CN110627732A - A method for synthesizing nitroquinoxaline or derivatives thereof and aminoquinoxaline or derivatives thereof - Google Patents

Abstract

The present application relates to a method for synthesizing nitroquinoxaline or derivatives thereof, which comprises, in the presence of catalyst o-benzoylsulfonimide, making mononitro-substituted o-phenylenediamine or derivatives thereof and The mononitrosubstituted benzil or its derivatives are reacted in a solvent for a predetermined period of time to obtain the nitroquinoxaline or its derivatives. The present application also provides a method for synthesizing aminoquinoxaline or derivatives thereof. The application also provides an application of o-benzoylsulfonimide as a catalyst in the synthesis of nitroquinoxaline or its derivatives. The present application also provides a method for preparing 4-nitrobenzil. The synthesis process of the present application has low cost and high yield, and is helpful for large-scale preparation of nitroquinoxaline or its derivatives and aminoquinoxaline or its derivatives.

Description

A kind of synthetic nitroquinoxaline or derivative thereof and aminoquinoxaline or derivative thereof Methods

technical field

The application relates to the technical field of organic synthesis, specifically, the application relates to a method for synthesizing nitroquinoxaline or derivatives thereof and aminoquinoxaline or derivatives thereof.

Background technique

Quinoxaline is a benzopyrazine compound with excellent biological activity and thermal stability. It exists in a variety of compounds and is expected to be used in dyes, organic semiconductors, electroluminescent materials and anion acceptors has been extensively studied. Similarly, quinoxaline derivatives are also potentially applicable in many fields. Therefore, many methods have been developed in the art to synthesize quinoxaline derivatives, such as reacting o-phenylenediamine-containing monomers with α-hydroxy ketones or epoxides.

Aminoquinoxaline has higher chemical bond energy, larger molar volume and weaker polarity, which endows the polymer prepared by it with excellent heat resistance and oxidation resistance, higher environmental stability, low Dielectric constant, dielectric loss and high plasticity. Aminoquinoxaline can be dissolved in organic solvents and has good processing properties.

2-(4-aminophenyl)-3-phenyl-6-aminoquinoxaline and 3-(4-aminophenyl)-2-phenyl-6-aminoquinoxaline mixture is a new type of amino Quinoxaline diamine monomer. Polymers such as quinoxaline-based polyimide, polyether and polyester synthesized by using the mixture have good thermal stability, chemical stability and excellent electrical conductivity, and have good air permeability and toughness. In addition, the mixture has good solubility in organic solvents, low crystallinity, and a wide processing window.

Chinese invention patent publication CN105153144A discloses a main chain diamine-type quinoxalinyl benzoxazine and a preparation method thereof, in which 4-nitrobenzil, 4-nitro-o-phenylenediamine and glacial acetic acid are disclosed As the starting material, first synthesize 2-(4-nitrophenyl)-3-phenyl-6-aminoquinoxaline and 3-(4-nitrophenyl)-2-phenyl-6-aminoquinoxaline Oxaline mixture, the yield is 81.%. Then, obtain 2-(4-aminophenyl)-3-phenyl-6-aminoquinoxaline and 3-(4-aminophenyl)-2-phenyl-6-aminoquinoxaline through hydrazine hydrate reduction morphine mixture. The weak point of this patent document disclosure technique is that the yield when synthesizing the nitroquinoxaline mixture is not high, and the starting material 4-nitrobenzil used is expensive and difficult to obtain, thus resulting in higher production cost, not Suitable for industrial production.

