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Green synthesis of 2-fused phenyloxazoles using ionic liquid

Number of pages: 116 File Format: word File Code: 31897
Year: 2014 University Degree: Master's degree Category: Chemical - Petrochemical Engineering
Tags/Keywords: 2-Phenyloxazole - Green synthesis - Heterocyclic compounds - ionic liquid - Oxazole - Salicylic acid
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  • Summary of Green synthesis of 2-fused phenyloxazoles using ionic liquid

    Dissertation to receive M.Sc. Field of organic chemistry

    Abstract

    Green synthesis of fused 2-phenyloxazoles using ionic liquid

    Oxazoles are an important class of heterocyclic compounds. They are the structural subunits of various natural active products and are valuable synthetic and pharmaceutical precursors. Oxazoles have antibacterial, antifungal, anti-inflammatory and anti-tumor properties. In this thesis, a group of 2-phenylbenzaxazole derivatives were synthesized using various substituted salicylic acids and 2-amino-4-chlorophenol in the vicinity of an ionic liquid. rtl;">keywords: green synthesis, oxazoles, salicylic acid, ionic liquid.

    Introduction

         Oxazole is a five-membered heterocycle with an oxygen atom and a pyridine-type nitrogen atom in positions 1 and 3 of the ring, and similar to pyridines, it has weak basicity. (Figure 1-1). Oxazoles have antibacterial, antifungal, anti-inflammatory and anti-tumor properties [2].

    Benzoxazoles have various biological and pharmacological activities such as VEGFR-2 inhibitor, CSF-1R inhibitor, LPAAT-? inhibitor, EDGR inhibitor, GnRH receptor [3-7].

    1-2- Synthesis Oxazole-4-carboxylates

    Ferreira [1] and his colleagues, from the reaction of N-acyl-?-halo dihydroaminobutyric acid derivatives 2 with (2% DBU) in acetonitrile (MeCN), prepared various derivatives of oxazole-4-carboxylate 3 with a yield of 84-96% (Scheme 1-1) [2].

    Scheme 1-1: Synthesis of oxazole-4-carboxylate

    Also, these chemists prepared other various derivatives of oxazole-4-carboxylate 5 with a yield of 78-89% from the reaction of ?-bromodihydropeptides derivatives 4 with DBU (Scheme 1-1) [2].

    Scheme 1-2: Synthesis of oxazole-4-carboxylate

    1-3- Synthesis of 5-benzyloxazole-4-carboxylate

    Bersja[2] and his colleagues during a two-step reaction of various 5-benzyloxazole-4-carboxylates 8 were synthesized. 1-Azido-2-phenylethanone 7 was synthesized from the reaction of 2-phenylacetic acid 6 with diphenylphosphoryl azide (DPPA) in the vicinity of the triethylamine base catalyst, and in the reaction with methyl isocyanoacetate anion, oxazole 8 was prepared (Scheme 1-3) [8].

    Scheme 1-3: Synthesis 5- Benzyl oxazole-4-carboxylate

    1-4-Synthesis of 2-phenyloxazole

    Tai[3] and his colleagues from the combination of serine methyl ester hydrochloride 9 with 4-(((tert-butoxycarbonyl)amino)methyl)benzoic acid 10 under the conditions 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) and hydroxybenzotriazole (HOBt) prepared ester 11 with 90% yield. The reaction of ester 11 with Burgess reagent [4] from cyclic dehydration [5] gives oxazoline in 2 hours, which is oxidized with CBrCl3 / DBU and produces oxazole 12 with 73% yield (Scheme 1-4) [9].

    Scheme 1-4: Synthesis of 2-phenyloxazole

     

    1-5- Quinolyl oxazole synthesis

        Kuang[6] and his colleagues by optimizing the synthesis of phosphodiesterase 4 (PDE4) inhibitor, which includes oxazole, obtained a series of quinolyl oxazoles 17.

    Scheme 1-5: Synthesis of quinolyl oxazole

    1-6- Synthesis of trisubstituted oxazole derivatives in position 3, 4 and 5

    Hai Liang Zhu [8] and his colleagues invented a route for the synthesis of oxazole derivatives in position 3, 4 and 5 they did They prepared 1,2,3-trimethoxybenzene 19 from the etherification of pyrogallol 18. Trimethoxybenzene obtained substituted acetophenone 20 during Friedel-Crafts acylation reaction with acetic anhydride. Compound 21 was synthesized by bromination of acetophenone 20. Ethanone 22 was prepared by alkylation of thiol. The reaction of compound 22 with hydroxylamine in ethanol solvent and pyridine catalyst produced compound 23 within 5 hours at reflux temperature. Conversion of oxime to oxazole [9] was done under microwave irradiation conditions (Scheme 1-6) [11].

