Quinoxaline-5-carboxylic acid coordinated catalyst, composite catalyst, preparation method and application

Abstract

The invention discloses a quinoxaline-5-carboxylic acid coordinated catalyst and a preparation method thereof. B is a sodium ion, a magnesium ion, a calcium ion, an aluminum ion, a rubidium ion, a cesium ion, an ammonium ion, a tetradecyl dimethyl benzyl ammonium ion, a tetradecyl trimethyl ammonium ion, a hexadecyl trimethyl ammonium ion, a hexadecyl dimethyl benzyl ammonium ion, a tributyl octyl phosphonium ion, a tetrapropyl phosphonium ion and a dipropyl dibutyl phosphonium ion; the phosphonium ions are dibutyl dihexyl phosphonium ions, tetraheptyl phosphonium ions, tetrabutyl phosphonium ions, tetrabenzyl phosphonium ions, tetraheptyl ammonium ions, dimethyl diethylammonium ions, benzyl trihexyl ammonium ions, tribenzyl phenyl phosphonium ions or tetraphenyl ammonium ions; m is Sc, Ti, Mo, Fe, Ni, Tc, Zn, Zr, Cr, Mg or W; r is alkyl with 1 to 25 carbon atoms; x is an integer between 1 and 20; and y is an integer between 1 and 40. The catalyst can improve the oxidation reaction selectivity and conversion rate of ortho-nitrotoluene.

Description

Technical Field

[0001] The invention belongs to the technical field of organic chemistry, and specifically relates to a quinoxaline-5-carboxylic acid coordinated catalyst, a composite catalyst, a preparation method and an application. Background Art

[0002] o-Nitrotoluene is an important raw material, mainly used to produce o-toluidine and ditoluidine. In the pharmaceutical industry, it is used to produce nifedipine, metoclopramide, imipramine hydrochloride, bromhexidine hydrochloride, diclofenac sodium, and can also be used as a solvent. Under oxidative conditions, o-nitrotoluene is used to make o-nitrobenzaldehyde and o-nitrobenzoic acid; under catalysis, it can be reduced to o-toluidine; and azo components may also be produced. Nitrobenzoic acid is usually used as an intermediate. In organic synthesis, it is a 5HT2-D2 antagonist used to treat diseases such as schizophrenia and diabetic mania. At present, the preparation methods of o-nitrobenzoic acid mainly include 4-bromo-2-nitrobenzoic acid hydrogenation dehalogenation method, o-nitrotoluene nitration oxidation method, o-nitrobenzaldehyde photocatalytic oxidation method, 1-bromo-2-nitromethyl carbonylation-oxidation method, etc. Among them, the o-nitrobenzene toluene air oxidation method has outstanding environmental friendliness and the advantages of cheap and easy-to-obtain raw materials, and has the most application prospects.

[0003] At present, the most common research on the synthesis of phthalic acid by oxygen biocatalytic oxidation in alkaline medium is as follows: using metal phthalocyanine as a biomimetic catalyst in alkaline medium and using methanol as a solvent to catalyze the oxidation of o-nitrotoluene to phthalic acid. This method solves the problem of heavy mechanical corrosion and environmental pollution when producing o-nitrobenzoic acid in acidic medium.

[0004] Yu Yuanbin et al. reported the green synthesis of o-nitrobenzoic acid by substituted iron porphyrin-catalyzed oxidation of o-nitrotoluene, which used environmentally friendly ethanol aqueous solution as solvent to catalyze oxygen oxidation of o-nitrotoluene. However, this method has the disadvantages of high reaction pressure (2MPa), high alkalinity concentration (3.75mol / L), high alkalinity reaction (3.75mol / L), high reaction time (12h) and large resource consumption.

[0005] Chinese patent CN102093224A discloses a method for synthesizing o-nitrobenzoic acid using microwaves, which reduces reaction pressure, reduces the amount of alkali used, shortens reaction time, effectively reduces reaction energy consumption and operating costs, and improves reaction safety and efficiency. Although this method has a high conversion rate, the selectivity of the product is very low.