Chinese invention patent publication CN107089954A discloses a kind of synthetic 2-(4-aminophenyl)-3-phenyl-6-aminoquinoxaline and 3-(4-aminophenyl)-2-phenyl-6-amino The method of quinoxaline mixture, described method comprises (1) take 4-nitrophenylacetic acid as starting material, obtain 4-nitrophenylacetyl chloride through chlorination; (2) make 4-nitrophenylacetyl chloride React with benzene to obtain 2-(4-nitrophenyl)-1-acetophenone; (3) make 2-(4-nitrophenyl)-1-acetophenone and 4-nitro-o-phenylenediamine The reaction obtains 2-(4-nitrophenyl)-3-phenyl-6-aminoquinoxaline and 3-(4-nitrophenyl)-2-phenyl-6-aminoquinoxaline mixture; and (4) carry out catalytic hydrogenation to the nitroquinoxaline mixture in step (3), obtain 2-(4-aminophenyl)-3-phenyl-6-aminoquinoxaline and 3-(4-amino Phenyl)-2-phenyl-6-aminoquinoxaline mixture. The synthesis method disclosed in this patent document does not use 4-nitrobenzil, which reduces the production cost to a certain extent. However, step (3) in this process needs to be carried out at a relatively high temperature of 70-80° C. in the presence of a gaseous oxidant and a basic catalyst, and the yield is between 90.1% and 95.0%.

For this reason, there is a continuous need in the art to develop a low-cost, high-yield method for synthesizing nitroquinoxaline or derivatives thereof and aminoquinoxaline or derivatives thereof.

Contents of the invention

The purpose of this application is to provide a method for synthesizing nitroquinoxaline or its derivatives with low cost and high yield, so as to solve the technical problems in the above-mentioned prior art. Specifically, this application uses 4-nitroiodobenzene and phenylacetylene as starting materials to economically and efficiently synthesize 4-nitrobenzil. Then, by selecting o-benzoylsulfonimide (also known as saccharin) as a specific catalyst, 4-nitrobenzil and 4-nitrophthalamide can be synthesized with a yield of up to 98% at normal temperature and pressure. Amine reaction to prepare mixtures of 2-(4-nitrophenyl)-3-phenyl-6-aminoquinoxaline and 3-(4-nitrophenyl)-2-phenyl-6-aminoquinoxaline . Finally, 2-(4-aminophenyl)-3-phenyl-6-aminoquinoxaline and 3-(4-aminophenyl)-2-phenyl-6- Aminoquinoxaline mixtures.

The purpose of this application is also to provide a method for synthesizing nitro-substituted benzil.

The purpose of the application is also to provide a method for synthesizing aminoquinoxaline or derivatives thereof.

The purpose of the present application is also to provide a kind of o-benzoylsulfonimide as a catalyst in the preparation of nitroquinoxaline or its derivatives.

The purpose of this application is also to provide a method for preparing 4-nitrobenzil.

In order to solve the above technical problems, the application provides the following technical solutions:

In a first aspect, the application provides a method for synthesizing nitroquinoxaline or derivatives thereof, characterized in that the method comprises the following steps: in the presence of a catalyst o-benzoylsulfonimide, reacting mononitro-substituted o-phenylenediamine or its derivatives with mononitro-substituted benzil or its derivatives in a solvent for a predetermined period of time to obtain the nitroquinoxaline or its derivatives;

Wherein said mononitro-substituted o-phenylenediamine or its derivatives have a structure shown by the following general formula (I):

In the general formula (I), the groups R1, R2, R3 and R4 are each independently selected from H, C1-C10 alkyl or nitro, and there is one and only one of the groups R1, R2, R3 and R4 for nitro;

Wherein, the mononitro-substituted benzil has a structure shown by the following general formula (II):

In the general formula (II), the groups R5, R6, R7, R8, R9, R10, R11, R12, R13 and R14 are each independently selected from H, C1-C10 alkyl or nitro, and the groups R5, One and only one of R6, R7, R8, R9, R10, R11, R12, R13 and R14 is nitro;

Wherein, the nitroquinoxaline or its derivatives have the structure shown by the following general formula (III):

In the general formula (III), the groups R21, R22, R23 and R24 are each independently selected from H, C1-C10 alkyl or nitro, and only one of the groups R21, R22, R23 and R24 is Nitro; In general formula (III), group R31, R32, R33, R34, R35, R41, R42, R43, R44 and R45 are each independently selected from H, C1-C10 alkyl or nitro, and the group One and only one of groups R31, R32, R33, R34, R35, R41, R42, R43, R44 and R45 is nitro.

