CN111041515B - Method for synthesizing 3-alkylthio substituted quinoxalinone derivative under electrocatalysis - Google Patents
Method for synthesizing 3-alkylthio substituted quinoxalinone derivative under electrocatalysis Download PDFInfo
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Abstract
The invention discloses a method for synthesizing 3-alkylthio substituted quinoxalinone derivatives under electrocatalysis. The synthesis method comprises the following steps: under a certain current and in the presence of a proper amount of electrolyte, an additive is added, and the quinoxaline-2-ketone compound and the thiol compound are used as raw materials to synthesize the 3-alkylthio substituted quinoxalinone derivative with high yield. By adopting the technical scheme of the technology, the 3-alkylthio substituted quinoxalinone derivative is synthesized, and the method has the advantages of simple process, mild reaction conditions, high purity and yield, and the like, and the raw materials and the catalyst are cheap and easy to obtain, and the method is environment-friendly.
Description
Technical Field
The invention relates to a method for synthesizing 3-alkylthio substituted quinoxalinone derivatives under electrocatalysis, in particular to a method for synthesizing 3-alkylthio substituted quinoxalinone derivatives by carrying out electrolytic reaction on reactants with certain current in the presence or absence of an additive.
Background
The quinoxaline derivative is an important natural compound, is an important aromatic nitrogen heterocyclic compound containing a benzopyrazine structure, has good biological activity, particularly the 3-substituted quinoxalinone has various drug effects and is mainly used as an enzyme inhibitor to treat various diseases, such as cancer, diabetes, thrombus and the like, in addition, the 3-substituted quinoxalinone also has antibacterial effect and has the functions of enzyme inhibitor, receptor antagonist and the like, and the uniqueness of the 3-substituted quinoxalinone structure ensures that the 3-substituted quinoxalinone also plays an important role in the fields of organic synthesis and organic materials, and the synthesis of the 3-substituted quinoxalinone also becomes a hot topic researched by chemists based on the wide application of the 3-substituted quinoxalinone in the field of medicines.
In 2004, the quinoxaline 1, 4-dioxide C-3 thio-structural scaffold was confirmed to have anti-tubercular and anti-candida activities by assaying the 6, 7-difluoro-3-methyl-2-thiophenyl/phenylsulfinyl/benzenesulfonyl-quinoxaline-1, 4-dioxide obtained by screening according to a report of a. carta (eur.j. med.chem.2004, 39195-203).
In 2008, the report of b.yang (eur.j.pharmacol.2008,581, 262-269.) indicates that 3- (4-bromophenyl) -2- (ethylsulfonyl) -6-methylquinoxaline-1, 4-dioxide can induce cancer cell apoptosis, has strong antiproliferative effect in vitro, has good anticancer activity in hypoxia specific cancer cells, and reflects the effect of C-3 thio-structure quinoxaline derivatives in biological medicine and pharmacology.
Thus, the thioetherification method of the C-3 position of quinoxalinone is gradually attracting attention, but among the literature so far, literature reports on the synthesis of 3-alkylthio substituted quinoxalinone derivatives are rare, and C-3 dehalogenation coupling is the most common method (Eur.J.Org.Chem.2013,11, 2091-2105).
The method utilizes the C-3 halogenated quinoxaline-2-ketone and a sulfhydryl compound to carry out reflux reaction for 0.5 to 4 hours in an ethanol/sodium alkoxide system, and carries out dehalogenation coupling to form a corresponding 3-alkylthio substituted quinoxaline derivative. However, the method needs to introduce halogen at the C-3 position for pre-functionalization, which does not conform to the principle of atom economy, and the rare earth metal catalyst is introduced in the reaction process, so that the method is difficult to meet the requirements of environmental protection.
With the continuous development of chemical technology, a simpler, more convenient and more environment-friendly synthesis method is explored to become a hotspot, and in view of high atom economy of Cross Dehydrogenation Coupling (CDC) reaction, the synthesis method is one of the most direct and most effective methods for constructing C-S bonds at present.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for synthesizing 3-alkylthio substituted quinoxalinone derivatives under electrocatalysis, wherein the reaction temperature is room temperature, the operation is simple, and the product purity and the yield are higher.
