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Synthesis and Applications of Mixed Nano Copper/Zinc Oxides as New Catalyst in Organic Synthesis

Ph.D. DISSERTATION IN

ORGANIC CHEMISTRY

Synthesis and Applications of Mixed Nano Copper/Zinc Oxides as New Catalyst in Organic Synthesis

This study involves the synthesis and fully characterization of some Cu and Zn mixed metal oxide nanostructures and the utilization of them for catalytic applications as following:

1- Synthesis of propargylamines through a one-pot three-component coupling reaction of terminal alkynes, aldehydes/or ketones and secondary amines in excellent isolated yields under solvent-free conditions.

2- N-arylation of various N-heterocycles with aryl halides and arylboronic acids in the absence of additional ligand in air.

3- Synthesis of diaryl ethers under ligand and solvent-free conditions.

4- Synthesis of tetrazoles.

5- Synthesis of benzoxazoles and 2-oxazolines.

6- Synthesis of triazoles from in situ generated azides.

7- Synthesis of organophosphorus heterocycles through a one-pot three-component coupling reaction of diphenyl phosphate, aldehydes and primary amines in high isolated yields under solvent-free conditions.

دسته: زبان خارجه, زبان خارجه برچسب: Synthesis and Applications of Mixed Nano Copper/Zinc Oxides as New Catalyst in Organic Synthesis

توضیحات

Table of Contents
Content	Page

CHAPTER ONE:. 1

INTRODUCTION AND LITERATURE REVIEW… 1

1.1 . Nanotechnology. 2

1.2 . Nanomaterials. 2

1.2.1 . ZnO nanoparticles. 3

1.2.2 . Cu_xO nanoparticles (x=1, 2). 6

1.2.3 . Cu_XO/ZnO nanoparticles. 9

1.3 . A brief review onpropargylamines. 11

1.4 . A brief review ontriazoles. 19

1.5 . A brief review ontetrazoles. 23

1.6 . A brief review onbenzoxazoles and 2-oxazolines. 27

1.7 .A brief review ondiaryl ethers. 29

1.8 . A brief review on arylation of imidazole. 34

1.9 . A brief review onorganophosphorus heterocycles. 38

1.10 . The Objective of This Study. 40

CHAPTER TWO: EXPRIMENTAL.. 41

2.1 . General 42

2.2 . General procedure for the synthesis of nano Cu₂O.. 43

2.3 . General procedure for the synthesis of nano ZnO.. 43

2.4 . General procedure for the synthesis of nano Cu₂O/ZnO.. 43

2.5 . General procedure for the synthesis of nano CuO/ZnO.. 44

2.6 . General procedure for the three-component synthesis of propargylamines using ZnO: 44

2.7 . General procedure for the three-component synthesis of propargylamines containing atertiary carbon center using nano Cu₂O/ZnO: 45

2.7.1 . Physical data of representative products (4a-s and 5a-m): 46

2.8 . General procedure for the catalytic N-arylation of nitrogen-containing heterocycles witharyl halides andarylboronic acid: 57

2.8.1 . Physical data of representative products (8a-n): 57

2.9 . General procedure for thesynthesis of diaryl ether: 61

2.9.1 . Physical data of representative products(10a-o): 61

2.10 . General procedure for the synthesis of 5-substituted-1H-tetrazoles: 65

2.10.1 . Physical data of representative products(12a-o): 65

2.11 . General procedure for the synthesis of 2-arylbenzoxazole: 71

2.11.1 . Physical data of representative products(15a-i): 71

2.12 . General procedure for the synthesis of 2-oxazolines (16a-k): 74

2.12.1 . Physical data of representative products (16a-k): 74

2.13 . General procedure for the one-pot synthesis 1,2,3-triazoles of aryl boronic acids: 76

2.13.1 . Physical data of representative products: 77

2.14 . General procedure for the synthesis of 3-amino-2-hydroxy-2,3-dihydrobenzo[d][1,2]oxaphosphole 2-oxides: 83