In one embodiment of the first aspect, the mononitro-substituted benzil or its derivatives include 4-nitrobenzil, 3-nitrobenzil, 2-methyl-4-nitrobenzyl phenylil, 3-methyl-4-nitrobenzil, 2,3-dimethyl-4-nitrobenzil, 2,3,5-trimethyl-4-nitrobenzil Acyl;

And/or, the mononitro-substituted o-phenylenediamine or its derivatives are 3-nitro-o-phenylenediamine, 4-nitro-o-phenylenediamine, 5-nitro-o-phenylenediamine, 6-nitro O-phenylenediamine, 3-methyl-4-nitro-o-phenylenediamine, 5-methyl-4-nitro-o-phenylenediamine, 3,5-dimethyl-4-nitro-o-phenylenediamine or 3,5,6-trimethyl-4-nitro-o-phenylenediamine;

And/or, the solvent is one or more of glacial acetic acid, methanol, N N-dimethylformamide or acetonitrile.

In an embodiment of the first aspect, based on the number of moles, the ratio of the amount of the catalyst o-benzoylsulfonimide to mononitro-substituted benzil is less than or equal to 5%.

In one embodiment of the first aspect, the nitroquinoxaline or its derivatives include 2-(4-nitrophenyl)-3-phenyl-6-aminoquinoxaline and 3-(4 -nitrophenyl)-2-phenyl-6-aminoquinoxaline mixture.

In one embodiment of the first aspect, the 4-nitrobenzil is prepared by the following method:

(1) reacting nitrohalogenated benzene with phenylacetylene to obtain 1-nitro-4-phenylacetylene; and

(2) reacting 1-nitro-4-phenylacetylene with an oxidizing agent in the presence of a metal catalyst to obtain the 4-nitrobenzil.

In one embodiment of the first aspect, the nitrohalobenzene is 4-nitroiodobenzene, 4-nitrobromobenzene or 4-nitrochlorobenzene;

And/or, the metal catalyst is palladium dichloride, or a mixture of aluminum chloride and palladium acetate in equimolar amounts;

And/or, the oxidizing agent is dimethyl sulfoxide.

In a second aspect, the application provides a method for synthesizing aminoquinoxaline or derivatives thereof, characterized in that, the method comprises the synthesis of nitroquinoxaline or derivatives thereof as claimed in claim 1 The corresponding nitro group of the nitroquinoxaline or its derivatives prepared by the method is reduced to an amino group to obtain the aminoquinoxaline or its derivatives.

In one embodiment of the second aspect, the aminoquinoxaline or derivatives thereof are 2-(4-aminophenyl)-3-phenyl-6-aminoquinoxaline and 3-(4-amino Phenyl)-2-phenyl-6-aminoquinoxaline mixture.

In a third aspect, the present application provides an application of o-benzoylsulfonimide as a catalyst in the synthesis of nitroquinoxaline or its derivatives.

In a fourth aspect, the present application provides a method for preparing 4-nitrobenzil, the method comprising the following steps:

(1) reacting nitrohalogenated benzene with phenylacetylene to obtain 1-nitro-4-phenylacetylene; and

(2) reacting 1-nitro-4-phenylacetylene with an oxidizing agent in the presence of a metal catalyst to obtain the 4-nitrobenzil.

Compared with the prior art, the beneficial effect of the present application is that the synthesis process of the present application has low cost and high yield, which helps to realize the large-scale preparation of nitroquinoxaline or its derivatives and aminoquinoxaline or its derivatives .

Description of drawings

Figure 1 shows the H NMR spectrum of 1-nitro-4-phenylethynylbenzene.

Figure 2 shows the H NMR spectrum of 4-nitrobenzil.

Fig. 3 shows two isomers 2-(4-nitrophenyl)-3-phenyl-6-nitroquinoxaline and 3-(4 -Nitrophenyl)-2-phenyl-6-nitroquinoxaline mixture of the hydrogen spectrum nuclear magnetic resonance spectrum.