    Scheme 1-6: Synthesis of trisubstituted derivatives of oxazole in position 3, 4 and 5

    1-7- Synthesis of 2-aryl-naphtho[1,2-d]oxazole

         Kumar[10] and co-workers synthesized 2-arylnaphtho[1,2-d]oxazole 30 by a multistep synthesis. Friedel Crofts' benzylation [11] of ?-naphthol with 4-hydroxybenzoic acid 26 in the presence of BF3.Et2O or boron trifluoride ether and at a temperature of 100 °C gave naphthophenone 27, which produced naphthophenone oxime 28 in the reaction with hydroxylamine hydrochloride and sodium acetate under ethanol solvent reflux conditions. Compound 28 was reacted with acetic anhydride at room temperature to obtain naphthophenone oxime acetate 29. Naphtophenone oxime acetate reacts with pyridine at 110 °C during the Beckman rearrangement [12] giving compound 30 farokhian

         Oxazoles are considered as an important class of heterocyclic compounds since they are structural subunits of various biologically active natural products and are valuable synthetic precursors and pharmaceuticals. Oxazoles are associated with anti-bacterial, antifungal, anti-inflammatory and anti-tumor activities. In continuation of our studies, we were interested in the synthesis of novel 2-phenyl Benzoxazoles derivatives using different salicylic acid derivatives and 2-amino-4-chlorophenol in the presence of ionic liquid.

  • Contents & References of Green synthesis of 2-fused phenyloxazoles using ionic liquid

    List:

    Persian abstract..1

    English abstract..116

    Chapter 1- Introduction and theory

    1-1- Introduction..3

    1-2- Synthesis of oxazole-4-carboxylates.4

    1-3- Synthesis of 5-benzyl oxazole-4-carboxylate.5

    1-4-Synthesis of 2-phenyloxazole.5

    1-5-Synthesis of quinolyloxazole.6

    1-6-Synthesis of trisubstituted derivatives of oxazole in position 3, 4 and 5.7

    1-7-Synthesis of 2-aryl-naphtho[1,2-d]oxazole.9

    1-8- Synthesis of units Structure of oxazole amino acids. 10

    1-9-Synthesis of oxazole containing ?-Alkoxy acid group. 10

    1-10-Synthesis of 8-(4-phenyloxazol-2-ylamino)-1,2,3,4-tetrahydronaphthalene-2-L. 11

    1-11-Synthesis of 2-methyl-4-phenyl derivatives Oxazole-5-carbaldehyde. 12

    1-12- Synthesis of oxazole derivatives MMPAO, MDMAPAO, MOPAO and MDPAPAQ. 14

    1-13- Synthesis of 5-(3-indolyl) oxazole derivatives. 15

    1-14- Synthesis of 1,3-oxazole derivatives. 15

    1-15- Synthesis of ring Oxazole using 4-benzoylbenzoic acid. 17

    1-16- Synthesis of oxazoloquinoline and pyridine derivatives. 17

    1-17- Synthesis of 4-aryl-2-phenyloxazole. 18

    1-18- Synthesis of disubstituted and trisubstituted oxazole derivatives in acetonitrile. 19

    1-19- Synthesis of trisoxazoles.19

    1-20- Synthesis of oxazoles from oxazolines.20

    1-21- Ionic liquids..21

    1-21-1- Advantages of ionic liquids.22

    Chapter II- Discussion and conclusion

    2-1- Research objective..24

    2-2- Research method..24

    2-2-1-Preparation of acids with azo bond.24

    2-2-2- Preparation of 2-phenylbenzaxazole derivatives.25

    2-3- Proposed mechanism for preparation of 4-(2-(2,4-dinitrophenyl)diazenyl)-2-(5-chlorobenzo [d]) derivatives Oxazol-2-yl)phenol..33

    2-4- Conclusion..38

    2-5- Suggestion for future works.39

    Chapter III- Experimental works

    3-1- General techniques.41

    3-2- General method for preparing acids with azo bond.41

    3-3- Preparation of 5-(2-(4-nitro) Phenyl)diazenyl)-2-hydroxybenzoic acid.43

    3-4- Preparation of 5-(2-phenyldiazenyl)-2-hydroxybenzoic acid.43

    3-5- Preparation of 5-(2-(2-chloro-4-nitrophenyl)diazenyl)-2-hydroxybenzoic acid.44

