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  3. Reaction of arylglyoxals with different diamines under microwave conditions

Reaction of arylglyoxals with different diamines under microwave conditions

Number of pages: 91 File Format: word File Code: 31875
Year: 2013 University Degree: Master's degree Category: Chemical - Petrochemical Engineering
Tags/Keywords: Acetophenone oxidation - Arylglyoxal reaction - Condensation reaction - Diamine - Pyrazine - Quinoxaline
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  • Summary of Reaction of arylglyoxals with different diamines under microwave conditions

    Dissertation for obtaining a master's degree in organic chemistry

    Abstract:

    The new work done in this thesis includes the condensation reaction of arylglyoxals prepared during the oxidation of acetophenones related to selenium dioxide with 1,2-diaminobenzene, 2,3-diaminomalonitrile, 2,3-diaminopyridine and 4-nitro-1,2-diaminobenzene in order to prepare the corresponding quinoxalines and arylpyrazines under microwave conditions

    The products prepared with good efficiency were identified through 1H-NMR and 13C-NMR and FT-IR spectral data.

    Chapter First

    Introduction

    The first verse: Introduction

    1.  

    1-1. Pyrazines:

    Pyrazines are a group of diazines and diazines are benzene derivatives that have two nitrogen atoms instead of two carbon atoms. Diazines have three possible isomeric structures, which are called pyridazine (1), pyrimidine (2) and pyrazine (3), depending on the positions (1, 2), (1, 3) and (1, 4) of the nitrogen atoms in the ring. The structure of pyrazines:

    The structure of pyrazine (3) has been determined by X-ray analysis and electron diffraction. Flat six-membered ring pyrazine has two nitrogen atoms with D2h symmetry, and these atoms are placed in position (1 and 4) in the ring relative to each other. The measured heat capacity for crystalline pyrazine is in the range of 20-40°C [1]

    The 1H-NMR spectrum includes a peak for four equivalent hydrogens that appears at ?=8.63 ppm in deuterium chloroform solvent:

    Also has a carbon 13C-NMR peak at ?=144.9 ppm for four carbons It is equivalent to:

    Pyrazine compounds have biological and medicinal properties that are used in many cases to treat advanced diseases such as cancer. Pyrazine has many derivatives, among which pyridopyrazines (4) and (5) can be mentioned.

    The presence of a pyridine ring attached to pyrazine not only changes its physical characteristics, including melting and boiling temperature, but also affects its chemical properties. Biologicals have been introduced in some medical and chemical journals and sources. For example, two examples of these compounds such as pyrido[2,3-[bpyrazine (4) and pyrido[3,4-[bpyrazine (5)] are used for malignant tumors and the treatment of diseases related to harmful cell proliferation [2].

    pyrido[2,3-[bpyrazine] can act as the main base of compounds produced to prevent vascularization by cancer cells in the cancerous part [3]. Also, pyrido derivatives [3 and 4-[b]pyrazine, in addition to medicinal applications, act as inhibitors for polymerization in the range of macromolecules [4].

    1-3. Synthesis of pyrazines:

    The prediction of pyrazine synthesis is based on the system breaking method based on the main structure of other azines. Breaking the bond in the imine group (one-step synthesis) leads to the formation of 2,1-dicarbonyl compounds (6) and 2,1-diaminoethanes (7) as starting materials, which are used for the synthesis of specific pyrazines by ring condensation. (10) and (6) or obtained from a-amino ketone (11)[5].

    1-3-1.The use of 1,2-diamine compounds with 1,2-dicarbonyl compounds:

    In this synthetic method, which is the best way to make pyrazine, the amine groups of a compound attack the carbonyl groups of the dicarbonyl compound (12), creating a cyclic compound that leads to the removal of two water molecules and the production of the final product. If 1,2-diaminoalkane (13) is used, there is no need for an oxidant to produce pyrazine:

                                                  

    But if 1,2-diaminoalkane (14) is used, the presence of an oxidant is necessary for hydrogenation and creation of an aromatic compound to produce 2,3-dihydropyrazine (15) produced in the first step. convert to the final product:

    One ??of the best mild oxidants for the above reaction is MnO2 in EtOH/KOH, which only causes dehydrogenation [6].