Figure 4 shows two isomers 2-(4-aminophenyl)-3-phenyl-6-aminoquinoxaline and 3-(4-amino The hydrogen spectrum nuclear magnetic resonance spectrum of the mixture of phenyl)-2-phenyl-6-aminoquinoxaline.

Detailed ways

Aminoquinoxaline or its derivatives are a new type of diamine monomer, and polymers such as polyimides, polyethers, and polyesters synthesized from them have excellent thermal and chemical stability. Nitroquinoxaline or its derivatives are precursor compounds for the synthesis of aminoquinoxaline or its derivatives. There are mature processes in the industry for converting nitro groups into amino groups, such as catalytic hydrogenation reduction, hydrazine hydrate reduction, etc. However, some processes for synthesizing nitroquinoline or its derivatives in the prior art have high costs, some reaction yields are not high, and some reaction conditions are harsh. Therefore, there is a continuous need in the art to develop a low-cost, high-yield method for synthesizing nitroquinoxaline or derivatives thereof.

The application provides a method for synthesizing nitroquinoxaline or derivatives thereof, characterized in that the method comprises the following steps: in the presence of a catalyst o-benzoylsulfonimide, the mononitro-substituted o-Phenylenediamine or its derivatives react with mononitro-substituted benzil or its derivatives in a solvent for a predetermined period of time to obtain the nitroquinoxaline or its derivatives;

Wherein said mononitro-substituted o-phenylenediamine or its derivatives have a structure shown by the following general formula (I):

In the general formula (I), the groups R1, R2, R3 and R4 are each independently selected from H, C1-C10 alkyl or nitro, and there is one and only one of the groups R1, R2, R3 and R4 for nitro;

Wherein, the mononitro-substituted benzil has a structure shown by the following general formula (II):

In the general formula (II), the groups R5, R6, R7, R8, R9, R10, R11, R12, R13 and R14 are each independently selected from H, C1-C10 alkyl or nitro, and the groups R5, One and only one of R6, R7, R8, R9, R10, R11, R12, R13 and R14 is nitro;

Wherein, the nitroquinoxaline or its derivatives have the structure shown by the following general formula (III):

In the general formula (III), the groups R21, R22, R23 and R24 are each independently selected from H, C1-C10 alkyl or nitro, and only one of the groups R21, R22, R23 and R24 is Nitro; In general formula (III), group R31, R32, R33, R34, R35, R41, R42, R43, R44 and R45 are each independently selected from H, C1-C10 alkyl or nitro, and the group One and only one of groups R31, R32, R33, R34, R35, R41, R42, R43, R44 and R45 is nitro.

In a specific embodiment, the arrow in the general formula (III) indicates that there are two isomers at the same time, specifically referring to the exchange of substituents at the 2 and 3 positions on the nitrogen-containing six-membered ring of quinoxaline to form mixture of isomers.

As used herein, the term "C1-C10 alkyl" refers to a straight chain or branched alkyl group having 1 to 10 carbon atoms. In a specific embodiment, the C1-C10 alkyl group includes methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl and the like.

In a particularly preferred embodiment, the nitroquinoline or derivatives thereof are 2-(4-nitrophenyl)-3-phenyl-6-aminoquinoxaline and 3-(4-nitroquinoxaline phenyl)-2-phenyl-6-aminoquinoxaline mixture.

In a particularly preferred embodiment, the aminoquinoline or derivatives thereof are 2-(4-aminophenyl)-3-phenyl-6-aminoquinoxaline and 3-(4-aminophenyl )-2-phenyl-6-aminoquinoxaline mixture.

In another embodiment, the inventors of the present application surprisingly found that o-benzoylsulfonimide (also known as saccharin), which is commonly used as a sweetener, can significantly increase the concentration of mononitro substitution at a very low dosage. The yield of the reaction between benzil and mononitro-substituted o-phenylenediamine.

The present application also provides a cost-effective method for synthesizing 4-nitrobenzil. The method may comprise the steps of: (1) reacting nitrohalobenzene with phenylacetylene to obtain 1-nitro-4-phenylacetylene; and (2) reacting 1-nitrohalobenzene in the presence of a metal catalyst Base-4-phenylacetylene is reacted with an oxidizing agent to obtain the 4-nitrobenzil.