[0006] Publication number is that Chinese patent CN1944396A discloses a method using metalloporphyrin as raw material, the method uses 50-95% volume of ethanol containing o-nitrotoluene as solvent, 0.8-3MPa of oxygen is introduced into the high alkaline ethanol (sodium hydroxide) aqueous solution of 1-6mol / L, the reaction temperature is adjusted to 35-55 ℃, reacted for 2-14 hours, and o-nitrobenzoic acid is obtained. The reaction pressure of the method is relatively high (0.8 to 3MPa), resulting in high energy consumption of synthesis reaction and poor safety. Due to the relatively large consumption of sodium hydroxide (1-6mol / L), the amount of acid used for neutralization in the aftertreatment process increases, and a large amount of saline wastewater is produced. It not only wastes a large amount of resources, but also brings serious pollution.

[0007] The information disclosed in this background technology section is only intended to enhance the understanding of the overall background of the invention and should not be regarded as an acknowledgment or any form of suggestion that the information constitutes the prior art already known to a person skilled in the art. Summary of the invention

[0008] The purpose of the present invention is to provide a quinoxaline-5-carboxylic acid coordinated catalyst, a composite catalyst, a preparation method and an application, which can effectively improve the selectivity and conversion rate of the o-nitrotoluene oxidation reaction.

[0009] In order to achieve the above object, a technical solution provided by a specific embodiment of the present invention is as follows:

[0010] A quinoxaline-5-carboxylic acid coordinated catalyst, the catalyst having a general formula as shown in (I):

[0011]

[0012] wherein B is a sodium ion, a magnesium ion, a calcium ion, an aluminum ion, a rubidium ion, a cesium ion, an ammonium ion, a tetradecyldimethylbenzylammonium ion, a tetradecyltrimethylammonium ion, a hexadecyltrimethylammonium ion, a hexadecyldimethylbenzylammonium ion, a tributyloctylphosphonium ion, a tetrapropylphosphonium ion, a dipropyldibutylphosphonium ion, a dibutyldihexylphosphonium ion, a tetraheptylphosphonium ion, a tetrabutylphosphonium ion, a tetraheptylammonium ion, a dimethyldiethylammonium ion, a benzyltrihexylammonium ion, a tetrabenzylammonium ion, a tribenzylphenylphosphonium ion, or a tetraphenylammonium ion;

[0013] M is Sc, Ti, Mo, Fe, Ni, Tc, Zn, Zr, Cr, Mg or W;

[0014] R is selected from C1~C 25 alkyl;

[0015] x is selected from an integer between 1 and 20;

[0016] y is an integer selected from 1 to 40.

[0017] Another specific embodiment of the present invention provides a technical solution as follows:

[0018] A method for preparing the above-mentioned quinoxaline-5-carboxylic acid coordinated catalyst comprises the following steps:

[0019] Dissolve the metal compound in deionized water, adjust the solution pH to 2-4, and then add peroxide to obtain a metal peroxide solution;

[0020] Add alkyl-substituted quinoxaline-5-carboxylic acid and salt to the metal peroxide solution, filter and dry to obtain a quinoxaline-5-carboxylic acid coordinated catalyst.

[0021] In one or more embodiments of the present invention, the metal compound is selected from scandium chloride, magnesium sulfate, molybdenum nitrate, magnesium chloride, nickel chloride, potassium titanium oxalate, iron nitrate, zinc sulfate, iron chloride, iron sulfate, tungsten chloride, zirconium acetate and chromium nitrate.

[0022] In one or more embodiments of the present invention, the peroxide is selected from hydrogen peroxide and meta-chloroperbenzoic acid.