The method for synthesizing the 3-alkylthio substituted quinoxalinone derivative under electrocatalysis is characterized in that a quinoxaline-2-ketone compound shown in a formula (I) and a thiol compound shown in a formula (II) are added into an organic solvent according to a certain proportion, and are stirred and reacted for 5-20 hours at 0-40 ℃ in the presence of an additive or in the absence of an electrolyte by current, TLC tracks the reaction to be finished after the quinoxaline-2-ketone compound serving as a raw material is completely reacted, and the target compound 3-alkylthio substituted quinoxalinone derivative shown in a formula (III) is obtained by post-treatment;
wherein: r1Is C2-C14 alkyl, phenethyl, 3-mercaptopropyl or allyl; n is 1 and represents a substituent R2Is monosubstituted, n-2 represents R2Is disubstituted, R2Each independently selected from hydrogen, methyl, halogen or nitro, R3Hydrogen, C1-C8 alkyl, propynyl and ester.
The method for synthesizing the 3-alkylthio substituted quinoxalinone derivative under electrocatalysis is characterized in that the additive is hydrochloric acid, trifluoroacetic acid, trifluoromethanesulfonic acid, sulfuric acid or acetic acid, and preferably trifluoroacetic acid, sulfuric acid or acetic acid.
The method for synthesizing the 3-alkylthio substituted quinoxalinone derivative under electrocatalysis is characterized in that the current is 10-15 mA, preferably 10mA, 12mA or 15 mA.
The method for synthesizing the 3-alkylthio substituted quinoxalinone derivative under electrocatalysis is characterized in that the organic solvent is selected from one or the combination of any several of the following: acetonitrile, DMF, toluene, ethanethiol, tert-butylmercaptan, heptanethiol, phenethylthiol or DMSO, wherein the mass ratio of the feeding volume of the organic solvent to the mass of the quinoxaline-2-one compound represented by the raw material formula (I) is 5.0-30: 1.0, preferably 5.0 to 25: 1.0, volume in mL, amount of substance in mmol.
The method for synthesizing the 3-alkylthio substituted quinoxalinone derivative under electrocatalysis is characterized in that the constant voltage and the constant current are constant current and 10 mA.
The method for synthesizing the 3-alkylthio substituted quinoxalinone derivative under electrocatalysis is characterized in that the ratio of the quinoxaline-2-ketone compound to the thiol compound to the additive is 1.0: 5.0-30: 0 to 4.0, preferably 1.0: 5.0-25: 2.0 to 3.0.
The method for synthesizing the 3-alkylthio substituted quinoxalinone derivative under electrocatalysis is characterized in that a developing solvent tracked by TLC is a mixed solvent of petroleum ether and ethyl acetate with the volume ratio of 5: 1.
The method for synthesizing the 3-alkylthio substituted quinoxalinone derivative under electrocatalysis is characterized in that the electrolyte is selected from one or the combination of any of the following substances: tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium iodide, tetrabutylammonium bromide, aluminum perchlorate, potassium iodide, potassium bromide, preferably tetrabutylammonium bromide, and the feeding molar ratio of the electrolyte to the quinoxaline-2-one compound is 0.5-0.8: 1.
the method for synthesizing the 3-alkylthio substituted quinoxalinone derivative under electrocatalysis is characterized in that the reaction temperature is 20-40 ℃, and the reaction time is 5-20 hours.