In a specific embodiment, palladium chloride can be replaced by equimolar amounts of aluminum chloride and palladium acetate in the preparation of benzil, but the yield of aluminum chloride and palladium acetate as catalyst is low (about 40%).

In a specific embodiment, a higher yield can be achieved without using a catalyst under different temperature and duration conditions: glacial acetic acid is used as a solvent at room temperature for 12 hours and the yield can reach 98%; The yield can reach 98%; the yield can be greater than 80% when DMF is used as a solvent at 90°C for 36 hours, and the yield can be greater than 60% when acetonitrile is used as a solvent for 36 hours at 90°C. Using saccharin as a catalyst under the condition of glacial acetic acid as a solvent can shorten the reaction time to 1 h under the addition of 5%.

Example

In the following, the present application will be further described and illustrated in conjunction with the embodiments. Unless otherwise specified, all chemical raw materials used can be purchased from the market. Those skilled in the art can understand that the following embodiments are only exemplary.

Example 1

The synthetic route of the present embodiment is as follows:

In the following, the nuclear magnetic resonance spectrometer used is a Bruker 500M nuclear magnetic resonance spectrometer.

In the following nuclear magnetic data, ¹ H NMR (CDCl ₃ , 400 MHz) means hydrogen nuclear magnetic resonance spectrum at 400 MHz with deuterated chloroform as a solvent. ¹ H NMR (DMSO-d6, 500MHz) means hydrogen nuclear magnetic resonance spectrum at 500MHz using deuterated DMSO as solvent.

Step 1: Synthesis of 1-nitro-4-phenylethynylbenzene

12.5g (50mmol) of 4-nitroiodobenzene, 6.5mL (60mmol) of phenylacetylene, 112.3mg (0.5mmol) of palladium acetate, 95.3mg (0.5mmol) of ketone iodide, Xantphos (289.3mg (0.5mmol) CAS : 161265-03-8), cesium carbonate 32.6g (100mmol) was dissolved in 200mL N,N-dimethylformamide. Heated to 60°C and stirred for 16h. The end of the reaction was monitored by thin layer chromatography (TLC), and 200 mL of distilled water was added to the system to quench it. Extract with ethyl acetate (200mL*2), and wash the organic phase with saturated brine (200mL*2). It was dried over anhydrous magnesium sulfate, evaporated to dryness by rotary evaporation, and separated by column chromatography to obtain 10.47 g (yield rate: 94%) of yellow solid powder. The product was characterized by proton nuclear magnetic resonance, the spectrogram is shown in Figure 1, and the nuclear magnetic peak data are as follows:

¹ H NMR (CDCl ₃ , 400MHz): δ8.23(d, J=8.84Hz, 2H), 7.67(d, J=8.88Hz, 2H), 7.58-7.55(m, 2H), 7.40-7.39(m ,3H).

Step 2: Synthesis of 4-nitrobenzil

8.9 g (40 mmol) of 1-nitro-4-phenylethynylbenzene was uniformly dissolved in 250 mL of dimethyl sulfoxide, and 709.3 mg (4 mmol) of palladium dichloride was added. Heated to 145°C and stirred for 4h. The completion of the reaction was monitored by thin layer chromatography (TLC), and 250 mL of distilled water was added to the system to quench it. Extract with ethyl acetate (150ml*2), and wash the organic phase with saturated brine (100ml*2). Dry over anhydrous magnesium sulfate, rotary evaporate to dryness, and separate by column chromatography to obtain 8.78 g (86% yield) of yellow solid powder. The product was characterized by proton nuclear magnetic resonance, the spectrogram is shown in Figure 2, and the nuclear magnetic peak data are as follows:

¹ H NMR (CDCl ₃ , 400MHz): δ8.36(d, J=8.28Hz, 2H), 8.17(d, J=7.72Hz, 2H), 7.99(d, J=7.28Hz, 2H), 7.73- 7.70 (m, 1H), 7.58-7.54 (m, 2H).

