Synthesis of quinazolinones using metal organic frameworks (VNU 21 and sulfated mof 808) as heterogeneous catalysts

VIETNAM NATIONAL UNIVERSITY - HO CHI MINH CITY BACH KHOA UNIVERSITY - VO HOANG YEN SYNTHESIS OF QUINAZOLINONES USING METAL-ORGANIC FRAMEWORKS (VNU-21 AND SULFATED MOF-808) AS HETEROGENEOUS CATALYSTS Major: Chemical Engineering Number: 60.52.75 MASTER THESIS HO CHI MINH CITY, AUGUST 2018 CƠNG TRÌNH ĐƯỢC HOÀN THÀNH TẠI TRƯỜNG ĐẠI HỌC BÁCH KHOA –ĐHQG -HCM Cán hướng dẫn khoa học 1: GS TS Phan Thanh Sơn Nam Cán chấm nhận xét 1: PGS TS Nguyễn Thị Phương Phong Cán chấm nhận xét 2: PGS TS Trần Ngọc Quyển Luận văn thạc sĩ bảo vệ Trường Đại học Bách Khoa, ĐHQG Tp HCM ngày 04 tháng 08 năm 2018 Thành phần Hội đồng đánh giá luận văn thạc sĩ gồm: Chủ tịch: PGS TS Phạm Thành Quân Phản biện 1: PGS TS Nguyễn Thị Phương Phong Phản biện 2: PGS TS Trần Ngọc Quyển Ủy viên: PGS TS Nguyễn Đình Thành Thư ký: TS Lê Vũ Hà Xác nhận Chủ tịch Hội đồng đánh giá LV Trưởng Khoa quản lý chuyên ngành sau luận văn sửa chữa (nếu có) CHỦ TỊCH HỘI ĐỒNG TRƯỞNG KHOA KTHH ii ĐẠI HỌC QUỐC GIA TP.HCM CỘNG HÒA XÃ HỘI CHỦ NGHĨA VIỆT NAM TRƯỜNG ĐẠI HỌC BÁCH KHOA Độc lập – Tự – Hạnh phúc NHIỆM VỤ LUẬN VĂN THẠC SĨ Họ tên học viên: Võ Hoàng Yến MSHV: 1670681 Ngày sinh: 07/10/1992 Nơi sinh: Bình Dương Chun ngành: Kỹ thuật Hóa học Mã số: 60.52.75 I Tên đề tài Synthesis of quinazolinones using metal-organic frameworks (VNU-21 and sulfated MOF-808) as heterogeneous catalysts (Tổng hợp dẫn xuất quinazolinone sử dụng vật liệu khung hữu cơ-kim loại (VNU-21 MOF-808 sulfate hóa) làm xúc tác dị thể) Nhiệm vụ nội dung: Khảo sát hoạt tính xúc tác MOF VNU-21 cho phản ứng tổng hợp dẫn xuất quinazolinone có nhóm vịng thơm Khảo sát hoạt tính xúc tác MOF-808 sulfate hóa cho phản ứng tổng hợp dẫn xuất quinazolinone có nhóm alkyl II Ngày giao nhiệm vụ: 15/01/2018 III Ngày hoàn thành nhiệm vụ: 15/06/2018 IV Cán hướng dẫn: GS.TS Phan Thanh Sơn Nam TP.HCM, ngày 16 tháng 06 năm 2018 CÁN BỘ HƯỚNG DẪN CHỦ NHIỆM BỘ MÔN ĐÀO TẠO TRƯỞNG KHOA KỸ THUẬT HÓA HỌC iii ACKNOWLEDGEMENT First of all, I would like to express my gratitude to my advisor, Prof Dr Phan Thanh Son Nam, for his guidance, care, providing for a good condition and particularly financial support I would never accomplish this work without them Next, I would like to express my sincere thanks to To Anh Tuong, my best colleague in MANAR laboratory I always remember the time we spent together with all the joys, sorrows and challenges I also want to thank Ms Ha Thanh My Phuong and Mr Doan Hoai Son, my first supervisors in our laboratory Although the time we worked together was short, your guidance was the base for me to complete my thesis Furthermore, I want to thank all the co-authors in my papers, including Dr Tu Ngoc Thach, Ha Quang Hiep, Nguyen Dang Hieu, Le Van Thanh and Nguyen Thi Thu Hue for all the great supports and cooperation