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  3. Investigating the role of sodium hydrogen sulfate stabilized on silica bread to prepare some coumarin derivatives

Investigating the role of sodium hydrogen sulfate stabilized on silica bread to prepare some coumarin derivatives

Number of pages: 103 File Format: word File Code: 31861
Year: 2014 University Degree: Master's degree Category: Chemical - Petrochemical Engineering
Tags/Keywords: Coumarin - Coumarin derivatives - Nano silica - Pegman compression - Perkin reaction - Silica bread - Sodium hydrogen sulfate - Tonka beans
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  • Summary of Investigating the role of sodium hydrogen sulfate stabilized on silica bread to prepare some coumarin derivatives

    Chemistry - organic chemistry trend

    Abstract

    Coumarin or (2-H-chroman-2-one) and their derivatives are compounds that are mostly naturally present in many plants, including tonka beans. And they are considered an important class of the benzopyrone compound family.

    Coumarin and its derivatives are considered essential elements in many bioactive compounds such as anti-coagulant, anti-HIV, anti-tumor, antioxidant, anti-anxiety, anti-inflammatory, hypnotic, insecticide and anthelmintic. Derivatives (2-H-chromen-2-one) or coumarins are mainly synthesized through Pegman condensation reactions. This condensation includes Foli derivatives in the presence of -keto esters in the presence of an acid catalyst under reflux conditions, and the efficiency of the coumarin derivatives obtained in this way is very low and in a long period of time. Although many modified methods have been suggested, each of these proposed methods has disadvantages such as harsh conditions, low efficiency, short duration, expensive reagents, the formation of side products, and the difficulty of recovering the corresponding catalyst and reusing the catalyst. In this research work, we have used Pegman condensation reactions in the presence of phenolic derivatives and ethyl acetate and using sodium hydrogen sulfate stabilized on nano silica as a catalyst. We have presented an effective method for the synthesis of coumarin derivatives. This method has advantages, high product efficiency and reaction in a short period of time, easy purification and no risk for the environment

    Key words: Pegman condensation, sodium hydrogen sulfate, nano silica, coumarins

    -1- Introduction

    Coumarin, which can be identified with the suffix (2-H-chroman-2-one) in its compounds, is a colorless and aromatic crystalline substance from the benzopyrene family. Coumarins are mainly in the form of phenols in many plants, especially in high concentration in tonka bean, vanilla plant. So far, more than 1300 different types of these compounds have been identified. This compound was used as a fragrance in perfumery and also as an additive in food, which has been banned due to hepatotoxicity. Coumarin, after its laboratory synthesis in 1868, was used as an anticoagulant drug similar to dicoumarol, warfarin is the brand name of this drug (containing coumarin), which is used as an anticoagulant drug. [2-1] [

    Among the bioactive and medicinal activities of coumarin and its derivatives can be sleep-inducing, anthelmintic, insecticidal, and anticoagulant, anti-inflammatory, and anti-inflammatory activities. Due to the importance of coumarin and its derivatives, different methods have been presented for the synthesis of these compounds, which can be the condensation reaction of Packman [1], Perkin [2], Reformatsky [3], Whiting [4], Claisen [5] and He pointed out that Pacman's condensation reaction has been noticed due to its convenient synthesis. These reactions are carried out in the presence of phenolic derivatives and -ketoesters in the presence of acidic reagents such as HCl, H2SO4, COOH. Also, solid acid catalysts, which were less noticed due to the reaction in a long time and under high temperature and causing pollution from excess acid in the environment. In recent years, the use of Lewis acids such as AlCl3, InCl3, Yb(OTf)3, ZrCl4, some of which are sensitive to humidity and need to create special conditions to carry out the reaction, as well as their reaction mechanism is carried out at high temperature and for a long time. Recently, researchers have used catalysts containing metal hydrogen sulfates as a source of protonated and Lewis acids, which are both cheap and stable because the reaction is carried out in heterogeneous environments]. 3-4 We see coumarin as follows.                                         

    (images are available in the main file)

    1-2- History of coumarin

    Coumarin was first discovered in 1820 by the German scientist Vogel[6], who mistakenly thought this compound was benzoic acid. He determined that this substance is not benzoic acid, and in the next article in the Royal Academy of Medicine, he proposed a new substance called coumarin. After some studies were done, coumarin was synthesized in the laboratory for the first time in 1868 by the English chemist William Henry[8]. rtl;">1-3- The main methods of laboratory synthesis of coumarin derivatives

    1-3-1- Packman's compaction

    Usually in laboratories, coumarin is made by Perkin methods, which is done by the reaction between salicyl aldehyde and acid anhydride. and Packman's method, which in 1883 German scientist Hans von Packmann together with Karl Duesberg[9] was able to prepare coumarin derivatives from the condensation reaction between ketoester and phenolic derivatives. 