Step 3: 2-(4-Nitrophenyl)-3-phenyl-6-nitroquinoxaline and 3-(4-nitrophenyl)-2-phenyl-6-nitroquinoxaline Synthesis of the mixture

Under normal temperature and pressure, 6.7 g (26 mmol) of 4-nitrobenzil, 4.0 g (26 mmol) of 4-nitro-o-phenylenediamine and 241 mg (1.3 mmol) of saccharin were uniformly dissolved in 250 mL of glacial acetic acid. Stir at room temperature for 1 h. The completion of the reaction was monitored by thin layer chromatography (TLC), and 250 mL of distilled water was added to the system to quench it. Filter, wash with distilled water three times, and dry to obtain 9.49 g (98% yield) of yellow solid powder. The product is characterized by proton NMR (comprising a mixture of two isomers), the spectrogram is as shown in Figure 3, and the NMR peak data are as follows:

¹ H NMR (CDCl ₃ , 400MHz): δ9.10(1H), 8.59-8.56(1H), 8.34-8.32(1H), 8.24-8.22(2H), 7.78-7.75(2H), 7.54-7.39(5H ).

Step 4: Synthesis of a mixture of 2-(4-aminophenyl)-3-phenyl-6-aminoquinoxaline and 3-(4-aminophenyl)-2-phenyl-6-aminoquinoxaline

9 g (24 mmol) of the nitro mixture was uniformly dissolved in 250 mL of methanol, and 0.9 g of 5% palladium carbon was added. After replacing the hydrogen three times with a hydrogen bag, the mixture was stirred at room temperature for 12 hours under an atmospheric pressure. Thin-layer chromatography (TLC) monitored the completion of the reaction, filtered through diatomaceous earth, and recovered palladium carbon. The filtrate was concentrated and recrystallized from methanol to obtain 5.85 g (78% yield) of yellow solid powder. The product is characterized by proton NMR (comprising a mixture of two isomers), the spectrogram is as shown in Figure 4, and the NMR peak data are as follows:

¹ H NMR (DMSO-d6, 500MHz): δ7.74-7.71(1H), 7.45-7.41(2H), 7.37-7.33(3H), 7.23-7.16(1H), 7.12-7.06(2H), 6.94- 6.92 (1H), 6.47-6.44 (2H), 6.02-5.98 (2H), 5.36-5.27 (2H).

The above description of the embodiments is for those of ordinary skill in the art to understand and apply the present application. It will be apparent to those skilled in the art that various modifications to these embodiments can be easily made, and the general principles described here can be applied to other embodiments without creative efforts. Therefore, the present application is not limited to the embodiments here, and improvements and modifications made by those skilled in the art based on the contents disclosed in the present application without departing from the scope and spirit of the present application are within the scope of the present application.

Claims (10)

