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  3. One-step synthesis of new thiazole and bisthiazole derivatives with various connections

One-step synthesis of new thiazole and bisthiazole derivatives with various connections

Number of pages: 93 File Format: word File Code: 31895
Year: 2013 University Degree: Master's degree Category: Chemical - Petrochemical Engineering
Tags/Keywords: Biscetophenone - Bisthiazole - His method - One-step synthesis - synthesis - Thiazole - Tivaureh
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  • Summary of One-step synthesis of new thiazole and bisthiazole derivatives with various connections

    Dissertation for M.Sc.

    Abstract

    Title: One-step synthesis of new thiazole and bisthiazole derivatives with various connections

     

    Thiazoles have various applications such as antibacterial, anticancer, anti-HIV, vitamin B1, penicillins, anti-allergy, anti-hypertensive, anti-inflammatory and treatment of schizophrenia. In this research, the synthesis of new thiazole derivatives and bisthiazoles with different connections was investigated by click chemistry and green chemistry methods. First, the synthesis of bisacetophenones (b3-a3) was performed through the reaction of 4-hydroxy and 3-hydroxyacetophenone with o-butyl, o-pentyl, o-hexyl and o-aryl bonds in the presence of K2CO3 as a base and DMF as a solvent, after separating and purifying the compounds, they were identified. Then bisthiazoles (h4-a4) were obtained from the reaction of bis-acetophenones with bromine and thiourea in dry ethanol under reflux. The structure of the synthesized products after separation and purification were identified by IR, 1H NMR and 13 C NMR spectroscopy. style="direction: rtl;">1-1 Thiazole[1]

    Thiazole or 1,3-thiazole is a heterocyclic compound with two nitrogen and sulfur atoms as part of its five-membered aromatic ring. Thiazole and its derivatives are 3,1-azo in which one nitrogen and one other heteroatom in 5 members have been replaced by its other nitrogen. The thiazole ring system is found in many natural compounds and is of special biological importance. The thiazole ring is present in thiamine[2] (1) (vitamin B1, which is vital for normal function and carbohydrate metabolism), the antibiotics penicillin[3] and bacitracin[4]. Thiazoles are also used as an intermediate in the production of many synthetic drugs, such as the antimicrobial drug sulfathiazole [5] (2), the anticonvulsant drug riluzole [6] (3), the antidepressant pramipexole [7], the antiasthmatic drug cinaloxet [8], as well as fungicides and dyes.

    1-2 Synthesis

    1-2-1 Synthesis of thiazoles from ?-halocarbonyl compounds and its derivatives (synthesis [9])

    The most common method of synthesizing thiazoles is the Hanch method, which is an ?-halocarbonyl compound (4) with thioamide (5) (or thiourea) It reacts for the synthesis of 2-amino derivatives. The reaction proceeds with the nucleophilic attack of sulfur on the halogenated carbon atom. Then, the acyclic intermediate of ?-s-alkyl iminium salt (7) after a proton transfer undergoes cyclization followed by water removal and the desired thiazole product (6) is prepared (Scheme 1-1). In addition to thioamides (5), this reaction is also carried out with thioureas, thiosemicarbazides, and other compounds containing the N-C=S structure [11-9].

    Scheme 1-1 of thiazole synthesis by Hanch's method

    This reaction usually proceeds slowly and gives simple thiazoles with good yield. However, for some types of Istihalbadar, it has limitations and the yield is low. The use of unsubstituted thioamides and ?-halocarbonyl makes it possible to obtain thiazoles with substitution in the 2-position [12-16].

    Thioformamide is used for the synthesis of unsubstituted thiazoles in the 2-position, while the use of substituted thioamides and substituted ?-haloctones produces trisubstituted thiazoles in the positions It forms 2,4 and 5 [19-17].

    Chen[10] and his colleagues synthesized 2-aminothiazole-5-carboxamide[11] (13) with a new and efficient method, which is an intermediate in the production of the anticancer drug dasatinib[12]. In this method, ?-ethoxyacrylamide [13] (12) was prepared from the coupling of ?-ethoxyacryloyl chloride [14] (10) with 2-chloro-6-methylaniline (11). Then alpha-bromination and reaction with thiourea afforded 2-aminothiazole-5-carboxamide with 95% yield (Scheme 1-2)] 20[.