Next, I would like to say thank to my friends on MANAR laboratory: Duong Ngoc Tan Xuan, Pham Huy Hoang, Pham Hoang Phuc, Nguyen Ha Huy Vu and Nguyen Thi Bao Tran for all the joys and sorrows we shared together Last but not least, I would like to express my special thanks to my family Their constant encouragement gave me the important strength to successfully finish this research work Vo Hoang Yen iv ABSTRACT Herein, we would like to present two approaches for the synthesis of quinazolinone and their derivatives New iron-based metal organic framework, VNU-21, and Zirconiumbased MOF, MOF-808 were synthesized, characterized and employed as efficient heterogeneous catalyst for the synthesis of aryl-substituted and alkyl- substituted quinazolinone and their derivatives, respectively VNU-21 (formula as Fe3(BTC)(EDB)2•12.27H2O) was successfully synthesized by sovolthermal method and characterized for their properties such as chemical formula crystalinity, thermal stability, surface area The obtained VNU-21 was used as efficient heterogeneous catalyst for the decarboxylation of phenylacetic acids via oxidative Csp3-H following by oxidative cyclization of intermediate products with 2-aminobenzamides to produce corresponding quinazolinones Wide scopes with high to excellent yields were achieved and the VNU-21 was reused and recycled many times without catalytic degradation Zirconium-based metal-organic framework MOF-808 was synthesized, and sulfated with aqueous sulfuric acid solution The sulfated MOF-808 was utilized as a recyclable heterogeneous catalyst for the synthesis of alkyl- substituted quinazolinones from βketoesters and benzamides, and for the synthesis of benzimidazoles from β-ketoesters and ophenylenediamines in glycerol as environmentally benign solvent The sulfated MOF-808 was reused and recycled several times without catalytic degradation v CONTENTS ACKNOWLEDGEMENT iv ABSTRACT v CONTENTS vi LIST OF FIGURES viii LIST OF TABLES x LIST OF SCHEMES xi ABBREVIATION AND SYMBOLS xii CHAPTER I - LITTERATURE REVIEW 1 Introduction to Metal-organic frameworks General introduction Applications in catalysis The synthesis of quinazolinones Introduction Conventional approaches Our approach 13 CHAPTER II - SYNTHESIS OF ARYL-SUBSTITUTED QUINAZOLINONES 15 Experimental 15 Material and Instrument 15 Synthesis of metal-organic framework VNU-21 16 Catalytic studies 17 Result and Discussion 17 Synthesis and characterization of VNU-21 17 Catalytic studies 19 Conclusion 30 vi CHAPTER III - SYNTHESIS OF ALKYL-SUBSTITUTED QUINAZOLINONE AND THEIR DERIVATIVES 31 Experimental 31 Material and Instrument 31 Synthesis of catalyst 32 Catalytic experiments 33 Results and discussion 33 Synthesis and Charecterization of MOF-808 and sulfated MOF-808 33 Catalytic Studies 38 Conclusions 52 CHAPTER IV - CONCLUSION 54 Concluding remarks 54 Suggestions for future works 54 