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Method for preparing hexahydroquinoline derivatives through high-acidity ionic liquid catalysis one-pot method

An ionic liquid, hexahydroquinoline technology, applied in organic chemistry and other directions, can solve the problems of ionic liquids that are not easy to biodegrade, low utilization rate of raw materials, cumbersome processing, etc., and achieves easy mass production, high utilization rate of raw materials, catalytic activity Good results

Active Publication Date: 2015-12-09
兰陵财金产业发展有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] The purpose of the present invention is to overcome the disadvantages of ionic liquids in the process of preparing hexahydroquinoline derivatives by catalysis of acidic ionic liquids in the prior art, such as difficult biodegradation, high price, cumbersome pretreatment before recycling, and low utilization rate of raw materials. Provide a method for catalytically preparing hexahydroquinoline derivatives under the condition of easy biodegradation, high catalytic activity, simple recycling process, and high utilization rate of reaction raw materials. High acidity ionic liquid is used as a green catalyst and ethanol is used as a solvent.

Method used

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  • Method for preparing hexahydroquinoline derivatives through high-acidity ionic liquid catalysis one-pot method
  • Method for preparing hexahydroquinoline derivatives through high-acidity ionic liquid catalysis one-pot method
  • Method for preparing hexahydroquinoline derivatives through high-acidity ionic liquid catalysis one-pot method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] 2mmol benzaldehyde, 2mmol 5,5-dimethyl-1,3-cyclohexanedione, 2mmol ethyl acetoacetate, 2.5mmol ammonium acetate and 0.05mmol high-acidity ionic liquid were added to 10ml of ethanol with stirring In a 50ml single-necked bottle with a sub and a condenser tube. Reflux reaction under vigorous stirring for 9 minutes, TLC (thin plate chromatography) detection, the raw material point disappeared, a large amount of solids precipitated after the reaction was completed and cooled to room temperature, crushed the solids, stood still, and suction filtered, and the resulting filter residue was vacuum-dried to obtain pure 2,7 , 7-trimethyl-5-oxo-4-phenyl-1,4,5,6,7,8-hexahydroquinoline-3-acetate, the yield was 95%. Add benzaldehyde, 5,5-dimethyl-1,3-cyclohexanedione, ethyl acetoacetate and ammonium acetate to the filtrate for repeated use.

[0026] 2,7,7-trimethyl-5-oxo-4-phenyl-1,4,5,6,7,8-hexahydroquinoline-3-acetate: m.p.206~208℃; 1 HNMR (300MHz, DMSO-d 6 ): δ=0.83(s, 3H), 1.02(...

Embodiment 2

[0028] 2mmol of p-chlorobenzaldehyde, 2mmol of 5,5-dimethyl-1,3-cyclohexanedione, 2mmol of ethyl acetoacetate, 2.5mmol of ammonium acetate and 0.05mmol of high acidity ionic liquid were added to the belt containing 12ml of ethanol In a 50ml single-necked bottle with a stir bar and a condenser. Reflux reaction under vigorous stirring for 8 minutes, TLC (thin plate chromatography) detection, the raw material point disappeared, a large amount of solids precipitated after the reaction was completed and cooled to room temperature, crushed the solids, stood, and suction filtered, and the obtained filter residue was vacuum-dried to obtain pure 4-( 4-Chlorophenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-acetate, yield 92% . Add p-chlorobenzaldehyde, 5,5-dimethyl-1,3-cyclohexanedione, ethyl acetoacetate and ammonium acetate to the filtrate for repeated use.

[0029]4-(4-Chlorophenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-acetate: m.p.244 ~246°C; 1 HN...

Embodiment 3

[0031] 2mmol p-nitrobenzaldehyde, 2mmol 5,5-dimethyl-1,3-cyclohexanedione, 2mmol ethyl acetoacetate, 2mmol ammonium acetate and 0.04mmol high acidity ionic liquid were added to the belt containing 14ml ethanol In a 50ml single-necked bottle with a stir bar and a condenser. Reflux reaction under vigorous stirring for 7 minutes, TLC (thin plate chromatography) detection, the raw material point disappeared, a large amount of solids precipitated after the reaction was completed and cooled to room temperature, crushed the solids, stood, and suction filtered, and the resulting filter residue was vacuum-dried to obtain pure 4-( 4-nitrophenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-acetate, the yield was 94 %. Add p-nitrobenzaldehyde, 5,5-dimethyl-1,3-cyclohexanedione, ethyl acetoacetate and ammonium acetate to the filtrate for repeated use.

[0032] 4-(4-nitrophenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-acetate: m.p. 245~247℃; 1 HNMR (300MHz, DMS...

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Abstract

The invention discloses a method for preparing hexahydroquinoline derivatives through a high-acidity ionic liquid catalysis one-pot method and belongs to the technical field of organic synthesis. In a preparation reaction, the molar ratio of aromatic aldehyde, 5, 5- dimethyl-1, 3-cyclohexanedione, acetoacetic ester and ammonium acetate is 1 to 1 to 1 to 1-1.5, the molar weight of a high-acidity ionic liquid catalyst is 2%-3% that of the aromatic aldehyde, the volume dose of the reaction solvent ethyl alcohol metered in milliliter is 5-7 times the molar weight of the aromatic aldehyde metered in millimole, the reaction pressure is one atmosphere pressure value, a backflow reaction is conducted for 5-20 minutes, the mixture is cooled to room temperature after the reaction is finished, a great amount of solid is separated out, suction filtration is conducted, and the hexahydroquinoline derivatives are obtained after the obtained filter residues are dried in a vacuum mode. Compared with a preparing method adopting other acidic ionic liquid as the catalyst, the method has the advantages that the catalyst is biodegraded easily, little in consumption, low in price and easy to obtain, the whole preparing process is high in raw material utilization rate and easy and convenient to operate, and industrial large-scale production is facilitated.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a method for preparing hexahydroquinoline derivatives in a one-pot method catalyzed by a high-acidity ionic liquid. Background technique [0002] 1,4-Dihydropyridine is an important class of organic compounds with good physiological activity and has wide applications in biology, medicine, clinical and other aspects, and can be used to treat hypertension, angina pectoris, congestive heart failure, local heart failure, etc. Cardiovascular diseases such as blood and atherosclerosis can also be used to treat gastrointestinal diseases, Raynaud's disease, and as an adjuvant drug for the treatment of pulmonary hypertension and epilepsy. In recent years, it has been found that 1,4-dihydropyridine derivatives are a new type of high-efficiency calcium ion antagonists. Hexahydroquinoline has a skeleton of 1,4-dihydropyridine ring, has similar activity to 1,4-dihydropy...

Claims

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Application Information

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IPC IPC(8): C07D215/54C07D215/20
CPCC07D215/20C07D215/54
Inventor 储昭莲岳彩波吴胜华
Owner 兰陵财金产业发展有限公司
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