    Scheme 1-2 Synthesis of 2-Aminothiazole-5-Carboxamide

    Erlen Mayer [15] made modifications in H?nsch's synthesis, so that if the ?-halotone reagent is stable, instead of thio

    amide, a mixture of amide and phosphorus pentasulfide can be used. (Scheme 1-3) [21.]

    One ??method of modifying the synthesis of Hanch is to use ?-tosyl ketones instead of ?-halocarbonyl compounds [22]. One of the advantages of this method is avoiding the use of toxic and lachrymatory ?-halocarbonyl compounds. This method involves the reaction of a ketone with HTIB reagent[16]] hydroxy-(tosyloxy)iodobenzene[(19) to form ?-tosylketone (23) via intermediate (22) Title: One-pot synthesis of new thiazole and bis-thiazole derivatives with different linkages. Jafar Parvizi. In this research, click and green chemistry synthesis of new derivatives of thiazoles and bis-thiazoles with different linkages was investigated. First, the synthesis of bis-acetophenones (3a-3b) was performed via the reaction of 4-hydroxy and 3-hydroxy acetophenones with o-butyl, o-penthyl, o-hexyl and o-aryl linkages in the presence of K2CO3 as base and in DMF as solvent, after separation and purification the compounds were characterized. Then bis thiazoles (4a-4h) were obtained in treatment of bis-acetophenones with bromine and thiourea in dry ethanol as solvent under reflux condition. The structure of the synthesized compounds after isolation and purification was characterized by IR, 1H NMR and 13C NMR spectroscopy.

  • Contents & References of One-step synthesis of new thiazole and bisthiazole derivatives with various connections

    List:

    Persian summary........................

     

    Chapter one: Introduction and theory

    1 Introduction ..........................

    1-1 Thiazole.............................

    1-2 Synthesis................................

    1-2-1 Synthesis of thiazoles from ?-halocarbonyl compounds and its derivatives (synthesis).....

    1-2-2 Synthesis of thiazoles from acylaminocarbonyl compounds and phosphorus pentasulfide (Gabriel synthesis)..

    1-2-3 Synthesis of thiazoles from the rearrangement of ?-thiocyanato ketones............

    1-2-4 Synthesis of thiazoles from ?-aminonitriles................

    1-2-5 Synthesis of derivatives Thiazole based on pyrazole...............

    1-2-6 one-pot synthesis of thiazoles in aqueous phase................

    1-2-7 Thiazole synthesis from indanone...................

    1-2-8 Thiazole synthesis using cesium carbonate catalyst............

    1-2-9 Thiazole synthesis using asymmetric thiourea..............

    1-2-10 Synthesis of thiazole derivatives using carbutioamide derivatives...

    1-2-11 Synthesis of thiazole using piperazine thioamide.............

    Title

    1-2-12 Synthesis of thiazole thiosemicarbazone.................

    1-2-13 Synthesis of bisthiazole under conditions without Halal..............

    Chapter Two: Discussion and Conclusion

    2-1 Research Objective.......................

    2-2 Research Method.......................

    2-3 Mechanism of Reaction......................

    2-4 Examining the Antibacterial Effect of Synthesized Compounds Using the MIC Method ......

    2-5 Conclusions................................

    2-6 Suggestion for Future Works.................................

    Chapter Third: Experimental works

    3 Experimental works....................

    3-1 General techniques......................

    3-2 General method of preparation of bisacetophenone derivatives (a-h3)............

    3-3 Compound 1,?1-((butane-4,1-diylbis(oxy)bis(4,1-phenylene))diaethanone (a3)....

    3-4 compound 1,?1-((pentane-1,5-diylbis(oxy)bis(4,1-phenylene))diaethanone (b3)....

    3-5 compound 1,?1-((hexane-1,6-diylbis(oxy)bis(4,1-phenylene))diaethanone (c3)...

    3-6 compound 4,?4-((4,1-phenylenebis(methylene)bis(oxy)bis(4,1-phenylene)diaethanone (d3))..

    Title

    3-7 Compound 3,?3-((butane-4,1-diylbis(oxy)bis(1,3-phenylene))diaethanone (e3)....

    3-8 compound 3,?3-((pentane-1,5-diylbis(oxy)bis(1,3-phenylene))diaethanone (f3)....

    3-9 compound 3,?3-((hexane-1,6-diylbis(oxy)bis(1,3-phenylene))diaethanone (g3)...