The invention particularly recommends that the synthesis method of the 3-alkylthio substituted quinoxalinone derivative under electrocatalysis is carried out according to the following steps:
adding a compound (I) quinoxaline-2-ketone (1mol) into a 50mL open round bottom flask with magnetic stirring, adding a compound (II) with the mass ratio of (5.0-25 mol), adding an additive with the mass ratio of (2.0-3.0 mol) relative to the compound (I), dissolving the electrolyte (0.5-0.8 mol) in an organic solvent, electrolyzing the mixture under the current of 10mA, stirring and reacting at the temperature of 20-40 ℃ for 5-20 hours, and adding saturated common salt solution into the mixture after the reaction is finished for washing. The mixture was extracted with ethyl acetate, and the combined organic layers were extracted with anhydrous Na2SO4Dried and concentrated under reduced pressure. The crude product was purified on a silica gel column using n-hexane/ethyl acetate to obtain a pure product.
By adopting the technology, compared with the prior art, the invention has the beneficial effects that:
the quinoxaline-2-ketone compound and the thiol compound which are cheap and easy to obtain are adopted as raw materials, so that the quinoxaline-2-ketone compound and the thiol compound are cheap and easy to obtain, the use of a metal catalyst and an oxidant is avoided, the reaction is carried out under the environment-friendly electrolysis condition, and the quinoxaline-2-ketone compound and the thiol compound are simple to operate, mild in reaction condition and high in product purity and yield.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
Example 17-bromo-3- (ethylsulfanyl) -1-methylquinolin-2 (1H) -one (III-a)
Adding compound (I) 7-bromo-1-methylquinoxaline-2-one (95.2mg, 0.4mmol), ethanethiol (124.3mg, 2mmol), trifluoroacetic acid (91mg, 0.8mmol) into a 50mL open round bottom flask equipped with magnetic stirring, dissolving the mixture in DMF (10mL), reacting under electrolysis at 10mA and 20 deg.C with stirring for 15 hours, TLC following the end of the disappearance of the starting material (mixed solvent of petroleum ether and ethyl acetate in volume ratio of 5:1 as developing solvent), washing the reaction mixture with saturated common salt water, extracting with ethyl acetate, combining the organic layers, and extracting with anhydrous Na2SO4Drying and concentration under reduced pressure gave the crude product, which was purified on a silica gel column using n-hexane/ethyl acetate to give 88.03mg of the product 7-bromo-3- (ethylsulfanyl) -1-methylquinolin-2 (1H) -one in 74.1% yield and 97.6% HPLC purity.
Example 26-bromo-3- (isopropylsulfanyl) -1-methylquinolin-2 (1H) -one (III-b)
A50 mL open round bottom flask equipped with magnetic stirring was charged with compound (I) 6-bromo-1-methylquinoxalin-2-one (95.2mg, 0.4mmol), isopropylmercaptan (304.6mg, 4mmol), acetic acid (48mg, 0.8mmol), DMSO (5mL) was added to the mixture, the reaction was stirred at 25 ℃ for 15 hours under 12mA current electrolysis, TLC was followed until the reaction was complete (mixed solvent of petroleum ether and ethyl acetate in volume ratio of 5:1 as developing solvent), and the reaction mixture was washed with saturated brine. The mixture was extracted with ethyl acetate, and the combined organic layers were extracted with anhydrous Na2SO4Dried and concentrated under reduced pressure. Using n-hexane/ethyl acetate on silica gelThe crude product was purified on the column to give 90.6mg of product in 72.6% yield with 98.6% HPLC purity.
Example 36, 7-dichloro-3- (tert-butylsulfanyl) -1-methylquinolin-2 (1H) -one (III-c)
A50 mL open round bottom flask equipped with magnetic stirring was charged with 6, 7-dichloro-1-methylquinoxalin-2-one (I) (90.8mg, 0.4mmol), tert-butylmercaptan (541.1mg, 6mmol), trifluoromethanesulfonic acid (120mg, 0.8mmol), DMSO (5mL) was added to the mixture, the mixture was electrolyzed under a current of 15mA, stirred at 30 ℃ for 16 hours, TLC was followed until the reaction was completed (mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 5:1 as developing solvent), the reaction mixture was washed with saturated brine, the mixture was extracted with ethyl acetate, the combined organic layers were extracted with anhydrous Na2SO4Dried and concentrated under reduced pressure. The crude product was purified on a silica gel column using n-hexane/ethyl acetate to give 92.7mg of product, 73.4% yield, 96.8% HPLC purity.
