Method for preparing azide-substituted quinoline-2, 4-diketone through free radical tandem carbon cyclization reaction without metal catalysis

A metal-free catalysis, free-radical technology, used in organic chemistry, chemicals for biological control, fungicides, etc., can solve the problems of increased probability of side reactions, high production costs, and environmental pollution.

Inactive Publication Date: 2021-08-17
YANTAI UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] The purpose of the present invention is to solve the technical problems of high production cost, increased probability of side reactions and environmental pollution

Method used

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  • Method for preparing azide-substituted quinoline-2, 4-diketone through free radical tandem carbon cyclization reaction without metal catalysis
  • Method for preparing azide-substituted quinoline-2, 4-diketone through free radical tandem carbon cyclization reaction without metal catalysis
  • Method for preparing azide-substituted quinoline-2, 4-diketone through free radical tandem carbon cyclization reaction without metal catalysis

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specific Embodiment approach 1

[0034] Embodiment 1: In this embodiment, the method for preparing azide-substituted quinoline-2,4-dione by metal-free catalyzed series carbocyclization reaction is as follows:

[0035] At room temperature, add N-(2-cyanophenyl)-N-methacrylamide (1a) 60mg, diphenyldiselenide (PhSe) 2 46.8 mg, 145 mg of iodobenzenediethyl ester and 127 μL of azidotrimethylsilane (specification 93%) were finally reacted in 2 mL of dimethyl sulfoxide (DMSO), and the reaction tube was stirred at room temperature for 12 hours until Monitored by TLC analysis until the raw material is completely consumed, after the reaction is complete, the mixture was washed with H 2 O (15 mL) quenched with CH 2 Cl 2 (3×5mL) extraction, then the organic solvent was concentrated in vacuo, and the residue was purified by flash column chromatography, using a mixture of petroleum ether and ethyl acetate as eluent, Rf=0.44, to obtain 3-(azidomethyl) - 1,3-Dimethylquinoline-2,4(1H,3H)-dione (2a). Yield: 90%, 66 mg.

...

specific Embodiment approach 2

[0040] Specific embodiment 2: In this embodiment, the method for preparing azide-substituted quinoline-2,4-dione by metal-free catalyzed series carbocyclization reaction is as follows:

[0041] At room temperature, 65 mg of N-(2-cyano-3-fluorophenyl)-N-methacrylamide (1b), 46.8 mg of diphenyldiselenide, and iodobenzenediethyl ester were sequentially added to the reaction tube 145 mg and 127 μL of azidotrimethylsilane (93% strength) were finally reacted in 2 mL of dimethyl sulfoxide (DMSO) and the reaction tube was stirred at room temperature for 12 h until complete consumption of starting material as monitored by TLC analysis , after the reaction was complete, the mixture was washed with H 2 O (15 mL) quenched with CH 2 Cl 2 (3×5mL) extraction, then the organic solvent was concentrated in vacuo, and the residue was purified by flash column chromatography, using a mixture of petroleum ether and ethyl acetate as eluent, Rf=0.29, to obtain 3-(azidomethyl )-5-fluoro-1,3-dimethy...

specific Embodiment approach 3

[0045] Specific embodiment three: In this embodiment, the method for preparing azide-substituted quinoline-2,4-dione by metal-free catalyzed series carbocyclization reaction is as follows:

[0046] At room temperature, successively add 70 mg of N-(3-chloro-2-cyanophenyl)-N-methacrylamide (1c), 46.8 mg of diphenyldiselenide, and iodobenzenediethyl 145 mg and 127 μL of azidotrimethylsilane (93% strength) were finally reacted in 2 mL of dimethyl sulfoxide (DMSO) and the reaction tube was stirred at room temperature for 12 h until complete consumption of starting material as monitored by TLC analysis , after the reaction was complete, the mixture was washed with H 2 O (15 mL) quenched with CH 2 Cl 2 (3×5mL) extraction, then the organic solvent was concentrated in vacuo, and the residue was purified by flash column chromatography, using a mixture of petroleum ether and ethyl acetate as eluent, Rf=0.31, to obtain 3-(azidomethyl) -5-Chloro-1,3-dimethylquinoline-2,4(1H,3H)-dione (c...

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Abstract

The invention discloses a method for preparing azide-substituted quinoline-2, 4-diketone through free radical tandem carbon cyclization reaction without metal catalysis, and relates to the field of chemical preparation, in particular to a preparation method of quinoline-2, 4-diketone. The invention aims to solve the problems of high production cost, increased side reaction occurrence probability and environmental pollution due to adoption of metal catalysis. The method comprises the following steps: reacting methacrylamide, a pre-activated azidotrimethylsilane solution and dimethyl sulfoxide at room temperature, quenching the mixture with H2O, extracting for three times with CH2Cl2, concentrating an organic solvent in vacuum, and purifying residues through rapid column chromatography to obtain the azide-substituted quinoline-2, 4-diketone. The method solves the technical problems of high production cost, side reaction occurrence probability increase and environmental pollution caused by metal catalysis, and the compound prepared by the method has the activity of inhibiting phytopathogen, can be applied to prevention and treatment of phytopathogen, and can be applied to preparation of anti-phytopathogen drugs.

Description

technical field [0001] The invention relates to the field of chemical preparation, in particular to a preparation method of quinolinedione. Background technique [0002] Green sustainable chemistry is proposed to solve the global chemical pollution and resource depletion problems by establishing cleaner chemical production processes. The use of expensive metals and high temperature will lead to high production costs, increased chances of side reactions, and serious environmental pollution. In this case, organic reactions without metal participation and at room temperature are ideal strategies for green chemistry, but mild Reaction efficiency under certain conditions is a matter of great concern to chemists. It is a major challenge to find synthetic methods with high selectivity and high efficiency of chemical reactions to construct a series of valuable chemical structure frameworks. [0003] Organic azide compounds are widely used in fine chemical and pharmaceutical indust...

Claims

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Application Information

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IPC IPC(8): C07D215/22A01P3/00
CPCC07D215/22
Inventor 孙凯王薪张震李立梅刘颖杰
Owner YANTAI UNIV
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