2.14.1 . Physical data of representative products (20b, 20c): 83

CHAPTER THREE:. 85

RESULTS AND DISSCUSION.. 85

3.1 . Mixed metal oxide nanoparticles: 86

3.2 . Preparation and chracterization of nano Cu₂O/ZnO: 86

3.2.1 . XRD analysisof Cu₂O/ZnO nanoflake: 86

3.2.2 . SEM and TEMof Cu₂O/ZnO nanoflake: 87

3.2.3 . FT-IR spectrumof Cu₂O/ZnO nanoflake: 88

3.2.4 . Specific surface area of Cu₂O/ZnO nanoflake: 89

3.2.5 . ICP analysis of Cu₂O/ZnO nanoflake: 90

3.3 . Preparation and chracterization of nano CuO/ZnO: 90

3.3.1 . XRD analysis of CuO/ZnO nanosphere: 91

3.3.2 . SEM and TEM of CuO/ZnO nanosphere: 92

3.3.3 . FT-IR spectrum of CuO/ZnO nanosphere: 93

3.3.4 . Specific surface area of CuO/ZnO nanosphere: 94

3.3.5 . ICP analysis of CuO/ZnO nanosphere: 95

3.4 . Catalytic reactivity of nano Cu₂O/ZnO: 95

3.4.1 . Coupling of aldehydes/or ketones, secondary amines, and terminal alkynes under solvent-free conditions catalyzed by nano Cu₂O/ZnO: 95

3.4.1.1 . One-pot multi-component route to propargylamines using zinc oxide under solvent-free conditions: 109

3.4.2 . Nano Cu₂O/ZnOas heterogeneous catalyst for the N-arylation of heterocycles with aryl halides and arylboronic acids in the absence of additional ligand in air: 119

3.4.3 . Nano Cu₂O/ZnO as heterogeneous catalyst for the synthesis of diaryl ethers: 131

3.4.4 . Nano Cu₂O/ZnO as heterogeneous catalyst for the synthesis of tetrazole derivatives: 140

3.4.5 . Nano Cu₂O/ZnO as heterogeneous catalyst for the synthesis of oxazoline and benzoxazolederivatives: 145

3.5 . Nano Cu₂O/ZnO catalyzed homocoupling reaction of terminal alkynes: 151

3.6 . Catalytic reactivity of nano CuO/ZnO: 154

3.6.1 . Nano CuO/ZnO catalyzed one-pot synthesis of 1,4-disubstituted 1,2,3-triazoles from in situ generated azides: 154

3.6.2 . Nano CuO/ZnO catalyzed one-pot, three component synthesis of heterocyclic α-aminophosphonates: 159

3.7 . Unsuccessfull Reactions. 164

List of Schemes
Scheme	Page

Scheme 1.1. Synthesis of 3-indolyl-3-hydroxy oxindoles catalyzed by nano-rod ZnO. 5

Scheme 1.2. Synthesis of 2-amino-4H-chromen-4-yl phosphonats using nano-rod ZnO. 6

Scheme 1.3. Cu-catalyzed couplings of aryl iodonium salts with sodium trifluoromethanesulfinate. 8

Scheme 1.4. Copper-catalyzed synthesis of quinazolines in water starting from o-bromobenzylbromides and benzamidines. 9

Scheme 1.5. C-Arylation reactions catalyzed by CuO-nanoparticles under ligand free conditions. 9

Scheme 1.6. Nano copper oxide catalyzed synthesis of symmetrical diaryl sulfides under ligand free conditions. 9

Scheme 1.7. Azide–alkyne cycloaddition reactions catalyzed by the ZnO–CuO hybrid nanocatalysts under ultrasonic irradiation. 11

Scheme 1.8. Various procedures for the synthesis of propargylamines. 12

Scheme 1.9. Tentative mechanism of the A³-coupling. 13

Scheme 1.10. A³-coupling with polymer-supported aryl alkynes. 14

Scheme 1.11. CuBr-RuCl₃-co-catalyzed A³-coupling for the synthesis of N-arylpropargylamines. 14