    1-3-2. Use of -aminocarbonyl compound:

    In the reaction of two molecules of -aminocarbonyl (16) with the attack of the amine groups of the first molecule on the carbonyl groups of the second molecule, the desired pyrazine is created. To obtain the aromatic compound, there is a need for the presence of an oxidant to convert 2,5-dihydropyrazine (17) into pyrazine [5].

    1-3-3. The use of -amino hydroxyls:

    This reaction is performed using two primary -amino hydroxyl molecules (18) in the presence of an oxidant, which is accompanied by the attack of amine groups. Cr2O3 can be used as a mild oxidant [7].

    1-3-4. Use of oximes:

    Pyrazine derivatives have been synthesized from the reaction of ?-hydroxyketone and ?-ketoximes in the presence of a catalytic amount of ceric ammonium nitrate (CAN).[8]

    1-3-5. Use of ethylenediamine:

    Pyrazines are synthesized from ethylenediamine in the presence of copper oxide/copper chromite catalyst. [9]

    1-3-6. Using ?-halotones in the presence of microwaves: ?-halotones in 7% ammonia solution produce pyrazine derivatives under microwave radiation. 1-3-7. Intramolecular reaction :

    In addition to the above reactions, intramolecular reactions can also be used to produce pyrazines. Carrying out this type of reaction depends on the existence or creation of appropriate attacking and attacked groups. ]10[

    1-4. Synthesis of pyrido]3 and 4-[b pyrazine

    1-4-1. Reaction of 3,4-diaminopyridine with 1,2-dicarbonyl compounds:

    In the synthesis of pyrazine derivatives like pyrazine itself, the reaction of diamino compounds with different substitution groups with dicarbonyl compounds with various substitution groups is the best way to synthesize this class of compounds [11] and [12].

    1-4-2. The reaction of 5-bromo-3,4-diaminopyridine with 2-(methylthio)-1-phenylethanone:

    This method is not as common as the previous method, however, it is part of the reactions to produce pyrido [3,4-[b pyrazine] [12].

    1-5. Reactions of pyrazines:

    Like other diazines, the active nitrogen atoms of the ring determine the reactions of the pyrazine ring. They are attacked by electrophilic reactions. For example, protonation and oxidation, which greatly reduce the activity of the ring. Hence, very few substitution reactions perform aromatic electrophilic substitution. For example, if bromination occurs, the product is only formed in moderate yield.

    Electron-donating substituents, such as amino groups, activate the ortho- and para-hetero-positions of arenes. It also depends on the existence of other isthilafs. For example, 2-aminopyrazine (19) is easily converted to (20) during halogenation. 3-Aminopyrazine-2-carboxylic acid (21) undergoes N-halogenation and does not undergo any nucleophilic substitution [5].

  • Contents & References of Reaction of arylglyoxals with different diamines under microwave conditions

    List:

    Chapter One: Introduction

    1-1. Pyrazines 2

    1-2. Structure of pyrazines 2

    1-3. Synthesis of pyrazines 4

    1-3-1. The use of 1,2-diamine compounds with 1,2-dicarbonyl compounds 4

    1-3-2. The use of -aminocarbonyl compound. 5

    1-3-3. The use of - amino hydroxyls 5

    1-3-4. Use of oximes 6

    1-3-5. Use of ethylene diamine. 6

    1-3-6. Use of ?-halotones in the presence of microwaves. 6

    1-3-7. Intramolecular reaction 6

    1-4. Synthesis of pyrido]3 and 4-[b-pyrazine. 7

    1-4-1. Reaction of 3,4-diaminopyridine with 1,2-dicarbonyl compounds 7

    1-4-2. Reaction of 5-bromo-3,4-diaminopyridine with 2-(methylthio)-1-phenylethanone. 7