    1-3-2- Perkin reaction

    Our reaction between salicyl aldehyde and acid anhydride, which is known as the Perkin reaction, leads to coumarin according to the following reaction.

    Abstract:

    Coumarin or (2-H- chromen-2- one) and their derivatives are compounds that are naturally in many plants such as Tonka beans. That are an important class of benzopyrone compounds. Coumarin and its derivatives are in many bioactive components such as anticoagulants, anti-tumor, anti-oxidant, anti-anxiety, anti-inflammatory, anti HIV, sleeping, insecticides and anthelminticare important elements. coumarin and their derivatives mainly synthesized through condensation reactions. Thiscondensation involves phenol and ?-ketoesters that in the presence ofan acidcatalystunderrefluxoccurs.but the efficiency ofcoumarinderivativesobtainedin this methodis verylowandthereactiontimeisup. reaction time, expensive reagent, side products and difficulty in recovering the catalyst and reuseability of the catalysts.

    In thie work we repot an efficient method for the synthesis of coumarin using condensation reactions of phenols and ethyl acetoacetate in the presence of nano silica supported with sodium hydrogensulfate as a catalyst. This method has advantages, such as high yields and low reaction time, simple purification of the procedure, environmentally friendly procedure.

  • Contents & References of Investigating the role of sodium hydrogen sulfate stabilized on silica bread to prepare some coumarin derivatives

    List:

    Abstract

    1-1- Introduction. 1

    1-2- History of coumarin. 2

    1-3- The main laboratory synthesis methods of coumarin derivatives. 3

    1-3-1- Yepkman density. 3

    1-3-2- Perkin reaction. 3

    1-4- common methods of synthesis of coumarin derivatives. 4

    1-5- Biological properties. 7

    1-6- Pacman reaction mechanism. 8

    1-7- basic variables. 9

    1-7-1- Phenols 9

    1-7-2:-ketoesters 10

    1-8- Definition of nanomaterials. 11

    1-9- Nanocatalyst. 12

    1-9-1- Properties of nanocatalyst. 13

    1-9-2- nanosilica by sol-gel method. 15

    1-9-3- The method of performing the sol-gel process by chemical method. 18

    1-9-4- Cell-gel process steps. 20

    1-9-4-1- Preparation of homogeneous solution. 20

    1-9-4-2- sol formation 21

    1-9-4-3- gel formation. 23

    1-10- The importance of using ammonia in the process of forming sol-gel (silica nanoparticles) 25

    1-11- The importance of using hydrogen sulfate to stabilize nanoparticles 25

    1-11-2- Sodium hydrogen sulfate stabilized on silica. 26

    1-11-2-1- Preparation method of NaHSO4.SiO2 26

    1-11-3- Applications of sodium hydrogen sulfate stabilized on silica. 26

    1-12- The purpose of the research. 29

    1-13- Background of the research.. 30

    2-1- General specifications about solvents, raw materials, devices and work methods 34

    2-1-1- Solvents 34

    2-1-2- Raw materials. 35

    2-1-3- Devices 35

    2-2- Working method 36

    2-2-1- Nanosilica preparation method. 36

    2-2-2- Preparation method of catalyst NaHSO4.SiO2(nano) 36

    2-2-3- General method of synthesis of coumarin derivatives (2-H-chromen-2-one) 36