CHAPTER V - SUPPORTING INFORMATION 60 Aryl-Substituted Quinazolinone 60 Appendix 1: Calibration curve 60 Appendix 2: Characterization data 61 Appendix 3: Characterization data of quinazolinone derivatives: NMR data for all products 67 Alkyl-Substituted Quinazolinone 91 Appendix 1: Calibration curve calculation for 2-methylquinazolin-4(3H)one 91 Appendix 2: Characterization data 92 Appendix 3: Characterization data of alkyl-substituted quinazolinone and derivatives 96 vii LIST OF FIGURES Figure II.1 The crystal structure of VNU-21 was assembled from sinusoidal rod [Fe3(CO2)7]∞ (b) that are stitched horizontally by BTC3- and vertically by EDB2- (a, e and f) to form the red crystals (d) with structure highlighted by a rectangular window of 8.9 × 12.6 Å (c) Atom colors: Fe, blue, light blue and orange polyhedra; C, black; O, red All H atoms are omitted for clarity 18 Figure II Leaching test showed that the first step did not proceed in the absence of the VNU-21 22 Figure II Yield of 2-phenylquinazolin-4(3H)-one vs different catalysts 23 Figure II Catalyst reutilization studies 24 Figure II.5 FT-IR spectra of the fresh (a) and recovered (b) VNU-21 catalyst 25 Figure II.6 X-ray powder diffractograms of the fresh (a) and recovered (b) VNU-21 catalyst 26 Figure III.1 X-ray powder diffractograms of the sulfated MOF-808 (a) and the simulated sulfated MOF-808 34 Figure III.2 FT-IR spectra of H3BTC (a), and sulfated MOF-808 (b) 35 Figure III.3 Scanning electron microscopy (SEM) (a) and Transmission electron microscopy (TEM) (b) images of the sulfated MOF-808 35 Figure III.4 The Nitrogen adsorption and desorption isotherms for sulfated MOF808 36 Figure III.5 Pore size distribution of sulfated MOF-808 36 Figure III.6 TGA curve of the sulfated MOF-808 37 Figure III.7 The effect of solvents to the reaction yield 38 Figure III.8 Efect of different reactant molar ratio on reaction yield 39 Figure III.9 Effect of temperature on reaction yield 40 Figure III.10 Effect of catalyst amount on reaction yield 40 Figure III.11 The effect of reaction time to the reaction yield 41 Figure III.12 Leaching test 42 viii Figure III.13 The effect of other heterogeneous catalysts on reaction yield 43 Figure III 14 The effect of various homogenous catalysts on reaction yield 44 Figure III.15 Catalyst recycling studies 45 Figure III.16 X-ray powder diffractograms of the fresh (a) and recovered (b) catalyst 45 Figure III.17 FT-IR results of the fresh (a) and recovered (b) catalyst 46 ix LIST OF TABLES Table II Screening reaction conditions to maximize yield of 2-phenylquinazolin4(3H)-onea 20 Table II.2 Synthesis of different quinazolinones via oxidative Csp3-H bond activation using VNU-21 catalysta 27 Table III.1 Synthesis of various quinazolinones utilizing the sulfated MOF-808 as catalysta 47 Table III.2 Synthesis of benzimidazoles utilizing the sulfated MOF-808 catalysta 