    1-5. Reactions of pyrazines 8

    1-6. Quinoxalines 10

    1-7. Synthesis methods of quinoxalines 10

    1-7-1. Condensation of aromatic diamines with dicarbonyl compounds 10

    1-7-2. Intramolecular cyclization. 11

    1-7-3. Loop Decomposition. 12

    1-7-4. Synthesis of fused quinoxalines. 12

    1-7-5. Use of quinoxaline-alfactol or dione. 15

    1-7-6. Using free glyoxal as synten. 17

    1-7-7. Use of diketone or related synthene. 17

    1-7-8. Using diketones to produce a product. 18

    1-7-9. Using diketone to produce two isomeric products. 19

    1-8. Reactions of quinoxalines 20

    1-8-1. Substitution reactions. 20

    1-8-2. Reduction: 20

    1-8-3. Synthesis of pyrazoloquinoxalines from quinoxalines 21

    1-9. Application of quinoxalines 22

    1-9-1. Antibacterial activity. 22

    1-9-2. Anticancer activities of quinoxalines 23

    Chapter Two: Discussion and review

    2-1. Preparation methods of arylglyoxales 25

    2-2. General synthesis method of aryl pyrido]2 and 3-[b pyrazine derivatives 27

    2-2-1. Synthesis of 3-phenylpyrido]2,3-[b-pyrazine. 28

    2-2-2. Synthesis of 3-(4-nitrophenyl)pyrido]2,3-[b-pyrazine. 28

    2-2-3. Synthesis of 3-(4-chlorophenyl)pyrido]2,3-[bpyrazine. 29

    2-2-4. Synthesis of 3-(4-fluorophenyl)pyrido]2,3-[bpyrazine. 29

    2-2-5. Synthesis of 3-(3-methoxyphenyl)pyrido]2,3-[bpyrazine. 30

    2-2-6. Synthesis of 3-(4-methoxyphenyl)pyrido]2,3-[bpyrazine. 30

    2-2-7. Synthesis of 3-(3,4-dimethoxyphenyl)pyrido]2,3-[bpyrazine. 31

    2-2-8. Synthesis of 3-(1,1)-biphenyl[4-yl)-pyrido]2,3-[b-pyrazine. 32

    2-3. Synthesis of 5-arylpyrazine-2,3-dicarbonitrile derivatives. 33

    2-3-1. Synthesis of 5-phenylpyrazine-3,2-dicarbonitrile. 33

    2-3-2. Synthesis of 5-(4-chlorophenyl)pyrazine-3,2-dicarbonitrile. 33

    2-3-3. Synthesis of 5-(4-methoxyphenyl)pyrazine-3,2-dicarbonitrile. 34

    2-3-4. Synthesis of 5-(]1,1-biphenyl[4-yl)-pyrazine-3,2-dicarbonitrile. 34

    2-3-5. Synthesis of 3-(4-bromophenyl)pyrido]2,3-[bpyrazine. 35

    2-4. Synthesis of 2-aryl quinoxalines 36

    2-4-1. Synthesis of 2-phenylquinoxaline. 37

    2-4-2. Synthesis of 2-(4-nitrophenyl)quinoxaline. 37

    2-4-3. Synthesis of 2-(4-fluorophenyl)quinoxaline. 38

    2-4-4. Synthesis of 2-(3-methoxyphenyl)quinoxaline. 38

    2-4-5. Synthesis of 2-(]1,1-biphenyl[4-yl)-quinoxaline. 39

    2-4-6. Synthesis of 2-methoxy-4-(quinoxalin-2-yl)phenol. 39

    2-4-7. Synthesis of 2-(3,4-dimethoxyphenyl)quinoxaline. 40

    2-5. Synthesis of 2-aryl 6-nitroquinoxalines 41

    2-5-1. Synthesis of 2-(4-fluorophenyl)-6-nitroquinoxaline. 42

    2-5-2. Synthesis of 2-(3,4-dimethoxyphenyl)-6-nitroquinoxaline. 42

    2-5-3. Synthesis of 2-(4-bromophenyl)-6-nitroquinoxaline. 43

    2-6. conclusion 44

    The third chapter: Experimental part

    3-1. Materials and devices 46

    3-2. Synthesis method of derivatives. 47

    3-2-1. General synthesis method of arylpyrido]2 and 3-[b]pyrazine derivatives 48

    3-2-2. General method of synthesis of 5-arylpyrazine-3,2-dicarbonitrile derivatives. 55

    3-2-3. General synthesis method of 2-aryl quinoxalines 59

    3-2-4. The general method for the synthesis of 2-aryl 6-nitroquinoxalines 67

    The fourth chapter of the spectrum appendix. 72

    Resources and sources. 89

     

     

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