CN113620891B - Method for preparing quinoxaline-2-ketone derivative by controllable catalysis - Google Patents
Method for preparing quinoxaline-2-ketone derivative by controllable catalysis Download PDFInfo
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Abstract
The invention relates to a method for preparing quinoxaline-2-ketone derivatives by controllable catalysis, which comprises the following steps: adding a Selectfluor reagent into an organic solvent, carrying out ultrasonic dissolution, respectively adding a quinoxaline-2-ketone compound, an alcohol and an additive into the organic solvent, stirring and reacting at room temperature under the irradiation of a light source, tracking by TLC until the quinoxaline-2-ketone compound serving as a raw material completely reacts, finishing the reaction, carrying out post-treatment, and carrying out column chromatography separation and purification to obtain a 3-alkoxy quinoxaline-2-one derivative or a 3-hydroxyalkyl quinoxaline-2-ketone derivative. The method takes clean visible light as reaction energy, has simple and efficient preparation process, convenient operation, mild conditions, environmental protection and wide substrate application range, and is suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for preparing quinoxaline-2-ketone derivatives by controllable catalysis.
Background
The quinoxalinone is a pharmacophore of a plurality of compounds with biological activity, and the derivatives synthesized by taking the quinoxalinone as a structural mother nucleus have various biological activities, can be used as an antitumor agent, an HIV-1 reverse transcriptase inhibitor, an N-methyl-D-aspartate receptor antagonist, an anti (fungal) agent, an anticoagulant, a hypoglycemic agent and the like, and have important application values. In the past decades, great efforts have been made to synthesize quinoxalinone compounds, and especially C-3 functionalization, such as alkylation, arylation, acylation, amination and phosphorization, has been widely reported by researchers. Among them, 3-alkoxy quinoxaline-2-one and 3-hydroxyalkyl quinoxaline-2-one derivatives are very important compounds and have wide application in the field of medicines, thus becoming a popular subject for chemists to study.
For the preparation of 3-alkoxy quinoxaline-2-ketone, zhou et al report (adv. Synth. Catal.,2019,361,5371) that rhodamine 6G is used as a photocatalyst, quinoxaline-2-ketone and isopropanol are used as raw materials, and 3-alkoxy substituted quinoxaline-2-ketone is obtained by reaction.
The reaction of hydroxyalkylation at C-3 has also been reported in the past. Fu et al (org. Chem. Front.,2018,5,3382) reported that quinoxaline-2-ones were reacted with isopropanol to give 3-hydroxyalkyl-substituted quinoxaline-2-ones using copper oxide as catalyst and TBPB as oxidant.
However, the research methods for introducing alkoxy and hydroxyalkyl onto the quinoxalinone skeleton in the prior art are few, and especially the synthesis method for introducing alkoxy or hydroxyalkyl onto the C3 position of quinoxalin-2-one under the control of an oxidation system has not been reported so far, and the need for continuous research and exploration still exists, which is the basis and the motivation for completing the invention.
The photochemical reaction is a green and efficient reaction mode, the reaction condition is mild, and the operation is safe and simple. In addition, photochemical reaction has the characteristics of atom economy, high catalytic efficiency and the like, and has become a popular field of organic synthesis research in recent years. To date, photocatalysts have been dominated by homogeneous photocatalysts such as Ru or Ir complexes and organic dyes in the visible light catalysis process, limiting their scale-up and long-term use in the pharmaceutical industry. Therefore, there is still much room for development of a novel process for alkoxylation and hydroxyalkylation of the C3 position of quinoxalin-2-ones from the sustainable and environmental point of view.
Disclosure of Invention
The invention provides a method for preparing quinoxaline-2-ketone derivatives (3-substituent quinoxaline-2-ketone derivatives) by controllable catalysis, and particularly provides a method for preparing 3-alkoxy substituted quinoxalinone and 3-hydroxyalkyl substituted quinoxalinone derivatives by controllable catalysis.
