Synthetizing method of coumarin compound

A technology for coumarins and synthesis methods, applied in the direction of organic chemistry and the like, can solve the problems of inapplicability of microwave method, unstable yield, troublesome synthesis operation, etc., and achieves simple and efficient product separation, green reaction conditions, and high conversion rate. Effect

Inactive Publication Date: 2015-03-25
ANHUI HYEA AROMAS
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  • Description
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Problems solved by technology

The disadvantage is that the raw materials 5-substituted-2,4-dihydroxyacetophenone and phenylacetyl chloride required for the synthesis of this method are toxic substances, and the solvent acetone is a highly toxic substance, which is not conducive to the synthesis purpose of green chemistry
But the disadvantage is that there is ethyl cyanoacetate in the raw materials used, the synthesis operation of this type of compound is troublesome and the yield is not high, and cyano salts are formed in the by-products
The disadvantage is that the yield of this method is not stable, the scope of application is narrow, and it is not suitable for the synthesis of some coumarin derivatives
However, the operation of this method is relatively complicated, and the microwave method is not suitable for economically optimized conditions in industrial production.

Method used

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  • Synthetizing method of coumarin compound
  • Synthetizing method of coumarin compound
  • Synthetizing method of coumarin compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Embodiment 1: the preparation of coumarin

[0030]

[0031] Add palladium chloride (0.05mmol, 8.9mg), 1,10-phenanthroline (0.1mmol, 18mg), copper acetate (0.4mmol, 73mg), phenol (1mmol, 94.1mg), methyl acrylate (0.5mmol, 43.1mg), sodium acetate (1.5mmol, 123mg), 1,4-dichlorobutane (4mL), stirred at 100°C, and detected the reaction by thin-layer chromatography until the raw material The basic conversion is complete, and the 24 reaction ends. After completion of the reaction, add ethyl acetate (10 mL) to the reaction solution, then wash with 5% sodium bicarbonate solution to remove unreacted phenol, separate the organic phase, extract the aqueous phase with ethyl acetate (10 mL×3), combine the organic phases, It was dried with anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation to obtain coumarin (134.45 mg) with a yield of 92%.

[0032] 1 H NMR (400MHz, CDCl 3 )δ (ppm) 6.33 (d, J = 9.5Hz, 1H), 7.17–7.23 (td, J = 8.2, 7.4, 1.5Hz...

Embodiment 2

[0033] Embodiment 2: the preparation of coumarin

[0034] Add palladium chloride (5mmol, 89mg), 1,10-phenanthroline (10mmol, 180mg), copper acetate (20mmol, 4.7g), phenol (100mmol, 9.41g ), methyl acrylate (55mmol, 4.74g), sodium acetate (100mmol, 8.1g), 1,4-dichlorobutane (300mL), stirred and reacted at 110°C, condensed and refluxed for 20 hours, and the detection reaction was basically completed. After the reaction was completed, wash with 5% sodium bicarbonate solution to remove unreacted phenol, separate the organic phase, extract the aqueous phase with ethyl acetate (50mL×3), combine the organic phases, and dry with anhydrous magnesium sulfate, filter, and remove by rotary evaporation. solvent to obtain coumarin (12.72g), yield 87%.

Embodiment 3

[0035] Embodiment 3: the preparation of 4-methoxycoumarin

[0036]

[0037] Add palladium chloride (0.05mmol, 8.9mg), 1,10-phenanthroline (0.1mmol, 18mg), copper acetate (0.5mmol, 91mg), 4-methoxy Phenylphenol (1mmol, 124.14mg), methyl acrylate (0.5mmol, 43.1mg), sodium acetate (1.5mmol, 123mg), 1,4-dichlorobutane (4mL), stirred at 120°C, and used TLC The reaction was detected by chromatography until the conversion of the starting material was basically complete, and the 18 reaction was completed. After completion of the reaction, add ethyl acetate (10 mL) to the reaction solution, then wash with 5% sodium bicarbonate solution to remove unreacted phenol, separate the organic phase, extract the aqueous phase with ethyl acetate (10 mL×3), combine the organic phases, It was dried with anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation to obtain coumarin (160.3 mg) with a yield of 91%.

[0038] 1 H NMR (400MHz, CDCl 3 )δ(ppm)2.39(s,3H),...

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PUM

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Abstract

The invention provides a synthetizing method of a coumarin compound. The coumarin compound is mildly and efficiently prepared by using a phenols compound with a substituent group and methyl acrylate as raw materials, performing a reaction in 1,4-dichlorobutane under the action of a catalyst of Pa(II)-Cu(II), a ligand and weak alkali, and performing a C-C coupling reaction. The synthetizing method disclosed by the invention is simple and convenient, is easy to operate, is high in conversion rate, and is higher in yield; fewer by-products are generated in a synthetizing process, the synthetizing method conforms to the requirements of green chemistry, and the synthetizing method is mild and efficient, so that the synthetizing method is suitable for industrial production.

Description

technical field [0001] The invention relates to a method for preparing organic compounds, in particular to a method for synthesizing coumarin compounds. Background technique [0002] Coumarin is a lactone compound that widely exists in nature, and it exists most in Rutaceae and Umbelliferae, followed by Leguminosae, Orchidaceae, Oleaceae, Solanaceae and Compositae, and a small amount comes from microorganisms. . It has physiological activities such as anti-AIDS, anti-tumor, and immune enhancement; and through the substitution and modification of different positions on the coumarin ring, different ranges of absorption and fluorescence emission wavelengths can be obtained, thereby displaying different colors and derivatives with strong fluorescence. In addition to being widely used as fluorescent whitening agents, fluorescent dyes and laser dyes, coumarin compounds are also used in electroluminescent materials, organic photosensitive dyes for solar cells, and biological prote...

Claims

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Application Information

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IPC IPC(8): C07D311/10C07D311/14C07D311/16
CPCC07D311/10C07D311/14C07D311/16
Inventor 董金龙王天义汪民富徐基龙
Owner ANHUI HYEA AROMAS
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