Cu(BDC) heterogeneous catalyst Xúc tác dị thể
Industrial University of Ho Chi Minh City Faculty of Chemical Engineering COMPLEX CATALYST Mid-term Report QUINOXALINE SYNTHESIS VIA OXIDATIVE CYCLIZATION REACTION USING METAL-ORGANIC FRAMEWORK CU(BDC) AS AN EFFICIENT HETEROGENEOUS CATALYST Reporter: Lecturer: Reported Date: 11/5/20 Complex Catalyst ABSTRACT 2-Hydroxyacetophenone phenylenediamine 11/5/20 Quinoxaline derivative OUTLINE 1.Introduction 2.Experimental section 3.Results and discussions 4.Conclusions 11/5/20 INTRODUCTION Quinoxaline Joana A Pereira: Quinoxaline, its derivatives and applications: A State of the Art review, European Journal of Medicinal Chemistry 97 (2015), 664-672 11/5/20 INTRODUCTION Metal-organic framework (MOFs) • Outstanding catalytic performance in various organic transformation reaction • Copper based on Cu(BDC) MOF has been reported as a high catalyst for many organic reactions 11/5/20 EXPERIMENT Synthesis of Cu(BDC) and Catalytic studies Cu(NO₃)₂ DMF 130 °C 48 h Wash with DMF H₂BDC Solvent exchange days DCM Cu(BDC) Blue crystal α-hydroxyacetophenone Phenylenediamine Diphenylether Toluene Characterizations TEM, SEM TEM, SEM XRD, FT-IR XRD, FT-IR AAS AAS H₂TPR, H₂TPR, Nitrogen physisorption Nitrogen physisorption 11/5/20 Evacuated 160 °C for h 100 °C Reaction conversion GC GC Product identity GC-MS, GC-MS, ¹H-NMR, ¹H-NMR, ¹³C-NMR ¹³C-NMR 180’ Leaching test Recyclability of Cu(BDC) GC GC RESULTS AND DISCUSSION CHEMICAL REACTION α-hydroxy acetophenone phenylenediamine catalyst 2-phenylquinoxaline The oxidative cyclization reaction between α-hydroxy acetophenone and phenylenediamine using Cu(BDC) catalyst 11/5/20 RESULTS AND DISCUSSION Effect of temperature 99% 82% 74% < 10% Effect of temperature on the reaction conversion 11/5/20 RESULTS AND DISCUSSION Effect of catalyst 99% 86% 81% < 10% Effect of catalyst loading on reaction conversion 11/5/20 RESULTS AND DISCUSSION Effect of α-hydroxyacetophenone : phenylenediamine 1:1,0 → 98% conversion 1:1,1 → 99% conversion 1:1,5 → 94% conversion 1:2,0 → 90% conversion Effect of α-hydroxyacetophenone : phenylenediamine molar ratio on reaction conversion 11/5/20 10 RESULTS AND DISCUSSION Effect of solvents Effect of solvent 99% 74% Solvent Effect of solvents on reaction conversion 11/5/20 Rate conversion (%) Toluene 99 P-xylene 90 mesitylene 90 chlorobenzen 88 O-xylene 98 1,4-dioxane 74 11 RESULTS AND DISCUSSION Leaching test Temperature: 1000C; Time: 180 ; Molar ratio: 1:1.1; mol% Cu(BDC) catalyst After first 30 Cu(BDC) catalyst; The Cu(BDC) catalyst was separated additional 150 under identical condition No contribution from homogeneous catalysis of active species leaching into reaction solution 11/5/20 12 RESULTS AND DISCUSSION Pyridine test Pyridine test • Copper:pyridine molar ratio of 1:2 • Time: 180 The reaction kinetic was almost identical to that of the reaction without catalyst Pyridine test The profound impact of pyridine on the Cu(BDC) catalyzed quinoxaline synthesis reaction 11/5/20 • 30 with Cu(BDC) catalyst • Pyridine was introduced The reaction progress was significantly affected by the pyridine 13 RESULTS AND DISCUSSION Comparison Catalyst Conversion (%) 100% MOF-199 92% 87% Mn2(BDC)2(DMF)2 84% 82% N (BDC) (DABCO) 2 78% 73% ZSM-5 55 58 73 78 58% Amberlyst-15 82 55% Cu(BTC)encapsulated 84 Cu2(BDC)2(DABCO) 87 MOF-118 92 Cu(BDC) 100 The Cu(BDC) catalyst was the highest conversion for the quinoxaline synthesis 11/5/20 14 RESULTS AND DISCUSSION Argon test Argon test No significant further reaction was observed under Argon atmosphere Argon test It was observed that the reaction rate was significantly enhanced in the presence of air Argon test Only 15 % of conversion was achieved It is likely that oxygen in air was the actual oxidant for above transformation 11/5/20 15 RESULTS AND DISCUSSION FT-IR FT-IR spectra of the fresh (a) and reused (b) Cu(BDC) catalyst Cu(BDC) showed a similar absorption as compared to fresh Cu-MOF 11/5/20 16 RESULTS AND DISCUSSION XRD XRD spectra of the fresh (a) and reused (b) Cu(BDC) catalyst The crystallinity of the Cu-MOF catalyst could be maintained 11/5/20 17 RESULTS AND DISCUSSION Condition: • 100oC in toluene • 180 • mol% Cu(BDC) 98% The cyclization reaction: α-hydroxyacetophenone and 4chlorophenylenediamine proceeded with difficulty 65% 95% 85% Increasing the catalyst: Concentration to mol%, up to 85% The oxidative cyclization: 4-methyl-phenylenediamine 98% Flash chromatography: α-hydroxyacetophenone and phenylenediamine, the desired product, 2-phenylquinoxaline 11/5/20 The reaction between αhydroxyacetophenone and different 1,2aryldiamines 18 CONCLUSION XRD, SEM, TEM, FT-IR, TGA, AAS, H2TPR and nitrogen physisorption measurements The Cu(BDC) was used as a heterogeneous catalyst for the oxidative cyclization reaction between α-hydroxyacetophenone and phenylenediamine derivatives to form 2-arylquinoxaline as the principal product The Cu(BDC) exhibited higher catalytic activity in the quinoxaline synthesis reaction than that of others Cu-MOFs such as MOF-199, MOF118, and Cu2(BDC)2(DABCO), and higher than that of Mn(BDC), and Ni2(BDC)2(DABCO) The quinoxaline synthesis reaction could only proceed in the presence of the solid Cu(BDC) catalyst 11/5/20 19 11/5/20 Complex Catalyst 20 ... test Temperature: 1000C; Time: 180 ; Molar ratio: 1:1.1; mol% Cu(BDC) catalyst After first 30 Cu(BDC) catalyst; The Cu(BDC) catalyst was separated additional 150 under identical condition No... temperature on the reaction conversion 11/5/20 RESULTS AND DISCUSSION Effect of catalyst 99% 86% 81% < 10% Effect of catalyst loading on reaction conversion 11/5/20 RESULTS AND DISCUSSION Effect... acetophenone phenylenediamine catalyst 2-phenylquinoxaline The oxidative cyclization reaction between α-hydroxy acetophenone and phenylenediamine using Cu(BDC) catalyst 11/5/20 RESULTS AND DISCUSSION