In order to achieve the technical purpose, the invention adopts the technical scheme that:
a process for the controlled catalytic preparation of quinoxalin-2-one derivatives comprising the steps of:
adding a Selectfluor reagent into an organic solvent, carrying out ultrasonic dissolution, respectively adding a quinoxaline-2-ketone compound shown in a formula (I), an alcohol shown in a formula (II) and an additive into the organic solvent, stirring for reaction at room temperature under the irradiation of a light source, tracking by TLC until the quinoxaline-2-ketone compound as a raw material completely reacts, finishing the reaction, carrying out post-treatment, and carrying out column chromatography separation and purification to obtain a target compound 3-alkoxy quinoxaline-2-ketone derivative shown in a formula (III) or a target compound 3-hydroxyalkyl quinoxaline-2-ketone derivative shown in a formula (IV);
wherein R is 1 Is any one of H, methyl, ethyl, chlorine and bromine; r 2 Is any one of H, methyl, ethyl and benzyl; r 3 、R 4 Any one selected from the following groups: H. methyl, ethyl, cyclopentyl, cyclohexyl.
Preferably, the mass ratio of the quinoxaline-2-one compound to the Selectfluor reagent is 1:1 to 3, more preferably 1:1.5.
preferably, the organic solvent is selected from one of the following: acetone, acetonitrile, dichloroethane, more preferably acetonitrile.
Preferably, the mass ratio of the quinoxaline-2-one compounds, the alcohols and the additives is 1:3 to 10:1 to 5, more preferably 1:5:3.
preferably, the additive is any one of acetic acid, trifluoroacetic acid, sulfuric acid and hydrochloric acid. The product of this reaction is a 3-alkoxyquinoxalin-2-one derivative represented by formula (III), more preferably acetic acid.
Preferably, the additive is any one of tert-butyl hydroperoxide, tert-butyl perbenzoate, sodium persulfate, potassium persulfate, and ammonium persulfate. The product of this reaction is a 3-hydroxyalkyl quinoxaline-2-one derivative of formula (IV), more preferably tert-butyl perbenzoate.
Preferably, the light source is selected from one of the following: blue light, white light, green light, more preferably blue light.
Preferably, the preparation method comprises the following steps: under the irradiation of a blue LED lamp, the quinoxaline-2-ketone compound and alcohol are taken as substrates, acetonitrile is taken as a solvent, and under the action of a Selectfluor reagent and an additive, the quinoxaline-2-ketone compound is subjected to alkoxylation reaction or hydroxyalkylation reaction. When the additive is acidic substances such as acetic acid and the like, the product is a 3 alkoxy quinoxaline 2 ketone derivative; when the additive is an oxidant such as tert-butyl perbenzoate, the product is a 3 hydroxyalkyl quinoxaline 2 ketone derivative. The preparation route of the invention is shown in figure 1.
The reaction time is preferably 6 to 12 hours, more preferably 8 hours.
Preferably, the post-treatment step is: adding water and an organic extracting agent into a reaction liquid system for extraction and liquid separation, drying an obtained organic layer by anhydrous sodium sulfate, concentrating under reduced pressure to remove the solvent, separating the concentrate by column chromatography, collecting eluent containing a target product by taking a mixed solvent of petroleum ether and ethyl acetate as an eluent, and evaporating to remove the solvent to obtain the 3-alkoxy quinoxaline-2-one derivative shown in the formula (III) or the 3-hydroxyalkyl quinoxaline-2-one derivative shown in the formula (IV).
Preferably, the organic extractant is ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate in the eluent is 4-20: 1.
the invention has the beneficial effects that:
(1) The method takes the light energy as an energy source for realizing the C3-site alkoxylation and the hydroxyalkylation of the quinoxaline-2-ketone, and has the advantages of mild reaction conditions, clean energy, green and safe reaction;
(2) The method for synthesizing the 3-substituent quinoxaline-2-one derivative does not need the participation of a metal catalyst and an organic dye, saves resources and reduces the discharge of waste;
(3) According to the synthesis method of the 3-substituent quinoxaline-2-ketone derivative controlled by the oxidation system, under the action of a Selectfluor reagent, only an additive needs to be changed, such as acetic acid is changed into tert-butyl perbenzoate, and the reaction product 3-alkoxy quinoxaline-2-ketone derivative can be converted into the 3-hydroxyalkyl quinoxaline-2-ketone derivative;
(4) The method for synthesizing the 3-substituent quinoxaline-2-ketone derivative has the characteristics of easily obtained reaction substrate, good reaction selectivity, simple operation, high product yield and the like.
