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A kind of green catalytic method for synthesizing spirooxindole derivatives

A spirooxindole derivative and green technology, which is applied in the field of green catalytic synthesis of spirooxindole derivatives, can solve the problems of large loss and achieve the effects of less loss, high alkali density and good catalytic activity

Active Publication Date: 2015-09-23
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 large amount of basic ionic liquid used in the process of catalytic synthesis of spirocyclic indole derivatives in the prior art and the loss in recycling, which requires the use of a large amount of volatile organic solvents, etc. Disadvantages, but to provide a higher basicity containing OH - The basic ionic liquid is used as a catalyst, and water is used as a method for catalytically synthesizing spirocyclic indole derivatives under solvent conditions

Method used

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  • A kind of green catalytic method for synthesizing spirooxindole derivatives
  • A kind of green catalytic method for synthesizing spirooxindole derivatives
  • A kind of green catalytic method for synthesizing spirooxindole derivatives

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Add 2mmol of isatin, 2mmol of malononitrile, 2mmol of 1,3-cyclohexanedione and 0.04mmol of basic ionic liquid into a 25ml single-necked bottle containing 4ml of water with a stirring bar and a condenser tube. Reacted under vigorous stirring at 80°C for 13 minutes, detected by TLC (thin plate chromatography), the raw material point disappeared, cooled to room temperature, and filtered with suction, the obtained filter residue was recrystallized with 90% ethanol aqueous solution (mass ratio), and dried to obtain pure 2-amino- 5-oxo-spiro[(4H)-5,6,7,8-tetrahydrochroman-4,3'-(3')-indole]-(1'H)-2'one- 3-carbonitrile, the yield is 91%. Isatin, malononitrile and 1,3-cyclohexanedione were directly added to the filtrate for repeated use.

[0027] 2-Amino-5-oxo-spiro[(4H)-5,6,7,8-tetrahydrobenzopyran-4,3'-(3')-indole]-(1'H)- 2'keto-3-carbonitrile: m.p.295~297℃; 1 H NMR (500MHz, DMSO-d 6 ): δ=1.91~1.93(m, 2H, CH 2 ), 2.28~2.35 (m, 2H, CH 2 ), 2.61~2.65 (m, 2H, CH 2 ), 6.77~...

Embodiment 2

[0029] Add 2mmol of isatin, 2mmol of malononitrile, 2mmol of 5,5-dimethyl-1,3-cyclohexanedione and 0.04mmol of basic ionic liquid into a 25ml single port with stirring bar and condenser tube filled with 6ml of water in the bottle. Reacted under vigorous stirring at 80°C for 8 minutes, TLC (thin plate chromatography) detection, the raw material point disappeared, cooled to room temperature, and suction filtered, the resulting filter residue was recrystallized with 90% ethanol aqueous solution (mass ratio), and dried to obtain pure 2-amino- 5-oxo-7,7-dimethyl-spiro[(4H)-5,6,7,8-tetrahydrochromene-4,3'-(3')-indole]-(1 'H)-2'keto-3-carbonitrile, yield 97%. Isatin, malononitrile and 5,5-dimethyl-1,3-cyclohexanedione were directly added to the filtrate for repeated use.

[0030] 2-Amino-5-oxo-7,7-dimethyl-spiro[(4H)-5,6,7,8-tetrahydrochroman-4,3'-(3')-indole ]-(1'H)-2'keto-3-carbonitrile: m.p.287~289℃; 1 H NMR (500MHz, DMSO-d 6 ):δ=1.01(s, 3H, CH 3 ), 1.05(s, 3H, CH 3 ), 2.16...

Embodiment 3

[0032] 2mmol isatin, 2mmol malononitrile, 2mmol 5-hydroxycoumarin and 0.04mmol basic ionic liquid were added to a 50ml single-necked bottle containing 8ml water with a stirring bar and a condenser tube. Reacted under vigorous stirring at 85°C for 18 minutes, TLC (thin plate chromatography) detection, the raw material point disappeared, cooled to room temperature, and suction filtered, the obtained filter residue was recrystallized with 90% ethanol aqueous solution (mass ratio), and dried to obtain pure 2-amino- 5-Oxo-spiro[(3'H)-indole-3',4-4(H)-pyroneno(3,2-c)chroman]-(1')-(1'H )-2'keto-3-carbonitrile, the yield was 92%. Isatin, malononitrile and 5-hydroxycoumarin were directly added to the filtrate for repeated use.

[0033] 2-Amino-5-oxo-spiro[(3'H)-indole-3',4-4(H)-pyroneno(3,2-c)chroman]-(1')- (1'H)-2'keto-3-carbonitrile: m.p.289~290℃; 1 H NMR (500MHz, DMSO-d 6 ): δ=6.84~8.04(m, 8H, ArH), 7.56(br s, 2H, NH 2 ), 10.66(s, 1H, NH)

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Abstract

The invention provides a method for synthesizing a screw hydroxyl indole derivative by virtue of green catalysis and belongs to the technical field of organic synthesis. In the method, the molar ratio of isatin, methylene cyanide to beta-diketone in a synthetic reaction is 1:1:1 in a synthetic reaction, the molar weight of basic ionic liquid serving as a catalyst is 2-5% of isatin, the dosage of water which is used as a reaction solvent is 2-5 times the molar weight (mmol) of isatin, the reaction temperature is 80-100 DEG C, and the reaction time is 8-35 DEG C. After the synthetic reaction, the product is cooled to room temperature and filtered, and filter residues are recrystallized and dried by using 90% ethanol water in mass ratio to acquire the pure screw hydroxyl indole derivative. Compared with a method for synthesizing the screw hydroxyl indole derivative by adopting other basic ionic liquid as the catalyst, the method provided by the invention has the characteristics of good catalytic activity, small dosage of catalyst, low loss during recycling, environment-friendly and economical reaction process and good convenience for industrial mass production.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a green catalytic method for synthesizing spirooxindole derivatives. Background technique [0002] Spirooxindole derivatives, as a class of heterocycles with special structures, have many important pharmacological and biological activities, such as anti-infection, bactericidal, anti-anxiety, anti-tumor and anti-AIDS activities. Therefore, the synthesis of such compounds and applied research has aroused widespread concern. Recently, it has been reported in relevant literature that a large number of spirooxindole derivatives were synthesized in one pot with three components using isatin, malononitrile and various types of ketones. The catalysts used for this type of reaction mainly include proline, PEG-400, ammonium chloride, ethylenediaminediacetic acid, benzyltriethylammonium chloride, cerium ammonium nitrate, sodium stearate, etc. However, the above-menti...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D491/107C07D491/20C07D471/20
CPCY02P20/584
Inventor 岳彩波高学频吴胜华诸荣孙
Owner ANHUI UNIVERSITY OF TECHNOLOGY