Method for preparing pyrano [4,3-b] pyran derivatives by basic ionic liquid catalysis

A technology of pyran derivatives and basic ions, applied in chemical instruments and methods, chemical/physical processes, physical/chemical process catalysts, etc., can solve the problems of complex product purification process, high price, pollution, etc., and facilitate industrialization The effect of large-scale production, many times of recycling, and simple purification process

Active Publication Date: 2016-08-31
日照新睿招商发展有限公司
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AI Technical Summary

Problems solved by technology

[0004] The purpose of the present invention is to overcome the existing problems in the preparation of pyrano[4,3-b]pyran derivatives in ionic liquids in the prior art that the amount of ionic liquid used is large, the biodegradation is not easy, the preparation process is complicated and the price is relatively high. High, low raw material utilization rate, complex product purification process, and catalysts that cannot be recycled and easily cause environmental pollution, etc., and provide a basic ion with high catalytic activity, simple preparation process, low cost and easy biodegradation A liquid catalyst, a method for catalytically preparing pyrano[4,3-b]pyran derivatives with high raw material utilization rate, convenient product purification and direct recycling of the catalytic system

Method used

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  • Method for preparing pyrano [4,3-b] pyran derivatives by basic ionic liquid catalysis
  • Method for preparing pyrano [4,3-b] pyran derivatives by basic ionic liquid catalysis
  • Method for preparing pyrano [4,3-b] pyran derivatives by basic ionic liquid catalysis

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Experimental program
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Effect test

Embodiment 1

[0022] Add 1mmol p-chlorobenzaldehyde, 1mmol 4-hydroxyl-6-methylpyran-2-one, 1mmol malononitrile and 0.17mmol basic ionic liquid to the tank with stirring bar and condenser tube filled with 10ml water respectively. 50ml single mouth bottle. Heated to reflux for 21 minutes, TLC (thin plate chromatography) detection, the raw material point disappeared, cooled to room temperature, crushed the precipitated solid, stood still, filtered with suction, and the filter residue was washed with dimethylformamide and dried in vacuo to obtain 2-amino- 7-Methyl-5-oxo-4-(4-chlorophenyl)-4H, 5H-pyran[4,3-b]pyran-3-carbonitrile, the yield was 89%, the filtrate was directly added p-Chlorobenzaldehyde, 4-hydroxy-6-methylpyran-2-one and malononitrile were then reused.

[0023] 2-Amino-7-methyl-5-oxo-4-(4-chlorophenyl)-4H,5H-pyran[4,3-b]pyran-3-carbonitrile: m.p.231~233℃; IR (KBr): 3371, 3315, 3179, 2225, 1718cm -1 ; 1 H NMR (500MHz, DMSO-d 6 ): δ=2.14(s, 3H), 4.58(s, 1H), 6.51(s, 1H), 6.64(s,...

Embodiment 2

[0025] 1mmol o-chlorobenzaldehyde, 1mmol 4-hydroxy-6-methylpyran-2-one, 1mmol malononitrile and 0.18mmol basic ionic liquid were added to 10ml of water with stirring bar and condenser 50ml single mouth bottle. Heated to reflux for 27 minutes, TLC (thin plate chromatography) detection, the raw material point disappeared, cooled to room temperature, crushed the precipitated solid, stood still, filtered with suction, and the filter residue was washed with dimethylformamide and dried in vacuo to obtain 2-amino- 7-Methyl-5-oxo-4-(2-chlorophenyl)-4H, 5H-pyran[4,3-b]pyran-3-carbonitrile, the yield was 87%, and the filtrate was directly added o-Chlorobenzaldehyde, 4-hydroxy-6-methylpyran-2-one and malononitrile were then reused.

[0026] 2-Amino-7-methyl-5-oxo-4-(2-chlorophenyl)-4H,5H-pyran[4,3-b]pyran-3-carbonitrile: m.p.269~271℃; IR(KBr): 3379, 3312, 3173, 2204, 1715cm -1 ; 1 H NMR (500MHz, DMSO-d 6 ): δ=2.03(s, 3H), 4.39(s, 1H), 6.56(s, 1H), 6.91(s, 2H), 7.20~7.46(m, 4H)

Embodiment 3

[0028] 1mmol 2,4-dichlorobenzaldehyde, 1mmol 4-hydroxyl-6-methylpyran-2-one, 1mmol malononitrile and 0.19mmol basic ionic liquid were added to 14ml of water with stirring bar and a 50ml single-necked bottle with a condenser tube. Heated to reflux for 34 minutes, TLC (thin plate chromatography) detection, the raw material point disappeared, cooled to room temperature, crushed the precipitated solid, stood still, filtered with suction, and the filter residue was washed with dimethylformamide and dried in vacuo to obtain 2-amino- 7-methyl-5-oxo-4-(2,4-dichlorophenyl)-4H,5H-pyran[4,3-b]pyran-3-carbonitrile, the yield was 84%, the filtrate 2,4-dichlorobenzaldehyde, 4-hydroxy-6-methylpyran-2-one and malononitrile were directly added to the mixture for repeated use.

[0029] 2-Amino-7-methyl-5-oxo-4-(2,4-dichlorophenyl)-4H,5H-pyran[4,3-b]pyran-3-carbonitrile: m.p.233~ 235°C; IR (KBr): 3384, 3320, 3175, 2207, 1711cm -1 ; 1 H NMR (500MHz, DMSO-d 6): δ=2.16(s, 3H), 4.34(s, 1H), 6.4...

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Abstract

The invention discloses a method for preparing pyrano [4,3-b] pyran derivatives by basic ionic liquid catalysis, and belongs to the technical field of preparation of chemical materials. The molar ratio of aromatic aldehyde to 4-hydroxy-6-methylpyrane-2-ketone to an active methylene compound in preparation reaction is 1 to 1 to 1; the molar weight of the basic ionic liquid catalyst is 15%-20% of the molar weight of used aromatic aldehyde; the volume dose of reaction solvent water on the basis of milliliter is 10-14 times that of the aromatic aldehyde on the basis of millimole; the reflux reaction time is 15-45 minutes; the product is cooled to a room temperature after reaction is ended; suction filtration is carried out; filter residues are washed and dried in vacuum through dimethylformamide to obtain a pyrano [4,3-b] pyran derivative. Compared with the preparation method employing other ionic liquids as solvents, the method has the characteristics of being low in ionic liquid dosage, high in raw material utilization rate and the like; water is utilized as a reaction solvent; the operation in the overall preparation process is simple and convenient; and industrial large-scale application is facilitated.

Description

technical field [0001] The invention belongs to the technical field of chemical material preparation, and in particular relates to a method for preparing pyrano[4,3-b]pyran derivatives by catalyzing an alkaline ionic liquid. Background technique [0002] Pyran derivatives are a very important class of compounds with a wide range of biological and pharmacological activities, such as anti-allergic effects, hypoglycemic effects, antibacterial, anti-cancer activities, and are used for the treatment of allergic bronchitis, anti-developmental dysplasia and treatment diabetes etc. In addition, compounds containing pyran rings can also be transformed into pyridine series compounds with calcium ion regulating function. As one of the pyran derivatives, the pyrano[4,3-b]pyran derivative can also be used as an inhibitor of non-peptide HIV protease. Therefore, it is of great significance to study the preparation of pyrano[4,3-b]pyran derivatives. [0003] Ionic liquids are liquid salt...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D493/04B01J31/02
CPCB01J31/0239B01J31/0279C07D493/04
Inventor 岳彩波涂福燕吴胜华叶明富储昭莲彭金中
Owner 日照新睿招商发展有限公司
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