[0023] In one or more embodiments of the present invention, the alkyl-substituted quinoxaline-5-carboxylic acid is selected from 8-methylquinoxaline-5-carboxylic acid, 8-ethylquinoxaline-5-carboxylic acid, 8-isopropylquinoxaline-5-carboxylic acid, 8-n-butylquinoxaline-5-carboxylic acid, 8-tert-butylquinoxaline-5-carboxylic acid, 8-n-pentylquinoxaline-5-carboxylic acid or 8-isopentylquinoxaline-5-carboxylic acid.

[0024] In one or more embodiments of the present invention, the salt is selected from tetradecyldimethylbenzylammonium bromide, tetradecyltrimethylammonium chloride, tetradecyltrimethylammonium bromide, sodium bromide, magnesium bromide, calcium chloride, aluminum chloride, rubidium bromide, ammonium chloride, hexadecyltrimethylammonium bromide, hexadecyldimethylbenzylammonium ion, tributyloctylphosphonium chloride, tetrapropylphosphonium bromide, dipropyldibutylphosphonium bromide, tetrabenzylammonium bromide, dimethyldiethylammonium bromide, benzyltrihexylammonium bromide, tribenzylphenylphosphonium bromide and tetraphenylammonium bromide.

[0025] Another specific embodiment of the present invention provides a technical solution as follows:

[0026] A composite catalyst comprises the above-mentioned catalyst coordinated with quinoxaline-5-carboxylic acid.

[0027] In one or more embodiments of the present invention, a cocatalyst is further included, and the weight ratio of the catalyst coordinated by quinoxaline-5-carboxylic acid to the cocatalyst is 100:(1-200);

[0028] The cocatalyst is selected from cerium chloride, cerium nitrate, manganese chloride, manganese sulfate, manganese nitrate, manganese dioxide, vanadium chloride, cobalt nitrate, silver acetate, zirconium nitrate, zirconium sulfate, ferric acetate, ferric nitrate, ferric chloride, copper oxide, copper chloride, copper nitrate, magnesium chloride, magnesium sulfate, zinc acetate, zinc chloride, sodium nitrate, potassium acetate and potassium chloride.

[0029] In one or more embodiments of the present invention, a regulator is further included, and the weight ratio of the catalyst coordinated by quinoxaline-5-carboxylic acid to the regulator is 100:(1-400);

[0030] The regulator is selected from phosphoric acid, phosphomolybdic acid, tetrabutylammonium fluoride, boric acid, tetrabutylammonium chloride and phosphomolybdic vanadic acid.

[0031] In one or more embodiments of the present invention, a protective agent is further included, and the weight ratio of the catalyst coordinated by quinoxaline-5-carboxylic acid to the protective agent is 100:(1-600);

[0032] The protective agent is selected from magnesium acetate, sodium bromide, octadecyltripropylammonium bromide, diphenyldipropylammonium bromide, sodium tungstate and N-hydroxyphthalimide.

[0033] In one or more embodiments of the present invention, a solvent is further included, and the weight ratio of the catalyst coordinated by quinoxaline-5-carboxylic acid to the solvent is 100:(20-20000);

[0034] The solvent is selected from the group consisting of ethylene dichloride, tetrahydrofuran, methanol, ethanol, ethyl acetate, 1,4-dioxane, acetic acid, n-hexanoic acid and n-heptanoic acid.

[0035] The technical solution provided by a specific embodiment of the present invention is as follows:

[0036] A method for preparing a composite catalyst comprises the following steps:

[0037] Mix the protective agent and the solvent to obtain a solution;

[0038] Add the catalyst coordinated with quinoxaline-5-carboxylic acid to the solution and stir at 0-100° C. for 5-30 minutes;

[0039] Then add the auxiliary catalyst and ultrasonicate at 0-100°C for 10-40 minutes;

[0040] Then add a regulator, stir at 0-100°C for 20-30 minutes to obtain a composite catalyst.