Example 43- (cyclohexylthio) -1-methyl-6-nitroquinolin-2 (1H) -one (III-d)
In a 50mL open round bottom flask equipped with magnetic stirring was added compound (I) 1-methyl-6-nitroquinoxalin-2-one (82mg, 0.4mmol), acetic acid (48mg, 0.8mmol), acetonitrile (10mL) was added to the mixture, the reaction was stirred at 25 ℃ for 20 hours under electrolysis at 10mA, TLC was followed until the reaction was completed (mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 5:1 as developing solvent), and the reaction mixture was washed with saturated brine. The mixture was extracted with ethyl acetate, and the combined organic layers were extracted with anhydrous Na2SO4Dried and concentrated under reduced pressure. The crude product was purified on a silica gel column using n-hexane/ethyl acetate to give 102.7mg of product in 80.5% yield with HPLC purity 98.4%.
Example 53- (heptylthio) -1,6, 7-trimethylquinolin-2 (1H) -one (III-e)
In a 50mL open round bottom flask equipped with magnetic stirring was added compound (I)1,6, 7-trimethylquinoxalin-2-one (75.2mg, 0.4mmol), heptanethiol (793.6mg, 6mmol), sulfuric acid (117.6mg, 1.2mmol), acetonitrile (10mL) was added to the mixture, and the reaction was stirred at 30 ℃ under electrolysis at 10mAAfter 20 hours, TLC was carried out until the reaction was completed (using a mixed solvent of petroleum ether and ethyl acetate at a volume ratio of 5:1 as a developing solvent), and the reaction mixture was washed with saturated brine. The mixture was extracted with ethyl acetate, and the combined organic layers were extracted with anhydrous Na2SO4Dried and concentrated under reduced pressure. The crude product was purified on a silica gel column using n-hexane/ethyl acetate to give 116.3mg of product in 91.4% yield with HPLC purity 98.2%.
EXAMPLE 61-methyl-3- (tetradecylthio) quinoxalin-2 (1H) -one (III-f)
In a 50mL open round bottom flask equipped with magnetic stirring was charged compound (I), 1-methylquinoxalin-2-one (64mg, 0.4mmol), tetradecylthiol (1382.4mg, 6.0mmol), trifluoroacetic acid (91mg), acetonitrile (10mL) was added to the mixture, the reaction was stirred at 30 ℃ for 10 hours under electrolysis at 10mA, TLC was followed until the reaction was completed (mixed solvent of petroleum ether and ethyl acetate at a volume ratio of 5:1 as developing solvent), and the reaction mixture was washed with saturated brine. The mixture was extracted with ethyl acetate, and the combined organic layers were extracted with anhydrous Na2SO4Dried and concentrated under reduced pressure. The crude product was purified on a silica gel column using n-hexane/ethyl acetate to give 116.7mg, 75.2% yield, 96.7% HPLC purity.
EXAMPLE 71 methyl-3- (Phenylethylthio) quinoxalin-2 (1H) -one (III-g)
In a 50mL open round bottom flask equipped with magnetic stirring was added compound (I) 1-methylquinoxalin-2-one (64mg, 0.4mmol), phenethyl thiol (1105.8mg, 8mmol), trifluoromethanesulfonic acid (180mg, 1.2mmol), acetonitrile (10mL) was added to the mixture, the reaction was stirred at 40 ℃ for 18 hours under electrolysis at a current of 10mA, TLC was followed until the end of the reaction (mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 5:1 as developing solvent), and the reaction mixture was washed with saturated brine. The mixture was extracted with ethyl acetate, and the combined organic layers were extracted with anhydrous Na2SO4Dried and concentrated under reduced pressure. The crude product was purified on a silica gel column using n-hexane/ethyl acetate to give 94.2mg of product in 79.6% yield with HPLC purity 98.8%.