1. A method for synthesizing nitroquinoxaline or derivatives thereof, characterized in that, the method comprises the following steps: in the presence of a catalyzer o-benzoylsulfonimide, making the mononitro-substituted ortho phenylenediamine or its derivatives react with mononitro-substituted benzil or its derivatives in a solvent for a predetermined period of time to obtain the nitroquinoxaline or its derivatives; Wherein said mononitro-substituted o-phenylenediamine or its derivatives have a structure shown by the following general formula (I): In the general formula (I), the groups R1, R2, R3 and R4 are each independently selected from H, C1-C10 alkyl or nitro, and there is one and only one of the groups R1, R2, R3 and R4 for nitro; Wherein, the mononitro-substituted benzil has a structure shown by the following general formula (II): In the general formula (II), the groups R5, R6, R7, R8, R9, R10, R11, R12, R13 and R14 are each independently selected from H, C1-C10 alkyl or nitro, and the groups R5, One and only one of R6, R7, R8, R9, R10, R11, R12, R13 and R14 is nitro; Wherein, the nitroquinoxaline or its derivatives have the structure shown by the following general formula (III): In the general formula (III), the groups R21, R22, R23 and R24 are each independently selected from H, C1-C10 alkyl or nitro, and only one of the groups R21, R22, R23 and R24 is Nitro; In general formula (III), group R31, R32, R33, R34, R35, R41, R42, R43, R44 and R45 are each independently selected from H, C1-C10 alkyl or nitro, and the group One and only one of groups R31, R32, R33, R34, R35, R41, R42, R43, R44 and R45 is nitro. 2. the method for synthetic nitroquinoxaline or derivative thereof as claimed in claim 1, is characterized in that, the benzil or derivative thereof of described mononitro substitution comprises 4-nitrobenzil, 3 -Nitrobenzil, 2-methyl-4-nitrobenzil, 3-methyl-4-nitrobenzil, 2,3-dimethyl-4-nitrobenzil, 2 ,3,5-trimethyl-4-nitrobenzil; And/or, the mononitro-substituted o-phenylenediamine or its derivatives are 3-nitro-o-phenylenediamine, 4-nitro-o-phenylenediamine, 5-nitro-o-phenylenediamine, 6-nitro O-phenylenediamine, 3-methyl-4-nitro-o-phenylenediamine, 5-methyl-4-nitro-o-phenylenediamine, 3,5-dimethyl-4-nitro-o-phenylenediamine or 3,5,6-trimethyl-4-nitro-o-phenylenediamine; And/or, the solvent is one or more of glacial acetic acid, methanol, N N-dimethylformamide or acetonitrile. 3. the method for synthesizing nitroquinoxaline or derivative thereof as claimed in claim 1, is characterized in that, in molar basis, described catalyst o-benzoylsulfonimide and mononitro-substituted The proportion of the amount of diazamide is less than or equal to 5%. 4. the method for synthetic nitroquinoxaline or its derivative as claimed in claim 1, is characterized in that, described nitroquinoxaline or its derivative comprise 2-(4-nitrophenyl)-3 -Phenyl-6-aminoquinoxaline and 3-(4-nitrophenyl)-2-phenyl-6-aminoquinoxaline mixture. 5. the method for synthetic nitroquinoxaline or derivative thereof as claimed in claim 2, is characterized in that, described 4-nitrobenzil is prepared by following method: (1) reacting nitrohalogenated benzene with phenylacetylene to obtain 1-nitro-4-phenylacetylene; and (2) reacting 1-nitro-4-phenylacetylene with an oxidizing agent in the presence of a metal catalyst to obtain the 4-nitrobenzil. 6. the method for synthetic nitroquinoxaline or derivatives thereof as claimed in claim 5, is characterized in that, described nitrohalobenzene is 4-nitroiodobenzene, 4-nitrobromobenzene or 4- Nitrochlorobenzene; And/or, the metal catalyst is palladium dichloride, or a mixture of aluminum chloride and palladium acetate in equimolar amounts; And/or, the oxidizing agent is dimethyl sulfoxide. 7. a method for synthesizing aminoquinoxaline or its derivatives, it is characterized in that, described method comprises to the prepared nitro by the method for synthetic nitroquinoxaline or its derivatives as claimed in claim 1 The nitro group corresponding to the quinoxaline or its derivatives is reduced to an amino group to obtain the aminoquinoxaline or its derivatives. 8. the method for synthetic aminoquinoxaline or derivative thereof as claimed in claim 7, is characterized in that, described aminoquinoxaline or derivative thereof is 2-(4-aminophenyl)-3-phenyl -6-aminoquinoxaline and 3-(4-aminophenyl)-2-phenyl-6-aminoquinoxaline mixture. 9. An application of o-benzoylsulfonimide as a catalyst in the synthesis of nitroquinoxaline or derivatives thereof. 10. A method for preparing 4-nitrobenzil, said method comprising the steps of: (1) reacting nitrohalogenated benzene with phenylacetylene to obtain 1-nitro-4-phenylacetylene; and (2) reacting 1-nitro-4-phenylacetylene with an oxidizing agent in the presence of a metal catalyst to obtain the 4-nitrobenzil.