48 Table III.3 Synthesis of benzothiazoles utilizing the sulfated MOF-808 catalysta 51 x H N N Figure V 67 13C-NMR spectra of 2,5,6-trimethyl-1H-benzo[d]imidazole Characterization data for 2,5,6-trimethyl-1H-benzo[d]imidazole (Table 4, Entry 8) Prepared as shown in the general experimental procedure and purified by recrystalling with ethyl acetate: white solid, 81% yield 1H NMR (500 MHz, DMSO-d6, ppm) δ 11.86 (s, br, 1H), 7.17 (s, 2H), 2.39 (s, 3H), 2.23 (s, 6H); C NMR (125 MHz, DMSO-d6, ppm) δ 13 150.2, 129.0, 19.9, 14.6 125 Figure V 68 1H-NMR spectra of 2-methylbenzo[d]thiazole 126 Figure V 69 13C-NMR spectra of 2-methylbenzo[d]thiazole Characterization data for 2-methylbenzo[d]thiazole (Table 5, Entry 1) Prepared as shown in the general experimental procedure and purified by column chromatography on silica gel (hexane/ethyl acetate = 15/1): yellow oil, 86% yield 1H NMR (500 MHz, CDCl3, ppm) δ 7.95 (d, J = 8.0 Hz, 1H), 7.82 – 7.80 (m, 1H), 7.43 (dd, J = 8.0, 1.0 Hz, 1H), 7.35 – 7.32 (m, 1H), 2.83 (s, 3H); 13 C NMR (125 MHz, CDCl3, ppm) δ 167, 153.4, 135.6, 125.94, 124.7, 122.4, 121.4, 20.1 127 Figure V 70 1H-NMR spectra of 2-methylbenzo[d]thiazole 128 Figure V 71 13C-NMR spectra of 2-methylbenzo[d]thiazole Characterization data for 2-methylbenzo[d]thiazole (Table 5, Entry 2) Prepared as shown in the general experimental procedure and purified by column chromatography on silica gel (hexane/ethyl acetate = 15/1): yellow oil, 61% yield 1H NMR (500 MHz, CDCl3, ppm) δ 7.95 (d, J = 8.0 Hz, 1H), 7.82 – 7.80 (m, 1H), 7.43 (dd, J = 8.0, 1.0 Hz, 1H), 7.35 – 7.32 (m, 1H), 2.83 (s, 3H); 13 C NMR (125 MHz, CDCl3, ppm) δ 167, 153.4, 135.6, 125.94, 124.7, 122.4, 121.4, 20.1 129 Figure V 72 1H-NMR spectra of 2-methylbenzo[d]thiazole 130 Figure V 73 13C-NMR spectra of 2-methylbenzo[d]thiazole Characterization data for 2-methylbenzo[d]thiazole (Table 5, Entry 3) Prepared as shown in the general experimental procedure and purified by column chromatography on silica gel (hexane/ethyl acetate = 15/1): yellow oil, 39% yield 1H NMR (500 MHz, CDCl3, ppm) δ 7.95 (d, J = 8.0 Hz, 1H), 7.82 – 7.80 (m, 1H), 7.43 (dd, J = 8.0, 1.0 Hz, 1H), 7.35 – 7.32 (m, 1H), 2.83 (s, 3H); 13 C NMR (125 MHz, CDCl3, ppm) δ 167, 153.4, 135.6, 125.94, 124.7, 122.4, 121.4, 20.1 131 S N Figure V 74 1H-NMR spectra of 2-ethylbenzo[d]thiazole 132 S N Figure V 75 13C-NMR spectra of 2-ethylbenzo[d]thiazole Characterization data for 2-ethylbenzo[d]thiazole (Table 5, Entry 4) Prepared as shown in the general experimental procedure and purified by column chromatography on silica gel (hexane/ethyl acetate = 15/1): yellow oil, 75% yield 1H NMR (500 MHz, CDCl3, ppm) δ 7.97 (d, J = 8.0 Hz, 1H), 7.84 (d, J = 8.0 Hz, 1H), 7.45 (t, J = 7.5 Hz, 1H), 7.34 (t, J = 7.5 Hz, 1H), 3.15 (t, J = 7.5 Hz, 2H), 1.48 (t, J = 7.5 Hz, 3H); 13C NMR (125 MHz, CDCl3, ppm) δ 168.8, 160.6, 150.5, 134.2, 128.0, 127.2, 