    3-6- 5-(2-(4-chloro-2-nitrophenyl)diazenyl)-2-hydroxybenzoic acid. 44

    3-7- Preparation of 5-(2-(2,4-dinitrophenyl)diazenyl)-2-hydroxybenzoic acid. 45

    3-8- Preparation of 5-(2-(2,4,5-trichlorophenyl)diazenyl)-2-hydroxy Benzoic acid. 46

    3-9- Preparation of 5-(2-(2,4-dimethylphenyl)diazenyl)-2-hydroxybenzoic acid. 46

    3-10- Preparation of 5-(2-(2-nitrophenyl)diazenyl)-2-hydroxybenzoic acid. azenyl)-2-hydroxybenzoic acid.47

    3-12- Preparation of 5-(2-(2-chlorophenyl)diazenyl)-2-hydroxybenzoic acid.48

    3-13- General method of preparation of 2-phenylbenzaxazole derivatives with an azo bond.49

    3-14- Preparation of 4-(2-(4-nitrophenyl)di azenyl)-2-(5-chlorobenzo[d]oxazol-2-yl)phenol.50

    3-15- Preparation of 4-(2-phenyldiazenyl)-2-(5-chlorobenzo[d]oxazol-2-yl)phenol.51

    3-16- Preparation of 4-(2-(2-chloro-4-nitrophenyl)diazenyl)-2-(5-chlorobenzo) [d]oxazol-2-yl)phenol.52

    3-17- Preparation of 4-(2-(4-chloro-2-nitrophenyl)diazenyl)-2-(5-chlorobenzo [d]oxazol-2-yl)phenol.53

    3-18- Preparation of 4-(2-(2,4-dinitrophenyl)diazenyl)-2-(5-chlorobenzo [d] Oxazol-2-yl)phenol.54

    3-19- Preparation of 4-(2-(2,4,5-trichlorophenyl)diazenyl)-2-(5-chlorobenzo [d]oxazol-2-yl)phenol.55

    3-20- Preparation of 4-(2-(2,4-dimethylphenyl)diazenyl)-2-(5-chlorobenzo [d] Oxazol-2-yl)phenol.56

    3-21- Preparation of 4-(2-(2-nitrophenyl)diazenyl)-2-(5-chlorobenzo[d]oxazol-2-yl)phenol.57

    3-22- Preparation of 4-(2-mesityldiazenyl)-2-(5-chlorobenzo[d]oxazol-2-yl)phenol.58

    3-23- Preparation of 4-(2-(2-chlorophenyl)diazenyl)-2-(5-chlorobenzo[d]oxazol-2-yl)phenol.59

    3-24- Preparation of the two ionic liquids used.60

    3-24-1- Preparation method of BBIMB ionic liquid.60

    3-24-2- Preparation method of ionic liquid DBU-OAc.61

    3-25- General method for the preparation of 2-phenylbenzaxazole derivatives with an azo bond in the vicinity of the ionic liquid.62

    3-25-1- Preparation of 2-phenylbenzaxazole derivatives with an azo bond in the vicinity of the ionic liquid BBIMB.62

    3-25-2- Preparation of 2-phenylbenzaxazole derivatives with an azo bond in the vicinity62

    3-25-2- Preparation of 2-phenylbenzaxazole derivatives with an azo bond in the vicinity of DBU-OAc ionic liquid. 62

    Chapter 4- Spectra

    FT-IR spectrum of 5-(2-(4-nitrophenyl)diazenyl)-2-hydroxybenzoic acid (a5). 64

    FT-IR spectrum of 5-(2-phenyl) diazenyl)-2-hydroxybenzoic acid (b5).65

    FT-IR spectrum of 5-(2-(2-chloro-4-nitrophenyl)diazenyl)-2-hydroxybenzoic acid (c5).66

    FT-IR spectrum of 5-(2-(4-chloro-2-nitrophenyl)diazenyl)-2-hydroxybenzoic acid (d5).67 FT-IR spectrum of 5-(2-(2,4-dinitrophenyl)diazenyl)-2-hydroxybenzoic acid (e5).68 5-(2-(2,4-dimethylphenyl)diazenyl)-2-hydroxybenzoic acid (g5).70

    FT-IR spectrum of 5-(2-(2-nitrophenyl)diazenyl)-2-hydroxybenzoic acid (h5).71

    FT-IR spectrum of 5-(2-mesyldiazenyl)-2-hydroxybenzoic acid (i5).72

    FT-IR spectrum of 5-(2-(2-chlorophenyl)diazenyl)-2-hydroxybenzoic acid (j5).73

    4-(2-(4-nitrophenyl)diazenyl)-2-(5-chlorobenzo[d]oxazol-2-yl)phenol (a7)