Example 82 Ethyl- ((4-methyl-3-oxo-3, 4-dihydroquinoxalin-2-yl) thio) acetate (III-h)
In a 50mL open round bottom flask equipped with magnetic stirring was added compound (I) 1-methylquinoxalin-2-one (64mg, 0.4mmol), ethyl thioglycolate (721.0mg, 8mmol), sulfuric acid (117.6mg, 1.2mmol), DMF (10mL) was added to the mixture, the reaction was stirred at 35 ℃ for 20 hours under electrolysis at 10mA current, TLC was followed to the end of the reaction (mixed solvent of petroleum ether and ethyl acetate in volume ratio of 5:1 as developing solvent), and the reaction mixture was washed with saturated brine. The mixture was extracted with ethyl acetate, and the combined organic layers were extracted with anhydrous Na2SO4Dried and concentrated under reduced pressure. The crude product was purified on a silica gel column using n-hexane/ethyl acetate to give 83.8mg of product in 75.4% yield with an HPLC purity of 97.2%.
Example 93- ((3-mercaptopropyl) thio) -1-methylquinolin-2 (1H) -one (III-i)
In a 50mL open round bottom flask equipped with magnetic stirring was added compound (I) 1-methylquinoxalin-2-one (64mg, 0.4mmol), propanedithiol (216.4mg, 2mmol), acetic acid (72mg, 1.2mmol), the mixture was dissolved in toluene (8mL), the reaction was stirred at 25 ℃ for 18 hours under electrolysis at 10mA, TLC was followed until the end of the reaction (mixed solvent of petroleum ether and ethyl acetate in volume ratio 5:1 as developing solvent), and the reaction mixture was washed with saturated brine. The mixture was extracted with ethyl acetate, and the combined organic layers were extracted with anhydrous Na2SO4Dried and concentrated under reduced pressure. The crude product was purified on a silica gel column using n-hexane/ethyl acetate to give 81.39mg of product in 76.5% yield with HPLC purity 96.5%.
Example 103- (allylsulfanyl) -1-methylquinolin-2 (1H) -one (III-j)
In a 50mL open round bottom flask equipped with magnetic stirring was added compound (I) 1-methylquinoxalin-2-one (69mg, 0.4mmol), allylthiol (294.6mg, 4mmol), trifluoroacetic acid (91mg, 0.8mmol), toluene (8mL) was added to the mixture, the reaction was stirred at 25 ℃ for 15 hours under electrolysis at 10mA, TLC was followed to the end of the reaction (mixed solvent of petroleum ether and ethyl acetate in volume ratio of 5:1 as developing solvent), and the reaction mixture was washed with saturated brine. Will be mixed withThe mixture was extracted with ethyl acetate, and the combined organic layers were extracted with anhydrous Na2SO4Dried and concentrated under reduced pressure. The crude product was purified on a silica gel column using n-hexane/ethyl acetate to give 77.2mg of product in 83.1% yield with HPLC purity 98.2%.
Example 117-bromo-3- (ethylsulfanyl) -1-methylquinolin-2 (1H) -one (III-k)
In a 50mL open round bottom flask equipped with magnetic stirring was added compound (I) 7-bromo-1-methylquinoxalin-2-one (95.2mg, 0.4mmol), ethanethiol (124.3mg, 2mmol), trifluoroacetic acid (91mg, 0.8mmol), the mixture was dissolved in DMF (10mL), the reaction was stirred at 25 ℃ for 15 hours under electrolysis at 10mA, TLC was followed until the reaction was complete (mixed solvent of petroleum ether and ethyl acetate in volume ratio of 5:1 as developing solvent), and the reaction mixture was washed with saturated brine. The mixture was extracted with ethyl acetate, and the combined organic layers were extracted with anhydrous Na2SO4Dried and concentrated under reduced pressure. The crude product was purified on a silica gel column using n-hexane/ethyl acetate to give 82.92mg of the product 7-bromo-3- (ethylsulfanyl) -1-methylquinolin-2 (1H) -one in 69.8% yield and 97.6% HPLC purity.