Scheme 1.12. AuBr₃-catalyzed A³-coupling for the synthesis of tertiary propargylamines. 15

Scheme 1.13. AgI-catalyzed A³-coupling for the synthesis of propargylamines. 15

Scheme 1.14. Universal microwave-assisted CuI-catalyzed A³-coupling protocol. 16

Scheme 1.15. Recyclability of the CuCN catalyst in the A³-coupling process employing an ionic liquid. 17

Scheme 1.16. Microwave-assisted CuBr-catalyzed A³-coupling for the synthesis of secondary N-alkylpropargylamines. 18

Scheme 1.17. Synthesis of propargylamines catalyzed by nanocrystalline copper(II) oxide. 18

Scheme 1.18. Synthesis of triazolylcoumarins by CuAAC. 20

Scheme 1.19. Thermal 1,3-dipolar Huisgen cycloaddition between alkynes and azides. 20

Scheme 1.20. Cu(I)-catalyzed azide–alkyne cycloaddition. 21

Scheme 1.21. Synthesis of triazoles using bimetallic Pd(0)–Cu(I) catalyst. 21

Scheme 1.22. Synthesis of triazoles using microwave assisted Cu(0)–Cu(II). 21

Scheme 1.23. Microwave-assisted three-component synthesis of 1,4-disubstituted 1,2,3-triazoles. 22

Scheme 1.24. Solvent-free synthesis of triazoles using a polymer-supported copper (I) iodide. 22

Scheme 1.25. One-pot synthesis of 1,2,3-triazoles using copper catalysts in water. 23

Scheme 1.26. One-pot synthesis of 1,4-disubstituted 1,2,3-triazoles. 23

Scheme 1.27. Clay-Cu(II)/NaN₃ catalyzed aromatic azidonation and azide-alkyne cycloaddition. 23

Scheme 1.28. Preparation of 5-substituted 1H-tetrazoles from the corresponding nitriles and NaN₃. 25

Scheme 1.29. TBAF-catalyzed reaction of benzonitrile with TMSN₃ under solvent less condition. 25

Scheme 1.30. CuI-catalyzed reaction of nitriles with trimethylsilyl azide. 26

Scheme 1.31. Synthesis of 5-substituted 1H-tetrazole with γ -Fe₂O₃. 26

Scheme 1.32. Synthesis of 5-substituted tetrazoles catalyzed by Cu–Zn alloy nanopowder. 26

Scheme 1.33. Synthesis of 5-substituted tetrazoles catalyzed by AMWCNTs-O-Cu(II)-PhTPY. 27

Scheme 1.34. Preparation of 2-oxazines and 2-oxazolines. 28

Scheme 1.35. Synthesis of aryl 2-oxazolines catalyzed by Pd/Fe₃O₄. 29

Scheme 1.36. Palladium-catalyzed multicomponent process for the preparation of oxazolines and benzoxazoles. 29

Scheme 1.37. Copper(I)/diketone-based catalytic systems developed by Buchwald. 31

Scheme 1.38. Copper(I)/diketone-based catalytic systems developed by Bao. 31

Scheme 1.39. Copper(I)/diketone-based catalytic systems developed by Taillefer. 32

Scheme 1.40. Copper(I) bromide/ligand systems developed by Ding. 32

Scheme 1.41. Etherification of aryl bromides catalysed by CuSAr after 6 h. 33

Scheme 1.42. Room temperature, metal-free synthesis of diaryl ethers with use of diaryliodonium salts. 33

Scheme 1.43. Synthesis of polyfluoro-substituted unsymmetrical biaryl ethers. 34

Scheme 1.44. Copper-catalyzed arylation of imidazoles by aryl halides. 35

Scheme 1.45. Cu₂O-catalyzed arylation of imidazoles by aryl halides. 36

Scheme 1.46. CuI-catalyzed N-arylation of imidazole, pyrazole and benzimidazole with aryl bromides. 37

Scheme 1.47. CuSO₄-catalyzed arylation of imidazoles with aryl halides. 37

Scheme 1.48. Cu(OAc)₂.H₂O-catalyzed arylation of nitrogen-containing heterocycles with aryl iodides. 38

