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Method for preparing isocoumarin and derivatives thereof

A compound and reaction technology, applied in the field of preparation of isocoumarins and derivatives thereof, can solve the problems of complex preparation of raw materials, numerous synthesis routes, high price, etc., and achieve simple and easy-to-obtain raw materials, high synthesis yield and simple operation. Effect

Inactive Publication Date: 2012-03-21
TSINGHUA UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The traditional synthetic method has many synthetic routes and relatively low yield
Recently, transition metals (gold, palladium, silver, etc.) are used to catalyze the intramolecular cyclization of alkynes to synthesize isocoumarin structures. Although the yield of this method is high, the price of gold, palladium, etc. is expensive, and the preparation of raw materials is also complicated.

Method used

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  • Method for preparing isocoumarin and derivatives thereof
  • Method for preparing isocoumarin and derivatives thereof
  • Method for preparing isocoumarin and derivatives thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] The preparation of embodiment 1,3-methylisocoumarin (R in structural formula I 1 = Methyl, R 2 =R=H)

[0027] In the reactor of 25mL, add o-iodobenzoic acid (1.0mmol, 248.0mg) successively, CuI (0.1mmol, 19.0mg), K 3 PO 4 (2.0mmol, 424.0mg), finally add acetylacetone (1.0mmol, 102.0μL), DMF (2mL), seal the reactor, and stir at 120°C for 24h. After the reaction system was cooled, 5 mL of water was added to quench the reaction, and 15 mL of ethyl acetate was used to extract three times. The filtrates were combined and washed twice with water and once with saturated brine. Magnesium sulfate was added to dry for 30 minutes, filtered, and the filtrate was concentrated by rotary evaporation to obtain a crude product. The crude product is separated by column (200-300 mesh silica gel) with a mixture of petroleum ether: ethyl acetate = 5:1 (v / v) as eluent to obtain a white solid product with a purity of more than 99%. Soybean 120.0mg, isolated yield 76%.

[0028] Structura...

Embodiment 2

[0032] The preparation of embodiment 2,3-ethylisocoumarin (R in structural formula I 1 = ethyl, R 2 =R=H)

[0033] In the reactor of 25mL, add o-iodobenzoic acid (1.0mmol, 248.0mg) successively, CuI (0.1mmol, 19.0mg), K 3 PO 4 (2.0mmol, 424.0mg), finally added 3,5-heptanedione (1.0mmol, 138.0μL), DMF (2mL), sealed the reactor, and stirred at 120°C for 24h. After the reaction system was cooled, 5 mL of water was added to quench the reaction, and 15 mL of ethyl acetate was used to extract three times. The filtrates were combined and washed twice with water and once with saturated brine. Magnesium sulfate was added to dry for 30 minutes, filtered, and the filtrate was concentrated by rotary evaporation to obtain a crude product. The crude product is separated by column (200-300 mesh silica gel) with a mixture of petroleum ether: ethyl acetate=5:1 (v / v) as an eluent to obtain a white solid product 3-ethylisosin with a purity of more than 99%. Soybean 130.0mg, isolated yield 7...

Embodiment 3

[0038]The preparation of embodiment 3,3-phenylisocoumarin (R in structural formula I 1 = phenyl, R 2 =R=H)

[0039] In a 25mL reactor, add o-iodobenzoic acid (1.0mmol, 248.0mg), dibenzoylmethane (1.0mmol, 224mg), CuI (0.1mmol, 19.0mg), K 3 PO 4 (2.0 mmol, 424.0 mg), and finally 2 mL of DMF was added as a solvent, the reactor was sealed, and the mixture was stirred at 120° C. for 24 h. After the reaction system was cooled, 5 mL of water was added to quench the reaction, and 15 mL of ethyl acetate was used to extract three times. The filtrates were combined and washed twice with water and once with saturated brine. Magnesium sulfate was added to dry for 30 minutes, filtered, and the filtrate was concentrated by rotary evaporation to obtain a crude product. The crude product is separated by column (200-300 mesh silica gel) with a mixture of petroleum ether: ethyl acetate = 10:1 (v / v) as eluent to obtain a white solid product with a purity of more than 99%. Soybean 150.0mg, i...

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Abstract

The invention discloses a method for preparing isocoumarin and derivatives thereof, comprising the following steps of: putting an o-halogen benzoic acid, a 1, 3-dicarbonyl compound, cuprous salt and alkali in a reaction vessel, adding a dimethyl formamide (DMF) solvent into the reaction vessel, hermetically stirring at a temperature of 100-120 DEG C, reacting for 12-24 hours, quenching the reaction, extracting, washing, drying, concentrating and purifying the reaction liquid and obtaining an end product. The synthetic method of the isocoumarin and the derivatives thereof is scientific and reasonable and has the characteristics of high synthetic yield, good selectivity, easiness in purifying the products and the like; and the isocoumarin derivatives with various substituent groups, which cannot be synthetized by utilizing the other methods, can be synthetized and obtained.

Description

technical field [0001] The invention relates to a preparation method of isocoumarin and its derivatives. Background technique [0002] Isocoumarin refers to a class of compounds with a benzopyrone skeleton structure, which was originally isolated from metabolites of plants and microorganisms, and is named for its very similar skeleton and natural source to coumarin. [0003] Isocoumarin and its derivatives have physiological and biological activities such as antibacterial, anti-inflammatory, anticancer, protease inhibition and herbicide; at the same time, isocoumarin is a very useful intermediate for the synthesis of heterocyclic and carbocyclic compounds; in addition, it has recently been found that isocoumarin And its derivatives have obvious anticancer activity, so the research on the synthesis of such compounds is more active. Traditional synthetic methods have many synthetic routes and relatively low yields. Recently, transition metals (gold, palladium, silver, etc.) ...

Claims

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Application Information

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IPC IPC(8): C07D311/76
Inventor 席婵娟蔡尚军
Owner TSINGHUA UNIV
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