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  3. Synthesis of 5 and 4-dihydropyrrolo[3,2,1-hi]indole-2,1-dione and its reactivity study under conditions catalyzed by hexamethylenetetraamine and paratoluenesulfonic acid in water

Synthesis of 5 and 4-dihydropyrrolo[3,2,1-hi]indole-2,1-dione and its reactivity study under conditions catalyzed by hexamethylenetetraamine and paratoluenesulfonic acid in water

Number of pages: 80 File Format: word File Code: 31873
Year: 2014 University Degree: Master's degree Category: Chemical - Petrochemical Engineering
Tags/Keywords: Betadiketones - Green chemistry - Green water solvent - HMTA catalyst - Indole - One-pot synthesis - Spiro compounds - Synthesis of 5 and 4-dihydropyrrolo - Three-component one-pot synthesis
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  • Summary of Synthesis of 5 and 4-dihydropyrrolo[3,2,1-hi]indole-2,1-dione and its reactivity study under conditions catalyzed by hexamethylenetetraamine and paratoluenesulfonic acid in water

    Dissertation for Master's Degree in Organic Chemistry

    Abstract

    The research conducted in this thesis consists of two parts, the first part is the synthesis of the precursor 4,5-dihydropyrrolo[1,2,3-hi]indole-1,2-dione (compound 1) and one-pot synthesis, three It is part of new derivatives of spiro terkibate in water green solvent and in the presence of HMTA catalyst.

           

    Part II, synthesis of precursor 5 and 6 - dihydro H1-pyrrolo]3, 2, 1-[ij Quinoline-1 and 2(H4)-dione (compound 2) and one-pot, three-component synthesis of derivatives of spiro compounds in water solvent and in the presence of p-TSA catalyst. 

    The structure of the synthesized compounds has been identified with hydrogen and carbon nuclear magnetic resonance spectral data and infrared.

    Key words:

    one-pot synthesis of three components, spiro compounds, beta-ketones

    : Principles of Chemistry Green

    With the advancement of science and the passage of decades of industrialization in the West, mankind gradually realized the damage caused to the environment and tried to preserve its existing resources and prevent environmental pollution by establishing strict laws. Green chemistry, which was introduced in the early 90s, includes chemical processes and technologies that help preserve the environment and improve the quality of life. Green chemistry is also called by different names such as environmentally friendly chemistry, clean chemistry, atomic economy [1]. The term green chemistry accepted by (IUPAC) is defined as: the invention, design and application of chemical products, processes that reduce or eliminate the production and consumption of hazardous substances [2]. The principles of green chemistry [3] provided chemists with a new meaning of the term better environment. The twelve principles of green chemistry written by Paul Anastas (P.Anastas) and John Warner (J.Warner) include all matters including designing more effective synthesis, using less hazardous materials and using renewable resources. style="direction: rtl;">2-Synthetic methods should be in such a way that during the process of converting raw materials into final products, it is maximal.

    3-Applicable synthetic methods should be used or produced materials that are less toxic or have no toxicity for human health and the environment.

    4-Chemical products should be designed in such a way that the effect of toxicity reducing factors in They should not change (the product should be stable.)

    5- The use of auxiliary materials (solvents, separators.) should not be necessary as much as possible and should be harmless if used.

    6- The energy required from an economic and environmental point of view should be at the lowest possible level. So that synthetic methods can be performed at ambient temperature and pressure.

    7- The raw materials are from renewable sources.

    8- Avoid unnecessary derivatization (bulky group, protection/deprotection) as much as possible.

    9- Catalytic reagents (which act as selectively as possible) compared to stoichiometry is preferable.

    10-Chemical products should be designed in such a way that they do not remain in the environment after consumption and turn into harmless degradable compounds.

    11-Decomposition methods should be more advanced, to provide accurate time tracking in the process and control the formation of harmful substances before production.

    12- The materials required in a chemical process and the manufacturing method of these materials should be selected in such a way that the amount of accidental phenomena such as gas production, explosion and fire is minimized.