Scheme 1.49. Cyclization of allenic phosphonic acids with different electrophiles. 39

Scheme 1.50. Synthesis of 3-amino-2-hydroxy-2,3-dihydrobenzo[d][1,2]oxaphosphole 2-oxides. 39

Scheme 3.1. Synthesis of propargylamines catalyzed by Cu₂O/ZnO nanoflake under solvent-free condition. 96

Scheme 3.2. Three-component coupling of benzaldehyde, piperidine and phenylacetylene. 96

Scheme 3.3. Synthesis of propargylamines catalyzed by ZnO under solvent-free condition. 109

Scheme 3.4. A proposed mechanism of the ZnO-catalyzed synthesis of propargylamine. 117

Scheme 3.5. Synthesis of N-aryl heterocycles in air catalyzed by Cu₂O/ZnO nanoflake. 119

Scheme 3.6. Reaction conditions for synthesis of diaryl ether. 131

Scheme 3.7. Nano Cu₂O/ZnO catalyzed synthesis of 5-substituted 1H-tetrazoles. 140

Scheme 3.8. Synthesis of 2-oxazolines and benzoxazoles from the reaction of aromatic nitriles with 2-aminoalcohols and 2-aminophenols. 146

Scheme 3.9. Nano Cu₂O/ZnO -catalyzed homocoupling of phenylacetylene. 152

Scheme 3.10. One-pot synthesis of 1,4-disubstituted 1,2,3-triazoles. 155

Scheme 3.11. Synthesis of 3-amino-2-hydroxy-2,3-dihydrobenzo[d][1,2]oxaphosphole 2-oxides. 160

List of Figures
Figure	Page

Figure 1.1.The crystal structure of ZnO (a): Wurtzite structure, (b): Zinc blend unit cell, (c): Rocksalt structure. 4

Figure 1.2. Various morphologies of ZnO nanostructure, including (a): nanotube (b): hierarchical (c): nanobelt (d): nanorod (e): nanocomb and (f): nanowire. 5

Figure 1.3. Crystal structure of Left: CuO, monoclinic stucture. Right: Cu₂O, Cubicstructure. 7

Figure 1.4. Propargylamine inhibitors of type-B monoamine oxidase. 11

Figure 1.5. Two examples of 1,2,3-triazoles with anti-HIV properties. 19

Figure 1.6. Examples of pharmaceutically relevant biphenyl tetrazoles. 24

Figure 1.7. Example of several biological compounds. 27

Figure 1.8. Selected biologically active diaryl ethers. 30

Figure 1.9. Structures of some well-khown imidazoles containing bioactive molecules. 34

Figure 1.10. The structures of some ligands for arylation of N-heterocycles. 36

Figure 3.1. XRD pattren of Cu₂O/ZnO nanoflake. 87

Figure 3.2. The SEM image of Cu₂O/ZnO nanoflake. 88

Figure 3.3. TEM image of Cu₂O/ZnO nanoflake. 88

Figure 3.4. FT-IR spectrum of Cu₂O/ZnO nanoflake. 89

Figure 3.5. The XRD pattern of CuO/ZnO nanosphere. 92

Figure 3.6. The SEM image of CuO/ZnOnanosphere. 93

Figure 3.7. The TEM image of CuO/ZnOnanosphere. 93

Figure 3.8. FT-IR spectrum of CuO/ZnOnanosphere. 94

Figure 3.9. Recyclability of Cu₂O/ZnO nanoparticle for propargylamine synthesis 100

Figure 3.10. Comparison of FT-IR spectrum of Cu₂O/ZnO nanoflake, A: before and B: after 10 times reuses. 101

Figure 3.11. The XRD pattern of Cu₂O/ZnO nanoflake:a: before and b:after 10 times reuses. 101

Figure 3.12. The XRD pattern of Cu₂O/ZnO nanoflake after 6 times reuses. 124

Figure 3.13. The XRD pattern of Cu₂O/ZnO nanoflake: a) before and b) after 5 times reuses. 138