    FT-IR spectrum.74

    1H NMR spectrum. 75 13C NMR spectrum 76 NMR.79

    4-(2-(2-chloro-4-nitrophenyl)diazenyl)-2-(5-chlorobenzo[d]oxazol-2-yl)phenol (c7)

    FT-IR spectrum.80

    1H NMR spectrum.81

    13C NMR spectrum.82

    4-(2-(4-chloro-2-nitrophenyl)diazenyl)-2-(5-chlorobenzo[d]oxazol-2-yl)phenol (d7)

    FT-IR spectrum.83

    1H NMR spectrum.84

    13C NMR spectrum.85

    4-(2-(2,4-dinitrophenyl)di azenyl)-2-(5-chlorobenzo[d]oxazol-2-yl)phenol (e7)

    FT-IR spectrum.86

    1H NMR spectrum.87

    13C NMR spectrum.88

    4-(2-(2,4,5-trichlorophenyl)diazenyl)-2-(5-chlorobenzo[d] Oxazol-2-yl)phenol (f7)

    FT-IR spectrum.89

    1H NMR spectrum.90

    13C NMR spectrum.91

    4-(2-(2,4-dimethylphenyl)diazenyl)-2-(5-chlorobenzo[d]oxazol-2-yl)phenol (g7)

    FT-IR.92

    1H NMR spectrum.93

    13C NMR spectrum.95

    4-(2-(2-nitrophenyl)diazenyl)-2-(5-chlorobenzo[d]oxazol-2-yl)phenol (h7)

    FT-IR spectrum.96

    1H NMR spectrum.97

    13C NMR spectrum.98

    4-(2-mesethyldiazenyl)-2-(5-chlorobenzo[d]oxazol-2-yl)phenol (i7)

    FT-IR spectrum.99

    1H NMR spectrum.100

    13C NMR spectrum.102

    4-(2-(2-chlorophenyl)diazenyl)-2-(5-chlorobenzo[d]oxazol-2-yl)phenol (j7)

    FT-IR spectrum.104

    1H NMR spectrum.105

    13C NMR spectrum.106

    FT-IR spectrum of BBIMB ionic liquid.107

    DBU-OAc ionic liquid

    FT-IR spectrum.108

    1H NMR spectrum.109

     

     

    Resources.112

     

    Source:

     

    [1] Turchi, I. J.; Dewar, M. J. S. Chem. Rev. 1975, 75, 389.

    [2] Ferreira, P. M.; Castanheira, E. M.;  Monteiro, L. S.; Pereira, G.; Vilaca, H. Tetrahedron 2010, 66, 8672. [3] Potashman, M. H.; Bready, J.; Coxon, A.; DeMelfi, T. M.; DiPietro, L.; Doerr, N.; Elbaum, D.; Estrada, J.;  Gallant, P.; Germain, J.; Gu, Y.; Harmange, J. C.; Kaufman, S. A.; Kendall, R.; Kim, J. L.; Kumar, G. N.; Long, A. M.; Neervannan, S.; Patel, V. F.; Polverino, A.; Rose, P.; Plas, S.; Whittington, D.; Zanon, R.; Zhao, H. L. J. Med. Chem. 2007, 50, 4351.

    [4] Sutton, J. C.; Wiesmann, M.; Wang, W. B.; Livdvall, M. K.; Lan, J.; Ramurthy, S.; Sharma, A.; Mieuli, E. J.; Klivansky, L. M.; Lenahan, W. P.; Kaufman, S.; Yang, H.; Ng, S. C.; Keith, P.; Wagman, A.; Sung, V.; Sendzik, M. WO Patent 2007121484 A2, 2003.

    [5] Gong, B. Q.; Hong, F.; Kohm, C.; Bonham, L.; Klein, P. Bioorg. Med. Chem. Lett. 2004, 14, 1455. [6] Mi, Y.; Pan, S. F.; Gray, N.; Gao, W. Q.; Fan, Y. WO Patent 2005000833 A1, 2005.

    [7] Green, D. M.; Hauze, D.B.; Mann, C. M.; Pelletier, J.C.; Vera, M. D. WO Patent 20060264631 A1, 2006, 339, 299.

    [8] Brescia, M. R.; Rokosz, L. L.; Cole, A. G.; Stauffer, T. M.; Lehrach, J.M.; Auld, D.S.; Henderson, I.; Webb, M.

Green synthesis of 2-fused phenyloxazoles using ionic liquid
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