Drawings
FIG. 1 is a preparation scheme of the present invention;
FIG. 2 is a nuclear magnetic hydrogen spectrum of 3-isopropoxy-1-methylquinoxalin-2 (1H) -one obtained by the preparation of example 1;
FIG. 3 is a nuclear magnetic hydrogen spectrum of 3- (2-hydroxyprop-2-methyl) -1-methylquinoxalin-2 (1H) -one prepared in example 2.
Detailed Description
The invention is further illustrated by the following examples, without limiting the scope of the invention. Those skilled in the art can and should understand that any simple changes or substitutions based on the spirit of the present invention should fall within the protection scope of the present invention.
Example 1
Preparation of 1-methylquinoxalinone
2-hydroxyquinoxalinone (12mmol, 1.75g), potassium hydroxide (422mmol, 2.36g) and 15mL of N, N-Dimethylformamide (DMF) are respectively added into a 100mL round-bottomed flask, stirred under ice bath, then a DMF solution of methyl iodide (14.4mmol, 2g) is added dropwise into the round-bottomed flask, and after the dropwise addition is finished, the reaction is continued for 6 hours at room temperature, and the reaction is detected by TLC. After the reaction is finished, washing the reaction solution by using a saturated ammonium chloride solution, extracting by using ethyl acetate, washing an organic phase by using common salt water, separating out an organic phase, drying, spin-drying, purifying by using a column by using a ratio of petroleum ether to ethyl acetate (10.
Synthesis of 3-isopropoxy-1-methylquinoxaline-2 (1H) -one
In a 50mL round-bottom flask, a Selectfluor (15mmol, 5.3g) reagent is added into acetonitrile (20 mL), ultrasonic dissolution is carried out, 1-methylquinoxalinone (10mmol, 1.6 g), isopropanol (50mmol, 3g) and acetic acid (30mmol, 1.8g) are added into the solvent, stirring and reaction are carried out for 8 hours at room temperature under the irradiation of blue light, TLC is followed until the reaction of the quinoxaline-2-one compound is completed, water and ethyl acetate are added into a reaction liquid system for extraction and liquid separation, the obtained organic layer is dried by anhydrous sodium sulfate, reduced pressure concentration is carried out to remove the solvent, the concentrate is separated by column chromatography, a mixed solvent of petroleum ether and ethyl acetate is used as an eluent, eluent containing a target product is collected and the solvent is distilled off, and then 1.83g of 3-isopropoxy-1-methylquinoxalin-2 (1H) -one is obtained, and the yield is 84%.
The nuclear magnetic hydrogen spectrum of the prepared 3-isopropoxy-1-methylquinoxaline-2 (1H) -one is shown in figure 2.
Example 2
Synthesis of 3- (2-hydroxypropane-2-methyl) -1-methylquinoxalin-2 (1H) -one
In a 50mL round-bottom flask, selectfluor (15mmol, 5.3g) reagent is added into acetonitrile (20 mL), ultrasonic dissolution is carried out, 1-methylquinoxalinone (10mmol, 1.6 g), isopropanol (50mmol, 3g) and tert-butyl perbenzoate (30mmol, 5.8g) are added into the solvent, the mixture is stirred and reacted for 8 hours at room temperature under the irradiation of blue light, TLC is followed until the reaction of the raw material quinoxalin-2-one compound is completed, water and ethyl acetate are added into a reaction liquid system for extraction and liquid separation, the obtained organic layer is dried by anhydrous sodium sulfate, the solvent is removed by decompression concentration, the concentrate is separated by column chromatography, the eluent containing the target product is collected by taking a mixed solvent of petroleum ether and ethyl acetate as an eluent, and the solvent is distilled off, so that 1.81g of 3- (2-hydroxypropan-2-methyl) -1-methylquinoxalin-2 (1H) -one is obtained, and the yield is 83%.