    2-2-3-1- Method of synthesis, 4-methyl-2-H-chromen-2-one. 37

    2-2-3-2- how to synthesize, 6-chloro-4-methyl-chroman-2-one (chlorocoumarin) 38

    2-2-3-3- how to synthesize, 7-chloro-4-hydroxy-chroman-2-one. 38

    2-2-3-4-how to synthesize the compound, 8-chloro-4-methyl-chromen-2-one. 39

    2-2-3-5- method of synthesis, 6-nitro-4-methyl-chroman-2-one (nitrocoumarin) 39

    2-2-3-6- method of synthesis, 7-nitro-4-methyl-chroman-2-one. 40

    2-2-3-7-how to synthesize, 8-hydroxy-4-methyl-chroman-2-one. 40

    2-2-3-8-how to synthesize, 7-hydroxy-4-methyl-chromen-2-one. 41

    2-2-3-9- how to synthesize, 4-methylnaphtho[b-1,2]pyran-2-one. 41

    2-2-3-10- how to synthesize, 6-amino-4-methyl-chromen-2-one (aminocoumarin) 42

    2-2-3-11- how to synthesize, 7 and 8-dihydroxy-4-methyl-chromen-2-one. 42

    2-2-3-12- how to synthesize, 6-methoxy-4-methyl-chroman-2-one (methoxycoumarin) 43

    2-2-3-13- how to synthesize 7-methoxy-4-methyl-chroman-2-one. 44

    3-1- Results and discussion. 48

    3-1-1- The role of the catalyst in the reaction speed. 48

    3-2- Coumarin derivatives with reactions and tables. 52

    3-2-1- Reaction and statistical table of the compound, 2-H-chromen-2-one. 52

    3-2-1-2- Examination of the FT-IR spectrum. 52

    2-3-2-3 reaction and statistical table of the compound, 6-chloro-4-methyl-chromen-2-one. 53

    3-2-2-1- Examination of the FT-IR spectrum. 54

    3-2-3-reaction and statistical table of the compound, 7-chloro-4-methyl-chromen-2-one. 55

    3-2-4-reaction and composition table, 8-chloro-4-methyl-chromen-2-one. 56

    3-2-5-reaction and statistical table of the compound, 6-nitro-4-methyl-chromen-2-one. 57

    3-2-5-1- Examination of the FT-IR spectrum. 58

    3-2-6-reaction and statistical table of the compound, 7-nitro-4-methylchroman-2-one. 59

    3-2-7- reaction and statistical table of the compound, 8-hydroxy-4-methyl-chromen-2-one 60

    3-2-7-1- FT-IR spectrum investigation. 61

    3-2-8-reaction and statistical table of the compound, 4-methylnaphtho[b-1,2]pyran-2-one. 62

    3-2-8-1- Examination of FT-IR spectrum. 63

    3-2-8-2- Review of spectrum ..............................1HNMR. 64

    3-2-8-3- Review of 13CNMR spectrum. 66

    3-2-9-reaction and statistical table of the compound, 6-amino-4-methyl-chromen-2-one. 68

    3-2-9-1- Examination of the FT-IR spectrum. 68

    3-2-9-2- 1 HNMR spectrum investigation in CDCl3 70

    3-2-10- reaction and statistical table, 7-hydroxy-4-methyl-chromen-2-one compound 71

    3-2-10-1- FT-IR spectrum investigation. 72

    3-2-10-2- Examining the 1HNMR spectrum in DMSO)) 73

    3-2-11- Reaction and statistical table of the compound, 6-methoxy-4-methyl-chromen-2-one. 75

    3-2-11-1- Examination of FT-IR spectrum.76

    3-2-11-2- Examining the 1HNMR spectrum in CDCl3)) 77

    3-2-12- Reaction and statistical table of the compound 7-methoxy-4-methyl-chromen-2-one. 79

    3-2-13- reaction and statistical table of the compound, 7 and 8-dihydroxy-4-methyl-chromen-2-one 79

    3-2-13-1- FT-IR spectrum investigation. 80

    3-2-13-2- Examining the 1HNMR spectrum in DMSO. 81

    3-2-13-3- Examining the 13CNMR spectrum. 83

    3-3- General table of synthesis of coumarin derivatives in this research. 85

    3-3-1- Discussion of table (3-16). 88

    3-4- Comparative table. 88

    3-4-1- Discussion of table (3-17) 89

    Conclusion. 90

    Suggestions. 91

     

    Source:

     

     

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Investigating the role of sodium hydrogen sulfate stabilized on silica bread to prepare some coumarin derivatives
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