127.1, 123.2, 33.2, 13.1 133 S N Figure V 76 1H-NMR spectra of 2-isopropylbenzo[d]thiazole 134 S N Figure V 77 13C-NMR spectra of 2-isopropylbenzo[d]thiazole Characterization data for 2-isopropylbenzo[d]thiazole (Table 5, Entry 5) Prepared as shown in the general experimental procedure and purified by column chromatography on silica gel (hexane/ethyl acetate = 15/1): yellow oil, 82% yield 1H NMR (500 MHz, CDCl3, ppm) δ 7.98 (d, J = 8.0 Hz, 1H), 7.85 (d, J = 8.0 Hz, 1H), 7.46 – 7.43 (m, 1H), 7.36 – 7.32 (m, 1H), 3.47-3.39 (m,1H), 1.48 (d, J = 7.0 Hz, 6H); 13 C NMR (125 MHz, CDCl3, ppm) δ 178.8, 153.3, 134.8, 126.0, 124.7, 122.7, 121.7, 34.2, 23.0 135 O S N Figure V 78 1H-NMR spectra of 7-(benzo[d]thiazol-2-yl)heptan-2-one 136 O S N Figure V 79 13C-NMR spectra of 7-(benzo[d]thiazol-2-yl)heptan-2-one Characterization data for 7-(benzo[d]thiazol-2-yl)heptan-2-one (Table 5, Entry 6) Prepared as shown in the general experimental procedure and purified by column chromatography on silica gel (hexane/ethyl acetate = 5/2): brown oil, 85% yield 1H NMR (500 MHz, CDCl3, ppm) δ 7.95 (d, J = 8.0 Hz, 1H), 7.82 (d, J = 8.0 Hz, 1H), 7.43 (m, 1H), 7.33 (m, 1H), 3.10 (t, J = 7.5 Hz, 2H), 2.43 (t, J = 7.5 Hz, 2H), 2.11 (s, 3H), 1.91 – 1.85 (m, 2H), 1.66 – 1.60 (m, 2H), 1.46 – 1.39 (m, 2H); 13C NMR (125 MHz, CDCl3, ppm) δ 208.9, 172.0, 153.3, 135.2, 126.0, 124.8, 122.6, 121.6, 43.5, 34.2, 30.0, 29.5, 28.7, 23.5 137 O S N Figure V 80 1H-NMR spectra of 8-(benzo[d]thiazol-2-yl)-2-methyloctan-3-one 138 O S N Figure V 81 one 13C-NMR spectra of 8-(benzo[d]thiazol-2-yl)-2-methyloctan-3- Characterization data for 8-(benzo[d]thiazol-2-yl)-2-methyloctan-3-one (Table 5, Entry 7) Prepared as shown in the general experimental procedure and purified by column chromatography on silica gel (hexane/ethyl acetate = 5/2): brown oil, 75% yield 1H NMR (500 MHz, CDCl3, ppm) δ 7.96 (d, J = 8.0 Hz, 1H), 7.83 (d, J = 8.0 Hz, 1H), 7.46 - 7.43 (m, 1H), 7.36 - 7.33 (m, 1H), 3.11 (t, J = 7.5 Hz, 2H), 2.62 – 2.52 (m, 1H), 2.46 (t, J = 7.3 Hz, 2H), 1.92 – 1.96 (m, 2H), 1.67 – 1.61 (m, 2H), 1.47 – 1.36 (m, 2H), 1.07 (d, J = 7.0 Hz, 6H); 13C NMR (125 MHz, CDCl3, ppm) δ 214.8, 172.2, 153.3, 135.2, 126.1, 124.8, 122.6, 121.6, 41.0, 40.2, 34.3, 29.6, 28.9, 23.5, 18.4 139 ... tài Synthesis of quinazolinones using metal- organic frameworks (VNU- 21 and sulfated MOF- 808) as heterogeneous catalysts (Tổng hợp dẫn xuất quinazolinone sử dụng vật liệu khung hữu cơ-kim loại (VNU- 21. .. the synthesis of quinazolinone and their derivatives New iron-based metal organic framework, VNU -21, and Zirconiumbased MOF, MOF- 808 were synthesized, characterized and employed as efficient heterogeneous. .. diffractograms of the sulfated MOF- 808 (a) and the simulated sulfated MOF- 808 PXRD was used to determine the extent of formation and crystallinity of the sulfated MOF- 808 in comparison to simulated sulfated