The nuclear magnetic hydrogen spectrum of the prepared 3- (2-hydroxypropane-2-methyl) -1-methylquinoxaline-2 (1H) -ketone is shown in figure 3.
Example 3
Preparation of 1-ethylquinoxalinone
2-hydroxyquinoxalinone (12mmol, 1.75g), potassium hydroxide (422mmol, 2.36g) and 15mL of N, N-Dimethylformamide (DMF) are respectively added into a 100mL round-bottomed flask, stirred under ice bath, then a DMF solution of ethyl iodide (14.4mmol, 2 2g) is added dropwise into the round-bottomed flask, and after the dropwise addition is finished, the reaction is continued for 6 hours at room temperature, and the reaction is detected by TLC. After the reaction is finished, washing the reaction solution with saturated ammonium chloride solution, extracting with ethyl acetate, washing the organic phase with brine again, separating out the organic phase, drying, spin-drying, purifying by taking the ratio of petroleum ether to ethyl acetate (10.
Synthesis of 3-isopropoxy-1-ethylquinoxaline-2 (1H) -one
In a 50mL round bottom flask, selectfluor (15mmol, 5.3g) reagent is added into acetonitrile (20 mL), ultrasonic dissolution is carried out, 1-ethyl quinoxalinone (10mmol, 1.7g), isopropanol (50mmol, 3g) and acetic acid (30mmol, 1.8g) are added into the solvent, stirring reaction is carried out for 8 hours at room temperature under blue light irradiation, TLC is followed until the reaction of the quinoxaline-2-one compound is completed, water and ethyl acetate are added into a reaction liquid system for extraction and liquid separation, the obtained organic layer is dried by anhydrous sodium sulfate, reduced pressure concentration is carried out to remove the solvent, the concentrate is separated by column chromatography, mixed solvent of petroleum ether and ethyl acetate is used as eluent, eluent containing the target product is collected and is distilled to remove the solvent, and 1.97g of 3-isopropoxy-1-ethyl quinoxalin-2 (1H) -one is obtained, and the yield is 85%.
Example 4
Synthesis of 3- (2-hydroxypropane-2-methyl) -1-methylquinoxalin-2 (1H) -one
In a 50mL round bottom flask, selectfluor (15mmol, 5.3g) reagent is added into acetonitrile (20 mL), ultrasonic dissolution is carried out, 1-ethylquinoxalinone (10mmol, 1.7g), isopropanol (50mmol, 3g) and tert-butyl perbenzoate (30mmol, 5.8g) are added into the solvent, the mixture is stirred and reacted for 8 hours at room temperature under the irradiation of blue light, TLC is followed until the reaction of the raw material quinoxalin-2-one compound is completed, water and ethyl acetate are added into a reaction liquid system for extraction and liquid separation, the obtained organic layer is dried by anhydrous sodium sulfate, reduced pressure concentration is carried out to remove the solvent, the concentrate is separated by column chromatography, the eluent containing the target product is collected by taking a mixed solvent of petroleum ether and ethyl acetate as an eluent, and the solvent is distilled off, so that 1.97g of 3- (2-hydroxypropan-2-methyl) -1-ethylquinoxalin-2 (1H) -one is obtained, and the yield is 85%.
Example 5
Synthesis of 3-isopropoxy-1-methylquinoxaline-2 (1H) -one
In a 50mL round bottom flask, selectfluor (15mmol, 5.3g) reagent is added into dichloroethane (20 mL), ultrasonic dissolution is carried out, 1-methyl quinoxalinone (15mmol, 2.4g), isopropanol (50mmol, 3g) and acetic acid (30mmol, 1.8g) are added into the solvent, stirring reaction is carried out for 8 hours at room temperature under blue light irradiation, TLC tracking is carried out until the reaction of the raw material quinoxalin-2-one compound is completed, water and ethyl acetate are added into a reaction liquid system for extraction and liquid separation, the obtained organic layer is dried by anhydrous sodium sulfate, reduced pressure concentration is carried out to remove the solvent, the concentrate is separated by column chromatography, mixed solvent of petroleum ether and ethyl acetate is used as eluent, eluent containing the target product is collected and the solvent is distilled off, and then 1.57g of 3-isopropoxy-1-methyl quinoxalin-2 (1H) -one is obtained, and the yield is 72%.
