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A kind of preparation method of 4-aryl coumarin compound

An aryl coumarin and compound technology, which is applied in the field of preparation of 4-aryl coumarin compounds, can solve the problems of inability to recycle, long reaction time, poisonous catalyst, etc., and achieves short reaction time, simple operation, Ease of industrial production

Active Publication Date: 2019-03-26
INST OF PHARMACY SHANDONG PROV ACAD OF MEDICAL SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the above existing methods for synthesizing 4-aryl coumarins have disadvantages such as expensive raw materials, violent reaction, long reaction time, poisonous catalyst and cannot be recycled. Acyl chlorination of propiolic acid compounds and then combined with phenolic compounds (Synth.2001, 15:2247) is cumbersome to operate, and the acid chlorination needs to be strictly controlled anhydrous, and the conditions are harsh

Method used

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  • A kind of preparation method of 4-aryl coumarin compound
  • A kind of preparation method of 4-aryl coumarin compound
  • A kind of preparation method of 4-aryl coumarin compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0062] Embodiment one: the preparation of acidified montmorillonite K-10

[0063] Add 13g of montmorillonite K-10 to 130ml of sulfuric acid solution (mass concentration: 30%) to make a suspension, heat and reflux at 90-100°C for 4 hours, filter with suction, wash with distilled water until neutral, and vacuum at 40°C After drying, 12.95 g of acidified montmorillonite K-10 was obtained.

Embodiment 2

[0064] Example 2: Preparation of 4-(4'-methoxyphenyl)-7-hydroxycoumarin

[0065] 1. Add 25g (240mmol) malonic acid, 24ml (197.6mmol) p-methoxybenzaldehyde, 40ml (496mmol) pyridine, 2ml (20.4mmol) hexahydropyridine into a 100ml three-necked reaction flask, and heat to 75°C Reflux for 7 hours, complete the reaction, cool for 10 minutes, add 150ml of 3mol / ml glacial hydrochloric acid solution, let stand overnight, filter with suction, and wash the precipitate with 1000ml of water to obtain a white crude product. The crude product was recrystallized from absolute ethanol to obtain 31.2 g of white pure product 4-methoxyphenylacrylic acid, with a yield of 97.5%.

[0066] 2. Add 7.12g (40mmol) 4-methoxyphenylacrylic acid and 100ml (1717mmol) absolute ethanol to a 250ml three-necked reaction flask, add 4.4ml (60mmol) thionyl chloride dropwise, heat to 82°C, and reflux the reaction 2 hours until the raw material point completely disappeared, stop the reaction and cool for 10 minutes, ...

Embodiment 3

[0074] Example 3: Preparation of 4-(4'-methoxyphenyl)-7,8-dihydroxycoumarin

[0075] In a 100ml three-necked reaction flask, add 1.76g (10mmol) 4-methoxyphenylpropiolic acid, 1.39g (11mmol) pyrogallol, 20ml (196mmol) nitrobenzene, stir well, and heat to 100°C , then add 4g of sulfuric acid acidified montmorillonite K-10, TLC monitors the reaction progress (developing agent: dichloromethane:methanol=10:1), after 7 hours the reaction is complete, filter while hot, add 30ml petroleum ether in the filtrate, Stand overnight for natural crystallization, filter with suction, wash the precipitate with 20 ml of petroleum ether, and dry in a vacuum oven to obtain 1.9 g of white pure product with a yield of 66.9%.

[0076] IR: 3165(OH); 1685(C=O); 2971,1602,1560,1508,1442,1114,1043,1017,836(benzene ring); 1241,1177(C-O); 2841(-OCH 3 ).

[0077] 1 H NMR (600MHz, DMSO-d 6 )δ:3.84(s,3H),6.09(s,1H),6.80(d,J=8.8Hz,1H),6.85(d,J=8.7Hz,1H)7.10(d,J=8.7Hz,2H ), 7.46(t, J=5.7Hz, 2H), 9.42(s, 1...

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Abstract

The invention relates to the field of chemical synthesis, in particular to a preparation method of neoflavonoids. The preparation method is characterized by comprising the following steps of using substituted benzaldehyde as an initial raw material to be reacted with malonic acid to generate a substituted phenylacrylic acid compound; performing an addition reaction, an elimination reaction and the like on the substituted phenylacrylic acid compound, or performing acetylation so as to protect a phenolic hydroxyl group, then performing a bromination reaction and the elimination reaction so as to synthesize the substituted phenylpropiolic acid compound ; and using montmorillonite K-10 after being acidulated by sulfuric acid as a catalyst, enabling the substituted phenylpropiolic acid compound and a phenolic compound to perform a heating reaction so as to generate the neoflavonoids. Compared with the prior art, the preparation method of the neoflavonoids, disclosed by the invention, has the characteristics that raw materials are cheap, and easy to obtain, the operation is simple, the catalyst can be recovered for use, and the method is environmentally-friendly, the post-treatment is simple, and the production cost is low, and the method has a high popularization and application value.

Description

technical field [0001] The invention relates to the field of drug synthesis, in particular to a preparation method of 4-arylcoumarin compounds. Background technique [0002] 4-aryl coumarin natural compounds have various pharmacological activities, such as anti-oxidation (Synth, 2001, 15:2247; Biochimie. 2014, 107: 203; Chem. Biol. Interact. 2014, 214: 49), anti- Tumor (J.Med.Chem.2003,46(25):5437; Exp.Hematol.2008,36(12):1625; Bioorg.Med.Chem.Lett.2013,23(17):4785; J.Med .Chem.2011,54(9):3153), anti-plasmodium (Eur.J.Med.Chem.2010,45(3):864), antibacterial (Food.Chem.2010,121(4):1150; J.Ethnopharmacol.2013,147(1):259; Bioorg.Med.Chem.Lett.2013,23(22):6052), antifungal (Microbiology.2005,151(5):1691), anticoagulant ( Bioorg.Med.Chem.Lett.2006,16:257), etc., have important research value and application potential. [0003] At present, the method for synthesizing 4-aryl coumarin compounds mainly contains cross-coupling reactions such as Suzuki (Tetrahedron.Lett.2012,53(26):...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D311/18
CPCC07D311/18
Inventor 王晓静李娜孙捷孙敬勇王兵吴忠玉刘腾王英爱王双玲杨漫芸尚杰王建飞刘恒铫
Owner INST OF PHARMACY SHANDONG PROV ACAD OF MEDICAL SCI
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