    1-2: Green Solvent Water

    The discovery that happened in the laboratory of Berslow (Berslow) [4] and Grieco (Grieco)]5 [in 1980 and 1983 about the positive effect of water on the speed and selectivity of the Diels-Alder reaction was recognized as a major event in the synthesis of organic materials in the aqueous environment. Since then, significant progress has been made in the field of organic synthesis in water and continuously added to the list of organic reactions that can be performed in aqueous solvent. In addition to the Diels-Alder reaction, other examples are: Claisen rearrangement [6], aldol reaction [7], allylation reactions [8], oxidation [9] and hydrogenation of alkenes [10]. These types of reactions were and still are useful for the chemical industry. During the last decade, the concept of space-saving and efficient synthesis in water gained strength, and the observed speed, efficiency, and selectivity for many reactions that were performed in water could compete with the reactions performed in other organic solvents and even surpassed them. Increasing attention to organic reactions in water solvent helps our understanding of the basis of natural life mechanisms.

    1-3

    1-3-1: Why water?

    Until recently, the use of water as a solvent for organic reactions was limited to simple hydrolysis reactions. Anhydrous solvents were developed. Why should we now think of rediscovering reactions in water that were previously performed well in the family of organic solvents such as toluene, tetrahydrofuran and methylene chloride?                                                                        

    What are the many potential advantages of replacing these and other unnatural solvents with water?

    The most obvious reasons for this replacement are as follows:

    1- Cost, there is no cost to water.

    2- Safety, many organic solvents used in laboratories Dangers such as ignition, explosion, causing cancer diseases and so on.

    3- Environmental concerns, chemical industries are one of the main causes of environmental pollution. With the increasing regulatory pressures focused on organic solvents, the development of harmless solvent substitutes has become very important. However, the benefits mentioned above have no effect on synthesis costs. Even a small decrease in efficiency, catalyst performance, or reaction selectivity can lead to significant increases in cost and waste generation. Fortunately, in this sense, there are many advantages to using water as a solvent in the synthesis of organic compounds, which can be summarized as follows: First, the experimental processes may be simplified, and the separation of organic compounds and the recovery of water-soluble catalysts and other reagents can be done with a simple phase separation process. work described in this thesis involves the one pot, three component synthesis of new spiro compounds catalyzed by HMTA in water. Study of the one pot, three component synthesis of new spiro compounds catalyzed by p-TSA in water. The structure of new compounds were identified. by 1H-NMR, 13C-NMR and FT-IR spectral data.

  • Contents & References of Synthesis of 5 and 4-dihydropyrrolo[3,2,1-hi]indole-2,1-dione and its reactivity study under conditions catalyzed by hexamethylenetetraamine and paratoluenesulfonic acid in water

    List:

    Chapter One: Introduction

     

    1-1: Principles of green chemistry..2

    1-2: Green solvent water..3

    1-3-1: Why water?..3

    1-3-2: Solubility of organic compounds in water.4

    1-3-2-1: Help of organic solvent..4

    1-3-2-2: Ionic derivative (pH control).

    1-6. Synthesindoline and its derivatives..6

    1-7. Reactions of indoline..8

    1-7-1. Hydrogenation of indoline..8

    1-7-2. Oxidation of indoline..9

    1-7-3. Reaction with P450 and FMO enzymes.

    1-8. Hexamethylenetetramine catalyst (HMTA)).11

    1-9. Multicomponent reactions..11

    1-10. One-pot reactions..12

    1-10-1. Advantages of multicomponent reactions. 13

    1-11. Spiro compounds..14

    1-12.  Spiro-oxo-indole ring system. 14

    1-13. Synthesis of spirooxo indole compounds from isatin. 15

    1-14.  Synthesis of spiro compounds from starting material other than isatin. 21

    1-15. Synthesis of di-spiro compounds from isatins. 22

    1-16. Synthesis of three spiro compounds from isatin. 23

    1-17. Objective..24

    Chapter II: Experimental part

    2-1. Experimental methods..26

    2-2. Synthetic methods used. 26

    First part

    2-2-1.Synthesis of 4,5-dihydropyrrolo[1,2,3-hi]indole-1-2-dione.26

    2-2-1-1.Synthesis of 2-(indolin-1-yl)-2-oxoacetyl chloride.26

    2-2-1-2.Synthesis 4,5-Dihydropyrrolo[1,2,3-hi]indole-1,2-dione. 27

    2-2-2. General method of synthesis of spiro compounds. 27

    Second part

    2-3. Synthesis of 5,6-dihydro H1-pyrrolo]3,2,1-[ij quinoline-1,2(H4)-dione. 29

    2-3-1. Synthesis of 2-(3,4-dihydroquinolin-1(H2)-yl)-2-oxoacetyl chloride. 30

    2-3-2.  Synthesis of 5,6-dihydro H1-pyrrolo]3,2,1-[ijquinoline-1,2(H4)-dione.30

    2-3-3.  General method of synthesis of spiro compounds. 31

    2-4.  Spectral characteristics of spiro compounds.33

    Chapter three: discussion and conclusion

     