    3-10 compound 3,?3-((4,1-phenylene)bis(methylene)bis(oxy)bis(1,4-phenylene))diathanone (h3).

    3-11 general method of preparing thiazole compounds................

    3-12 compound 4-(4-(4-(4-(2-aminothiazol-4-yl)phenoxy)butoxy)phenyl)thiazol-2-amine (a4).............................

    3-13 compound 4-(4-(5-(4-(2-aminothiazol-4-yl)phenoxy)pentyloxy)phenyl)thiazol-2-amine (b4).

    3-14 compound 4-(4-(6-(4-(2-aminothiazol-4-yl)phenoxy)hexyloxy)phenyl)thiazol-2-amine (c4)

    3-17 compound 4-(3-(5-(3-(2-aminothiazol-4-yl)phenoxy)pentyloxy)phenyl)thiazol-2-amine (f4).

    3-18 compound 4-(3-(6-(3-(2-aminothiazol-4-yl)phenoxy)hexyloxy)phenyl)thiazol-2-amine

    (g4)

    Chapter IV: Spectra

    IR spectrum of 1,?1-((butane-4,1-diylbis(oxy)bis(4,1-phenylene))diaethanone.

    IR spectrum of 1,?1-((pentane-1,5-diylbis(oxy)bis(4,1-phenylene))diaethanone.

    IR spectrum 1,?1-((hexane-1,6-diylbis(oxy)bis(4,1-phenylene))diaethanone.

    IR spectrum 4,?4-((4,1-phenylenebis(methylene)bis(oxy)bis(4,1-phenylene))diaethanone.

    IR spectrum 3,?3-((butane-4,1-diylbis(oxy)bis(1,3-phenylene))diaethanone.

    IR spectrum 3,?3-((pentane-1,5-diylbis(oxy)bis(1,3-phenylene))diaethanone.

    IR spectrum

    IR spectrum of 3,?3-((hexane-1,6-diylbis(oxy)bis(1,3-phenylene))diaethanone.

    IR spectrum of 3,?3-((4,1-phenylene)bis(methylene)bis(oxy)bis(1,4-phenylene))diaethanone.

    IR spectrum 4-(4-(4-(4-(2-aminothiazol-4-yl)phenoxy)butoxy)phenyl)thiazol-2-amine.

    1H NMR spectrum 4-(4-(4-(4-(2-aminothiazol-4-yl)phenoxy)butoxy)phenyl)thiazol-2-amine.

    13C NMR spectrum 4-(4-(4-(4-(2-amino) Thiazol-4-yl)phenoxy)butoxy)phenyl)thiazol-2-amine.64

    IR spectrum 4-(4-(5-(4-(2-aminothiazol-4-yl)phenoxy)pentyloxy)phenyl)thiazol-2-amine.

    1H NMR spectrum 4-(4-(5-(4-(2-amino) Thiazol-4-yl)phenoxy)pentyloxy)phenyl)thiazol-2-amine.

    13C NMR spectrum 4-(4-(5-(4-(2-aminothiazol-4-yl)phenoxy)pentyloxy)phenyl)thiazol-2-amine.

    IR spectrum 4-(4-(6-(4-(2-amino) Thiazol-4-yl)phenoxy)hexyloxy)phenyl)thiazol-2-amine.

    1H NMR spectrum 4-(4-(6-(4-(2-aminothiazol-4-yl)phenoxy)hexyloxy)phenyl)thiazol-2-amine.

    13C NMR spectrum 4-(4-(6-(4-(2-aminothiazol-4-yl)phenoxy)methyl)benzyloxy)phenyl)thiazol-2-amine.

    IR spectrum 4-(3-(4-(3-(2-aminothiazol-4-yl)phenoxy)butoxy)phenyl)thiazol-2-amine.

    1H NMR spectrum 4-(3-(4-(3-(2-amino) Thiazol-4-yl)phenoxy)butoxy)phenyl)thiazol-2-amine.

    13C NMR spectrum of 4-(3-(4-(3-aminothiazol-4-yl)phenoxy)butoxy)phenyl)thiazol-2-amine.

    IR spectrum of 4-(3-(5-(3-(2-amino) Thiazol-4-yl)phenoxy)pentyloxy)phenyl)thiazol-2-amine.

    1H NMR spectrum 4-(3-(5-(3-(2-aminothiazol-4-yl)phenoxy)pentyloxy)phenyl)thiazol-2-amine.