Example 126-bromo-3- (isopropylsulfanyl) -1-methylquinolin-2 (1H) -one (III-l)
In a 50mL open round bottom flask equipped with magnetic stirring was added compound (I) 6-bromo-1-methylquinoxalin-2-one (95.2mg, 0.4mmol), isopropylmercaptan (304.6mg, 4mmol), acetic acid (48mg, 0.8mmol), DMSO (5mL) was added to the mixture, the reaction was stirred at 20 ℃ for 10 hours, TLC was followed until the reaction was complete (mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 5:1 as developing solvent), and the reaction mixture was washed with saturated brine. The mixture was extracted with ethyl acetate, and the combined organic layers were extracted with anhydrous Na2SO4Dried and concentrated under reduced pressure. The crude product was purified on a silica gel column using n-hexane/ethyl acetate to give 85.4mg of product in 68.5% yield with HPLC purity 98.7%.
Example 133- (Phenylethylthio) quinoxalin-2 (1H) -one (III-m)
Into a 50mL open bottom round bottom flask equipped with magnetic stirring was added the quinoxalinone of compound (I) (73.1mg, 0.5mmol), 2-benzeneEthane-1-thiol (552.2mg, 4mmol), acetic acid (48mg, 0.8mmol), DMSO (5mL) was added to the mixture, the reaction was stirred at 20 ℃ for 10 hours, TLC was followed until the reaction was completed (using a mixed solvent of petroleum ether and ethyl acetate as a developing solvent at a volume ratio of 5: 1), and the reaction mixture was washed with saturated brine. The mixture was extracted with ethyl acetate, and the combined organic layers were extracted with anhydrous Na2SO4Dried and concentrated under reduced pressure. The crude product was purified on a silica gel column using n-hexane/ethyl acetate to give 112.1mg of product in 79.5% yield with HPLC purity 98.6%.
Example 142 Ethyl- ((3-oxo-3, 4-dihydroquinoxalin-2-yl) thio) acetate (III-n)
A50 mL open round bottom flask equipped with magnetic stirring was charged with quinoxalinone of compound (I) (73.1mg, 0.5mmol), ethyl 2-mercaptoacetate (480.1mg, 4mmol), acetic acid (48mg, 0.8mmol), DMSO (5mL) was added to the mixture, the reaction was stirred at 20 ℃ for 10 hours, TLC was followed until the reaction was complete (using a 5:1 by volume mixture of petroleum ether and ethyl acetate as developing solvent), and the reaction mixture was washed with saturated brine. The mixture was extracted with ethyl acetate, and the combined organic layers were extracted with anhydrous Na2SO4Dried and concentrated under reduced pressure. The crude product was purified on a silica gel column using n-hexane/ethyl acetate to give 112.5mg of product in 85.2% yield with HPLC purity 98.5%.
Example 153- (tert-butylthio) -1- (prop-2-yn-1-yl) quinoxalinone (III-o)
In a 50mL open round bottom flask equipped with magnetic stirring was added compound (I)1- (prop-2-yn-1-yl) quinoxalin-2 (1H) -one (92.1mg, 0.5mmol), 2-methylpropane-2-thiol (360.2mg, 4mmol), acetic acid (48mg, 0.8mmol), DMSO (5mL) was added to the mixture, the reaction was stirred at 20 ℃ for 10 hours, TLC was followed until the reaction was complete (mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 5:1 as developing solvent), and the reaction mixture was washed with saturated brine. The mixture was extracted with ethyl acetate, and the combined organic layers were extracted with anhydrous Na2SO4Dried and concentrated under reduced pressure. The crude product was purified on a silica gel column using n-hexane/ethyl acetate to give 41.1mg of product in 30.2% yield with HPLC purity 98.9%.