    3-1. Synthesis of spiro compounds..37

    3-1-1. General..37

    Part I

    3-1-2.Synthesis of 4,5-dihydropyrrolo[1,2,3-hi]indole-1,2-dione.37

    3-1-2-1.Synthesis of 2-(indolin-1-yl)-2-oxoacetyl chloride.37

    3-1-2-2.Synthesis 4,5-Dihydropyrrolo[1,2,3-hi]indole-1,2-dione. 38

    3-1-3. General method of synthesis of spiro compounds. 38

    3-1-4. The general mechanism of the synthesis of spiro compounds. 39

    3-1-5. Spiro compounds..40

    3-1-5-1. 2-amino-7,7-dimethyl-2,5-dioxo-4,5,5,6,7,8-hexahydro-H2-spiro]chromene-4,1-pyrrolo] 3,2,1-[hiindole[-3-carbonitrile(a 4).40

    3-1-5-2. Ethyl2-amino-7, 7-dimethyl-2, 5-dioxo-4, 5, 5, 6, 7, 8-hexahydroH-2-spirochromene-4, 1-pyrrolo

     ]             3, 2, 1-[hi indole[-3-carboxylate(b4).40

    3-1-5-3. 2-amino-2,5-dioxo-4,5,5,6,7,8-hexahydro-H 2-spiro]chromen-4,1-pyrrolo] 3,2,1-[hi indole[-3-carbonitrile(c4).41

    3-1-5-4. Ethyl 2-amino-2, 5-dioxo-4, 5, 5, 6, 7, 8-hexahydro-H 2-spiro]chromen-4, 1-pyrrolo

    ]              3, 2, 1-[hi indole[-3-carboxylate(d4).41

    Part II

    3-1-6. Synthesis of 5,6-dihydro H1-pyrrolo]3,2,1-[ij quinoline-1,2(H4)-dione. 42

    3-1-6-1. Synthesis of 2-(3,4-dihydroquinolin-1(H2)-yl)-2-oxoacetyl chloride. 42

    3-1-6-2. Synthesis of 5,6-dihydro H1-pyrrolo]3, 2, 1-[ij quinoline-1,2(H4)-dione. 42

    3-1-7. General method of synthesis of spiro compounds. 43

    3-1-8. The general mechanism of the synthesis of spiro compounds. 43

    3-1-9. Spiro compounds. Quinoline[-3-carbonitrile(a' 4).44

    3-1-9-2.  Ethyl2-amino-7,7-dimethyl-2,5-dioxo-2,4,5,5,6,6,7,8-octahydrospiro]chromene-4,1-pyrrolo] 3,2,1[ij-quinoline[-3-carboxylate(b'4).45

    3-1-5-3.  2-amino-2,5-dioxo-2,4,5,5,6,6,7,8-octahydrospiro]chromen-4,1-pyrrolo]3,2  2-Amino-2,5-dioxo-2,4,5,5,6,6,7,8-octahydrospiro]chromene-4,1-pyrrolo]3,2,1[ij-

                                   Quinoline[-3-carbonitrile (c'4).46

    3-1-9-4.  Ethyl2-amino-2,5-dioxo-2,4,5,5,6,6,7,8-octahydrospiro]chroman-4,1-pyrrolo]3,2,1[ij-

                          Quinoline[-3-carboxylate(d'4).46

    3-1-9-5.  2-amino-6 and 6-dimethyl-2, 5-dioxo-2, 4, 5, 5, 6, 6, 7, 8-octahydrospiro]chromene-4, 1-pyrrolo

    3-1-5-6-ethyl2-amino-6, 6-dimethyl-2, 5-dioxo-2, 4, 5, 5, 6, 6, 7, 8-octahydrospiro]chroman-4, 1-pyrrolo

    f4).48

    Conclusion. 49

     

     

     

    Chapter Four

     

    Appendixes and appendices. 51

    Sources and references.