    13C NMR spectrum 4-(3-(5-(3-(2-amino) Thiazol-4-yl)phenoxy)pentyloxy)phenyl)thiazol-2-amine.

    IR spectrum of 4-(3-(6-(3-(2-aminothiazol-4-yl)phenoxy)hexyloxy)phenyl)thiazol-2-amine.

    1H NMR spectrum of 4-(3-(6-(3-(2-amino) Thiazol-4-yl)phenoxy)hexyloxy)phenyl)thiazol-2-amine.

    13C NMR spectrum 4-(3-(6-(3-(2-aminothiazol-4-yl)phenoxy)hexyloxy)phenyl)thiazol-2-amine.

    1H NMR spectrum 4-(3-(6-(3-(2-amino) Thiazol-4-yl)phenoxy)methyl)benzyloxy)phenyl)

    thiazol-2-amine.

    IR spectrum of 4-(3-(6-(3-(2-aminothiazol-4-yl)phenoxy)methyl)benzyloxy)phenyl)thiazol-2-amine. .

    13C NMR spectrum of 4-(3-(6-(3-(2-aminothiazol-4-yl)phenoxy)methyl)benzyloxy)phenyl)

    thiazol-2-amine.

    IR spectrum of 4-(naphthalen-6-yl)thiazol-2-amine.

    1H NMR spectrum 4-(Naphthalen-6-yl)thiazol-2-amine.

    13C NMR spectrum of 4-(naphthalen-6-yl)thiazol-2-amine.

    References.

     

    Source:

    [1] Jin, Z. Nat. Prod. Rep. 2005, 22, 196.

    [2] Jin, Z. Nat. Prod. Rep. 2003, 20, 584.

    [3] Jin, Z.; Li, Z.; Huang, R. Nat. Prod. Rep. 2002, 19, 454.

    [4] Jin, Z. Nat. Prod. Rep. 2006, 23, 464.

    [5] Rowe, D. Spec. Chem. Mag. 2001, 21, 17.

    [6] Grayson, I. Spec. Chem. Mag. 2001, 21, 10.

    [7] Mori, A.; Sekiguchi, A.; Masui, K.; Shimada, T.; Horie, M.; Osakada, K.; Kawamoto, M.; Ikeda, T. J. Am. Chem. Soc. 2003, 125, 1700. [8] Turner, G. L.; Morris, J. A.; Greaney, M. F. Angew. Chem. Int. Ed. 2007, 46, 7996.

    [9] Hantzsch, A.; Weber, J. H. Ber. Dtsch. Chem. Ges. 1887, 20, 3118.

    [10] Hantzsch, A. Ber. Dtsch. Chem. Ges. 1888, 21, 942.

    [11] Zhao, R.; Gove, S.; Sundeen, J.E.; Chen, B. C. Tetrahedron Lett. 2001, 42, 2101.

    [12] Faucher, A. M.; White, P. W.; Brochu, C.; Grand-Maiter, C.; Rancourt, J.; Fazal, G. j. Med. Chem. 2004, 47, 18.

    [13] Miller, T. J.; Farquar, H. D.; Sheybani, A.; Tallini, C. E.; Saurage, A. S.; Fronczek F. R.; Hammer, R. P. Org. Lett. 2002, 6, 877.

    [14] Lee, B.W.; Lee, S. D. Tetrahedron Lett. 2000, 41, 3883.

    [15] Arda, A.; Soengas, R. G.; Nieto, M. I.; Jimenez, C.; Rodriguez, J. Org. Lett. 2008, 10, 2175.

    [16] Kim, S. H.; Tokarski, J. S.; Leavitt, K. J.; Fink, B. E.; Salvati, M.E.; Moquin, R.; Obermeier, M. T.; Trainor, G. L.; Vite, G. G.; Stadnick, L. k.; Lippy, J. S.; You, D.; Lorenzi, M.V.; Chen, P. Bioorg. Med. Chem. Lett. 2008, 18, 634.

    [17] Liu, C. L.; Li, L.; Li, Z. M. Bioorg. Med. Chem. 2004, 12, 2825. [18] Kuramoto, M.; Sakata, Y.; Terai, K.; Kawasaki, I.; Kunitomo, J.; Ohishi, T.

One-step synthesis of new thiazole and bisthiazole derivatives with various connections
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