Effect of reactant molar ratios on the conversion reaction 76 3.2.2.3 Effect of solvent volume ratios on the conversion reaction 76 3.2.2.4 Effect of catalyst amount on the conversion reaction 77 3.2.2.5 Effect of solvent types on the conversion reaction 78 3.2.2.6 Effect of different catalysts on the conversion reaction 80 3.2.2.7 The mechanism proposal of reaction 82 3.2.2.8 Effect of catalyst loading on reaction conversion 83 3.2.2.9 Catalyst recycling and reusing 85 3.2.2.10 Effect of quinoxalin-2(1H)-one derivative on reaction conversion 88 3.2.3 The catalytic activity investigation of the nano CuFe2O4 for synthesis reaction of phenyl(2-phenylimidazo[1,2-a]pyrimidin-3-yl)methanone 94 3.2.3.1 Effect of different temperatures on the conversion reaction 95 3.2.3.2 Effect of different catalytic amounts on reaction conversion 96 3.2.3.3 Effect of different ratios of the reactant on reaction conversion 97 3.2.3.4 Effect of iodine amount on reaction conversion 98 3.2.3.5 Effect of solvent types on reaction conversion 99 3.2.3.6 The effect of homogeneous and heterogeneous catalysts on reaction conversion 100 3.2.3.7 The mechanism proposal of reaction 102 3.2.3.8 Effect of catalyst loading on reaction conversion 103 vi 3.2.3.9 Catalyst recycling and reusing 104 3.2.3.10 Effect of aroylimidazo[1,2-a]pyrimidines and aroylimidazo[1,2a]pyridines derivatives on reaction conversion 107 CHAPTER CONCLUSIONS 119 4.1 Conclusions 119 4.2 Contribution of the thesis 119 4.3 Future works 120 LIST OF PUBLICATIONS 122 REFERENCES 123 APPENDIXES 142 vii ... highlighting the catalytic ability of superparamagnetic nanoparticles for C? ? ?N coupling reactions Meanwhile, in the superparamagnetic nanoparticle field, CuFe2O4 and Fe2O3 nanoparticles are continuously...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... ra, ch c n ng c a x? ?c t? ?c c ng đ c ch ng minh C? ?c x? ?c t? ?c nano siêu thu n t c? ? th thu h i tái s d ng nhi u l n mà ho t tính x? ?c t? ?c gi m không đáng k Theo hi u bi t c a chúng tôi, nh ng ph n ng