Example 6
Synthesis of 3- (2-hydroxypropane-2-methyl) -1-methylquinoxalin-2 (1H) -one
In a 50mL round-bottom flask, selectfluor (15mmol, 5.3g) reagent is added into acetone (20 mL), ultrasonic dissolution is carried out, 1-methylquinoxalinone (5mmol, 0.8g), isopropanol (50mmol, 3g) and tert-butyl perbenzoate (25mmol, 4.8g) are added into the solvent, the mixture is stirred and reacted for 8 hours at room temperature under the irradiation of blue light, TLC is followed until the reaction of the raw material quinoxalin-2-one compound is completed, water and ethyl acetate are added into a reaction liquid system for extraction and liquid separation, the obtained organic layer is dried by anhydrous sodium sulfate, the solvent is removed by decompression concentration, the concentrate is separated by column chromatography, the eluent containing the target product is collected by taking a mixed solvent of petroleum ether and ethyl acetate as an eluent, and the solvent is distilled off, so that 1.53g of 3- (2-hydroxypropan-2-methyl) -1-methylquinoxalin-2 (1H) -one is obtained, and the yield is 70%.
It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, and these are all within the scope of protection of the present application.
Claims (8)
1. A method for preparing quinoxaline-2-ketone derivatives by controlled catalysis is characterized by comprising the following steps:
adding a Selectfluor reagent into an organic solvent, carrying out ultrasonic dissolution, respectively adding a quinoxaline-2-ketone compound shown in a formula (I), an alcohol shown in a formula (II) and an additive into the organic solvent, stirring for reaction at room temperature under the irradiation of a light source, tracking by TLC (thin layer chromatography) until the quinoxaline-2-ketone compound serving as a raw material completely reacts, finishing the reaction, carrying out post-treatment, and carrying out column chromatography separation and purification to obtain a target compound; when the additive is acetic acid, the target compound 3-alkoxy quinoxaline-2-one derivative shown as a formula (III) is obtained; when the additive is tert-butyl perbenzoate, the target compound 3-hydroxyalkyl quinoxaline-2-one derivative shown in the formula (IV) is obtained;
wherein R is 1 Is any one of H, methyl, ethyl, chlorine and bromine; r 2 Is any one of H, methyl, ethyl and benzyl; r 3 、R 4 Are each methyl.
2. The process for the controlled catalytic preparation of quinoxalin-2-one derivatives according to claim 1, characterized in that: the mass ratio of the quinoxaline-2-one compound to the Selectfluor reagent is 1:1 to 3.
3. The process for the controlled catalytic preparation of quinoxalin-2-one derivatives according to claim 1, characterized in that the organic solvent is selected from one of the following: acetone, acetonitrile, dichloroethane.
4. The method for preparing quinoxaline-2-one derivatives under controlled catalysis according to claim 1, wherein the mass ratio of the quinoxaline-2-one compounds, the alcohols and the additives is 1:3 to 10:1 to 5.
5. The process for the controlled catalytic preparation of quinoxalin-2-one derivatives according to claim 1, wherein the light source is selected from one of the following: blue light, white light, green light.
6. The process for the controlled catalytic preparation of quinoxalin-2-one derivatives according to claim 1, characterized in that: the reaction time is 6 to 12 hours.
7. The process for the controlled catalytic preparation of quinoxalin-2-one derivatives according to claim 1, characterized in that the work-up step is: adding water and an organic extracting agent into a reaction liquid system for extraction and liquid separation, drying an obtained organic layer by anhydrous sodium sulfate, concentrating under reduced pressure to remove a solvent, separating the concentrate by column chromatography, taking a mixed solvent of petroleum ether and ethyl acetate as an eluent, collecting an eluent containing a target product, and evaporating to remove the solvent to obtain the 3-alkoxy quinoxaline-2-one derivative shown in the formula (III) or the 3-hydroxyalkyl quinoxaline-2-one derivative shown in the formula (IV).
8. The process for the controlled catalytic preparation of quinoxalin-2-one derivatives according to claim 7, wherein the organic extractant is ethyl acetate.
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