Claims (12)
1. A method for synthesizing 3-alkylthio substituted quinoxalinone derivatives under electrocatalysis is characterized in that quinoxaline-2-ketone compounds shown in a formula (I) and thiol compounds shown in a formula (II) are added into an organic solvent according to a certain proportion, and then current is introduced, and the mixture is stirred and reacted for 5-20 hours at 0-40 ℃ in the presence of an additive or without the additive, TLC tracks until the reaction of the quinoxaline-2-ketone compounds serving as raw materials is completed, the reaction is finished, and the target compound 3-alkylthio substituted quinoxalinone derivatives shown in a formula (III) are obtained through post-treatment;
wherein: r1Is C2-C14 alkyl, phenethyl, 3-mercaptopropyl or allyl; n (R)2) Represents R2Each independently or randomly combined mono-or di-substituted, R2Is hydrogen, methyl, halogen or nitro, R3Hydrogen, C1-C8 alkyl, propynyl and ester group;
the current is 10-15 mA;
the electrolyte is selected from one or a combination of any of the following: tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium iodide, tetrabutylammonium bromide, aluminum perchlorate, potassium iodide and potassium bromide, wherein the feeding molar ratio of the electrolyte to the quinoxaline-2-one compound is 0.5-0.8: 1.
2. the method for synthesizing 3-alkylthio-substituted quinoxalinone derivatives under electrocatalysis according to claim 1, characterized in that the additive is hydrochloric acid, trifluoroacetic acid, trifluoromethanesulfonic acid, sulfuric acid or acetic acid.
3. The method for synthesizing 3-alkylthio-substituted quinoxalinone derivatives under electrocatalysis according to claim 1, characterized in that the magnitude of the current is 10mA, 12mA or 15 mA.
4. The method for synthesizing 3-alkylthio substituted quinoxalinone derivatives under electrocatalysis according to claim 1, characterized in that the organic solvent is selected from one or a combination of any of the following: acetonitrile, DMF, toluene, ethanethiol, tert-butylmercaptan, heptanethiol, phenethylthiol or DMSO, wherein the mass ratio of the feeding volume of the organic solvent to the mass of the quinoxaline-2-one compound represented by the raw material formula (I) is 5.0-30: 1.0, volume in mL, amount of substance in mmol.
5. The method for synthesizing 3-alkylthio-substituted quinoxalinone derivatives under electrocatalysis according to claim 3, characterized in that the constant current is 10mA and is constant voltage and constant current.
6. The method for synthesizing 3-alkylthio substituted quinoxalinone derivatives under electrocatalysis according to claim 1, characterized in that the ratio of quinoxaline-2-one compound, thiol compound and additive is 1.0: 5.0-30: 0 to 4.0.
7. The electrocatalytic synthesis method of 3-alkylthio substituted quinoxalinone derivatives according to claim 1, characterized in that the developing solvent for TLC tracking is a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 5: 1.
8. The method for synthesizing 3-alkylthio-substituted quinoxalinone derivatives under electrocatalysis according to claim 1, characterized in that the electrolyte is tetrabutylammonium bromide.
9. The method for synthesizing 3-alkylthio substituted quinoxalinone derivatives under electrocatalysis according to claim 1, characterized in that the reaction temperature is 20-40 ℃ and the reaction time is 5-20 hours.
10. The electrocatalytic synthesis method of 3-alkylthio-substituted quinoxalinone derivatives according to claim 1, characterized in that the additive is trifluoroacetic acid, sulfuric acid or acetic acid.
11. The method for synthesizing 3-alkylthio-substituted quinoxalinone derivatives under electrocatalysis according to claim 1, characterized in that the mass ratio of the feeding volume of the organic solvent to the material of the quinoxaline-2-one compound represented by the raw material formula (I) is 5.0-25: 1.0, volume in mL, amount of substance in mmol.
12. The method for synthesizing 3-alkylthio substituted quinoxalinone derivatives under electrocatalysis according to claim 1, characterized in that the ratio of quinoxaline-2-one compound, thiol compound and additive is 1.0: 5.0-25: 2.0 to 3.0.
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