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Method for preparing 2-amino-2-chromene derivatives by using polyamino ionic liquid as catalyst

An ionic liquid, catalytic preparation technology, applied in the direction of organic chemistry, etc., can solve the problem of the amount of alkaline ionic liquid and the loss of large amount in recycling.

Active Publication Date: 2014-12-10
ANHUI UNIVERSITY OF TECHNOLOGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] The purpose of the present invention is to overcome the disadvantages of the large amount of alkaline ionic liquid used in the prior art and the large amount of loss in the circulation during the preparation of 2-amino-2-chromene derivatives by alkaline ionic liquids, and provide a A method for catalytically preparing 2-amino-2-chromene derivatives under the condition of using an ionic liquid with a higher basicity with polyamino groups as a catalyst and water as a solvent

Method used

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  • Method for preparing 2-amino-2-chromene derivatives by using polyamino ionic liquid as catalyst
  • Method for preparing 2-amino-2-chromene derivatives by using polyamino ionic liquid as catalyst
  • Method for preparing 2-amino-2-chromene derivatives by using polyamino ionic liquid as catalyst

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Experimental program
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Effect test

Embodiment 1

[0022] 5mmol of benzaldehyde, 5mmol of malononitrile, 5mmol of α-naphthol and 0.25mmol of polyamino ionic liquid were added to 2ml of water in a 50ml single-necked bottle with a stirring bar and a condenser. Reflux reaction for 5 minutes under vigorous stirring, TLC (thin plate chromatography) detection, the raw material point disappeared, cooled to room temperature, suction filtered, and the resulting filter residue was recrystallized with a mixed solution of dimethylformamide and water (volume ratio: 30:70) , and obtained pure 2-amino-3-cyano-4-phenyl-4H-benzo[h]chromene after vacuum drying with a yield of 95%. Add benzaldehyde, malononitrile and α-naphthol directly to the filtrate for repeated use.

[0023] 2-Amino-3-cyano-4-phenyl-4H-benzo[h]chromene: 1 H NMR (300MHz, CDCl 3 ): δ=4.91(s, 1H, CH), 7.00(d, J=8.4Hz, 1H, ArH), 7.24~7.36(m, 5H, ArH), 7.50~7.62(m, 3H, ArH), 7.77 (d, J=7.8Hz, 1H, ArH), 8.19(d, J=8.4Hz, 1H, ArH)

Embodiment 2

[0025] 5mmol of benzaldehyde, 5mmol of malononitrile, 5mmol of β-naphthol and 0.25mmol of polyamino ionic liquid were respectively added to 2ml of water in a 50ml single-necked bottle with a stirring bar and a condenser tube. Reflux reaction for 10 minutes under vigorous stirring, TLC detection, the raw material point disappeared, cooled to room temperature, suction filtration, the resulting filter residue was recrystallized with a mixture of dimethylformamide and water (volume ratio: 30:70), and dried in vacuo to obtain Pure 2-amino-3-cyano-4-phenyl-4H-benzo[f]chromene in 93% yield. Add benzaldehyde, malononitrile and β-naphthol directly to the filtrate for repeated use.

[0026] 2-Amino-3-cyano-4-phenyl-4H-benzo[f]chromene: 1 H NMR (300MHz, CDCl 3 ): δ=5.27(s, 1H, CH), 6.93(s, 2H, NH 2 ), 7.14~7.36(m, 5H, ArH), 7.38~7.41(m, 3H, ArH), 7.77~7.92(m, 3H, ArH)

Embodiment 3

[0028] 5mmol of 4-methoxybenzaldehyde, 5mmol of malononitrile, 5mmol of α-naphthol and 0.30mmol of polyamino ionic liquid were respectively added to a 50ml single-necked bottle containing 3ml of water with a stirring bar and a condenser tube. Reflux reaction for 25 minutes under vigorous stirring, TLC detection, the raw material point disappeared, cooled to room temperature, suction filtration, the resulting filter residue was recrystallized with a mixture of dimethylformamide and water (volume ratio: 30:70), and dried in vacuo to obtain Pure 2-amino-3-cyano-4-(4-methoxyphenyl)-4H-benzo[h]chromene in 92% yield. Directly add 4-methoxybenzaldehyde, malononitrile and α-naphthol to the filtrate for repeated use.

[0029] 2-Amino-3-cyano-4-(4-methoxyphenyl)-4H-benzo[h]chromene: 1 H NMR (400MHz, CDCl 3 ):δ=3.83(s, 3H, CH 3 ), 4.75 (s, 2H, NH 2), 4.84(s, 1H, CH), 6.86(d, J=8.4H, 2H, ArH), 7.05(d, J=8.4Hz, 1H, ArH), 7.17(d, J=8.4Hz, 2H, ArH), 7.51~7.60(m, 3H, ArH), 7.81(d, J=6.0H...

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Abstract

The invention provides a method for preparing 2-amino-2-chromene derivatives by using a polyamino ionic liquid as a catalyst, belonging to the technical field of organic synthesis. The method comprises the following steps: reacting aromatic aldehyde, malononitrile and naphthol in a mol ratio of 1:1:1 under reflux for 4-40 minutes, wherein the polyamino ionic liquid catalyst accounts for 5-8 mol% of the aromatic aldehyde, and the volume (ml) of the reaction solvent water is 40-60% of the molar weight (mmol) of the aromatic aldehyde; and after the reaction is finished, cooling to room temperature, carrying out vacuum filtration, recrystallizing, and drying to obtain the pure 2-amino-2-chromene derivatives. The filtrate can be repeatedly used without any treatment, and the reaction yield is not obviously lowered. Compared with other preparation methods using a Lewis alkaline ionic liquid as a catalyst, the method provided by the invention has the characteristics of higher catalytic activity, lower catalyst consumption, low loss due to cyclic use, and the like, and is convenient for industrialized large-scale production in the preparation process.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a method for preparing 2-amino-2-chromene derivatives by catalyzing polyamino ionic liquids. Background technique [0002] 2-Amino-2-chromene is a very important class of organic compounds, and its derivatives have a wide range of pharmacological and biological activities, such as anti-hypoplastic, anti-allergic and anti-cancer activities. In addition, it can also be used as dyes, cosmetics and biodegradable pesticides. Such compounds are usually prepared by a three-component "one-pot" reaction of aromatic aldehydes, active methylene compounds and phenols, and organic bases such as piperidine and hexahydropyridine are commonly used as catalysts. However, it has the disadvantages of long reaction time, medium yield, and cumbersome post-treatment. In recent years, some environmentally friendly catalysts such as (NH 4 ) 2 HPO 4 、KF / Al 2 o 3 , I 2 / K 2 ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D311/92
CPCC07D311/92
Inventor 岳彩波杜勤杰吴胜华储昭莲陆良俊朱琳
Owner ANHUI UNIVERSITY OF TECHNOLOGY