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Method for synthesizing coumarin and derivatives thereof under catalysis of choline ionic liquids

A technology of ionic liquids and phenolic compounds, which is applied in the field of synthesis of coumarin and its derivatives, can solve the problems of expensive catalysts, cumbersome experimental treatment process, and environmental hazards, and achieve easy separation, good catalytic effect, and reaction conditions simple effect

Inactive Publication Date: 2014-03-05
HENAN NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, these methods still have certain disadvantages, such as expensive catalysts, cumbersome experimental treatment process, and environmental hazards.

Method used

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  • Method for synthesizing coumarin and derivatives thereof under catalysis of choline ionic liquids
  • Method for synthesizing coumarin and derivatives thereof under catalysis of choline ionic liquids
  • Method for synthesizing coumarin and derivatives thereof under catalysis of choline ionic liquids

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] Effect of Different Catalysts on Pechmann Reaction

[0020] Based on the reaction of resorcinol and ethyl acetoacetate, different choline ionic liquids are used to catalyze the reaction. The ratio of the amount of choline ionic liquid to the amount of resorcinol is 1:1 , the temperature of the oil bath was controlled at 90°C, no solvent was added, and the progress of the reaction was followed by TLC to optimize a suitable ionic liquid. The experimental results are shown in Table 1. It can be seen from Table 1 that [DMEA][HSO in entry1 4 ] has the best catalytic effect, and the yield can reach 87% after 1.5h of reaction.

[0021] Table 1 Catalytic effects of different choline-based ionic liquids on the Pechmann reaction

[0022]

Embodiment 2

[0024] Effects of Catalyst Consumption and Reaction Temperature on Pechmann Reaction

[0025] With resorcinol and ethyl acetoacetate as the reaction raw materials, the choline-based ionic liquid [DMEA][HSO 4 ] The conditions such as the dosage and temperature are optimized, and the results are shown in Table 2. First, we optimized the amount of choline ionic liquid in the range of 0.02-1.5 mmol, and found that when the amount of catalyst was in the range of 0.05-1.5 mmol, with the increase of the amount of choline ionic liquid, the yield of the target product was reversed. Decrease, continue to reduce the amount of choline-based ionic liquid to 0.02mmol (entry8), the yield dropped to 90%, which shows that the most appropriate when the amount of choline-based ionic liquid is 0.05mmol. The reaction was carried out at 25°C, 60°C, 90°C, and 120°C. At 25°C, no product was produced for 4 hours; at 60°C, for 5.5 hours, the yield was only 75%; at 120°C, Solids were quickly formed in...

Embodiment 3

[0029]Expansion of reaction substrates

[0030] According to the above optimization results, we choose to synthesize coumarin and its derivatives by Pechmann reaction under the optimal conditions. As can be seen from Table 3, in the choline-based ionic liquid [DMEA] [HSO 4 ] Under the condition of catalyst, monohydric phenol, dihydric phenol and trihydric phenol can all undergo Pechmann condensation reaction with ethyl acetoacetate, among which resorcinol has the highest activity. Due to the low activity of monohydric phenols, in [DMEA][HSO 4 ] almost no reaction when used as a catalyst, so the reaction (entry1-3) was carried out with substrates containing amino, methoxy and other strong electron-donating substituents, and the yields were 50% and 70% respectively. In addition, the activity of phenols is related to the position of substituents, such as p-aminophenol, p-hydroxyanisole (entry4, 5) does not react with ethyl acetoacetate; the electron-withdrawing substituents con...

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Abstract

The invention discloses a method for synthesizing coumarin and derivatives thereof under catalysis of choline ionic liquids. According to the technical scheme, the method is characterized in that the coumarin and the derivatives thereof are prepared from a phenolic compound and beta-ketonic acid or keto ester under the catalytic action of choline ionic liquids and the choline ionic liquids include an ionic liquid of melted binary acid and choline chloride, a functionalized acidic choline ionic liquid and a protonized choline ionic liquid. According to the method disclosed by the invention, the synthesized choline ionic liquid is used for Pechmann condensation reaction; the negative and positive ions of the ionic liquids are adjusted according to the catalytic effect based on different acid-base properties of the ionic liquids, so that better catalytic effect can be achieved; the choline ionic liquids take the place of dangerous concentrated sulfuric acid when the choline ionic liquids are used for catalyzing the Pechmann reaction; the reaction conditions are simple, the product is easy to separate and no by-product is generated; more importantly, the catalyst can be reused.

Description

technical field [0001] The invention relates to a synthesis method of coumarin and its derivatives, in particular to a method for catalyzing the synthesis of coumarin and its derivatives by a choline ionic liquid. Background technique [0002] Coumarin and its derivatives play an important role in natural products and organic synthesis. These compounds have important pharmaceutical and biological activities. They are intermediates in synthetic medicine, pesticides, dyes, and spices. They can also be used in fluorescent indicators, acid Alkaline indicators and food additives. In recent years, studies have found that coumarin and its derivatives are also of great research value in the preparation of anticoagulant, anticancer and other drugs. The traditional synthesis method of coumarin is to use resorcinol and ethyl acetoacetate as raw materials, and use concentrated sulfuric acid as a catalyst to carry out through condensation reaction. However, the selectivity of this synth...

Claims

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Application Information

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IPC IPC(8): C07D311/16B01J31/02B01J31/04
CPCB01J31/0285C07D311/16
Inventor 朱安莲李凌君李倩倩王键吉
Owner HENAN NORMAL UNIV
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