Figure 3.14. The XRD pattern of Cu₂O/ZnO nanoflake:a: before and b:after 5 times reuses. 145

List of Tables
Table	Page

Table 3.1. Results of BET surface area measurements for nano Cu₂O/ZnO nanocatalyst. 90

Table3.2. Results of BET surface area measurements for nano CuO/ZnO nanocatalyst 95

Table 3.3. Investigation of the catalytic activity various metal oxides in the three-component coupling of benzaldehyde, piperidine and phenylacetylene^a 97

Table 3.4. The optimization of solvent^a 98

Table 3.5. The optimization oftemperature^a 99

Table 3.6. One-pot synthesis of propargylamine derivatives 4a from aldehydes, amines, and alkynes, by using Cu₂O/ZnO nanoparticle as catalyst^a 103

Table 3.7. One-pot synthesis of propargylamine deriveatives 5 from ketones, amines, and alkynes, using Cu₂O/ZnO nanoparticle as catalyst^a 106

Table 3.8. Amount ofcatalyst effect in the three-component synthesis of propargylamine 4a^a 110

Table 3.9. Solvent and temperatureoptimization^a 111

Table 3.10. A³-coupling of aldehydes or ketones, amines, and alkynes catalyzed by ZnO^a 113

Table 3.11. Ruse-ability of ZnO^a 116

Table 3.12. Comparison of protocols for synthesis of propargylamine from benzaldhyde, piperidine and phenylacetylene. 118

Table 3.13. Investigation of a few zinc and copper metal oxides in N-arylation of imidazole with iodobenzene^a 121

Table 3.14. The optimization of solvent and base^a 122

Table 3.15. The optimization of temperature^a 123

Table 3.16. Ruse-ability of Cu₂O/ZnO nanoflake^a 123

Table 3.17. N-Arylation of imidazole with aryl halide or arylboronic acid^a 126

Table 3.18. N-Arylation of various nitrogen heterocycles^a 129

Table 3.19. Comparison of activity of different copper catalysts in the N-arylation reaction of iodobenzene and imidazole. 130

Table 3.20. The optimization of the reaction^a 132

Table 3.21.The optimization oftemperature^a 133

Table 3.22. Reaction of aryl halides with substituted phenols using nano Cu₂O/ZnO as catalyst^a 134

Table 3.23. Reusability of the recovered catalyst.^a 138

Table 3.24. Comparison of activity of different catalysts in the O-arylation of phenol with iodobenzene. 139

Table 3.25.Comparison of the conditions used for the reaction of benzonitrile with NaN₃.^a 141

Table 3.26. Synthesis of 5-substituted 1H-tetrazoles.^a 142

Table 3.27. Reusability of the recovered catalyst.^a 144

Table 3.28. Condition screening of reaction between 2-aminophenol and benzonitrile^a 147

Table 3.29. Synthesis of benzoxazoles using Cu₂O/ZnO nanoparticles at 120 °C under solvent-free condition.^a 148

Table 3.30. Synthesis of 2-oxazoline using Cu₂O/ZnO nanoparticle^a 150

Table 3.31. The optimization of the reaction^a 153

Table 3.32. The optimization oftemperature^a 153

Table 3.33. Cu₂O/ZnO-catalyzed homocoupling of alkynes.^a 154

Table 3.34. CuO/ZnO nanosphere catalyzed aromatic azidonationa and azide-alkyne cycloaddition^a 156

Table 3.35. Nano CuO/ZnO-catalyzed one-pot reaction of arylboronic acids with sodium azide in water followed by a click cyclization with an alkyne.^a 157

Table 3.36. Reusability of the recovered catalyst.^a 159

Table 3.37. Comparison of the conditions used for the reaction between 2-hydroxybenzaldehye, ethylamine and diphenyl phosphate ^a 160

Table 3.38. Thereaction ofvarious o-hydroxybenzaldehydes and amines were investigated with diphenyl phosphite.^a 161

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