     

    Source:

     

    [1].  K. A. Parker, T. L. Mindt., Org. Lett., 2001, 3, 3875.

    [2].  J. Y. Geujon, F. Zamattio, B, Kirschleger., Tetrahedron, Asymmetry., 2000, 11, 2409.

    [3].  R. Admas, R. E. Rindfvz., J. Am. Chem. Soc., 1919, 4, 648.

    [4].  D.C. Rideout, R. Breslow., J. Am., Chem. Soc., 1980, 102, 7816.

    [5].  P. A. Grieco, P. Garner., Z. He., Tetrahedron Lett., 1983, 48, 3137.

    [6].  J. J. Gajewski., Acc. Chem., Res., 1997, 30, 219. [7].  F. Fringuelli, O. Piermatti, F. Pizzo., In Organic Synthesis in Water; P. A. Grieco., Ed.;

           Blackie Academic & Professional ; London., 1998.

    [8]. W. Lu, T. H. Chem., J. Org. Chem., 2001, 66, 3467.

    [9].  V. V. Fokin, K. B. Sharpless., Angew. Chem., Int.Ed.Engl., 2001, 40, 3455.

    [10].U. Nagel, J. Albrecht., Top. Catal., 1998, 5, 3. [11]. S. H. Yalkowsky, Solubility and Solubilization in Aqueous Media, Oxford University Press, New York, 1990 [12]. B. D. Anderson, K. P. Flora., In The Practice Of Medicinal Chemistry; C.G. Wermuth., Ed., Academic Press: London, 1996. [13].  P. A. Grieco, K. Yoshida, P. J. Garner., Org. Chem, 1983, 48, 3137. [14].  S. Tascioglu., Tetrahedron., 1996, 52, 11113.

    [15].  C. G. Wermuth., The Practice Of Medicinal Chemistry; C. G. Wermuth., Ed; Academic Press: London, 1996 [16].   K. Itami, T. Nokami, J. I. Yoshida., Angew. Chem., Int.Ed.Engl., 2001, 40, 1074.

    [17].   A. R. Katritzky., A. F. Pozharskii (2000)., Handbook of Heterocyclic Chemistry (Second Ed ed.). Academic Press.ISBN 0080429882.

    [18].   G. He, C. Lu, Y. Zhao, W. A. ??Nack, G. Chen., Org. Lett., 2012, 14, 2936.

    [19].   T. S. Mei, X. Wang, J. Q. Yu., J. Am. Chem. Soc., 2009, 131, 10806. [20].   C. E. Houlden,  C. D. Bailey,  J. G. Ford,  M. R. Gagné, G. C. Lloyd-Jones, K. I. Booker

               Milburn.,  J. Am. Chem. Soc., 2008, 130, 10066. [21].   S. Chandrasekhar, D. Basu, C. R. Reddy., Synthesis, 2007, 1509.

    [22].   M. Rueping, C. Brinkmann, A. P. Antonchick,  I. Atoresei., Org. Lett., 2010, 12, 4604.

    [23].   S. Coulton, T. L. Gilchrist, and K. Graham., Tetrahedron, 1997, 53, 791.

    [24].   W. Hao Sun., J. Ehlhard., PalaniappanKulanthaivel, Diane L. Lanza, Christopher

               A. Reilly, andGaroldS. YostJPET 322: 843, 2007.

    [25].   M. Fatehi., J. Ethnopharmacol., 2005, 46, 102.

    [26].    J.C. Duff, E.J. Bills., J. Chem., Soc., 1945, 276, 547

    [27].    P. L. Henaff., Acad, C, R,; Sci. Paris. 1961, 253, 2706. [28].   I. M. Lapina, A. A. Pevzner;  Potekhin, Russ, A, A. J. Gen.  Chem., 2006, 76, 1304. [29].  N. Blazevic, D. Kolbah., Synthesis., 1979, 3, 161.

     

    [30].   H. Patel Cushman, and A. McKenzie., J. Org. Chem., 1988, 53, 5088. [31].   B. M, Trost, I. Fleming., Comprehensive Organic Synthesis;  Eds.

Synthesis of 5 and 4-dihydropyrrolo[3,2,1-hi]indole-2,1-dione and its reactivity study under conditions catalyzed by hexamethylenetetraamine and paratoluenesulfonic acid in water
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