[0041] A use of the above-mentioned quinoxaline-5-carboxylic acid coordinated catalyst, the quinoxaline-5-carboxylic acid coordinated catalyst prepared by the preparation method of the above-mentioned quinoxaline-5-carboxylic acid coordinated catalyst, or the above-mentioned composite catalyst in catalytic oxidation of o-nitrotoluene to prepare o-nitrobenzoic acid.

[0042] Compared with the prior art, the catalyst and composite catalyst coordinated by quinoxaline-5-carboxylic acid in the present invention can improve the selectivity and reaction activity of the o-nitrotoluene oxidation reaction, and can be applied multiple times with a high utilization rate. DETAILED DESCRIPTION

[0043] In order to enable those skilled in the art to better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention.

[0044] A specific embodiment of the present invention provides a quinoxaline-5-carboxylic acid coordinated catalyst, the catalyst general formula is shown as (I):

[0045]

[0046] Wherein, B is sodium ion, magnesium ion, calcium ion, aluminum ion, rubidium ion, cesium ion, ammonium ion, tetradecyldimethylbenzylammonium ion, tetradecyltrimethylammonium ion, hexadecyltrimethylammonium ion, hexadecyldimethylbenzylammonium ion, tributyloctylphosphonium ion, tetrapropylphosphonium ion, dipropyldibutylphosphonium ion, dibutyldihexylphosphonium ion, tetraheptylphosphonium ion, tetrabutylphosphonium ion, tetrabenzylphosphonium ion, tetraheptylammonium ion, dimethyldiethylammonium ion, benzyltrihexylammonium ion, tetrabenzylammonium ion, tribenzylphenylphosphonium ion or tetraphenylammonium ion; M is Sc, Ti, Mo, Fe, Ni, Tc, Zn, Zr, Cr, Mg or W; R is selected from Cl~C 25 alkyl; x is selected from an integer between 1 and 20; y is selected from an integer between 1 and 40.

[0047] Preferably, B is selected from magnesium ion, calcium ion, tributyloctylphosphonium chloride, tetrapropylphosphonium ion, dipropyldibutylphosphonium ion, tetraphenylammonium ion, dimethyldiethylammonium ion, tetrabenzylammonium ion, benzyltrihexylammonium ion; M is Ti, Mo, Fe, Zn, Cr or Zr; R is selected from C1-C 10 Alkyl; x is selected from an integer between 1 and 5; y is selected from an integer between 1 and 10.

[0048] More preferably, B is selected from magnesium ion, tetraphenylammonium ion, benzyltrihexylammonium ion and tetrabenzylammonium ion; M is selected from Ti, Fe, Cr or Mg; R is selected from methyl, ethyl, isopropyl; x is 1; y is 1 or 2.

[0049] Exemplary, quinoxaline-5-carboxylic acid coordinated catalysts are:

[0050]

[0051] Another specific embodiment of the present invention provides a method for preparing a catalyst coordinated by quinoxaline-5-carboxylic acid, comprising the following steps 1-2.

[0052] Step 1, dissolving the metal compound in deionized water, adjusting the solution pH to 2-4, and then adding peroxide to obtain a metal peroxide solution.

[0053] Specifically, deionized water is added to the metal compound at 0-5°C to dissolve it, and sulfuric acid and hydrochloric acid are used to adjust the pH of the solution. The metal compound is selected from scandium chloride, magnesium sulfate, molybdenum nitrate, magnesium chloride, nickel chloride, potassium titanium oxalate, ferric nitrate, zinc sulfate, ferric chloride, ferric sulfate, tungsten chloride, zirconium acetate and chromium nitrate; and the peroxide is selected from hydrogen peroxide and meta-chloroperbenzoic acid.

[0054] Step 2, adding alkyl-substituted quinoxaline-5-carboxylic acid and salt to the metal peroxide solution, filtering and drying to obtain a quinoxaline-5-carboxylic acid coordinated catalyst.

[0055] Specifically, the alkyl-substituted quinoxaline-5-carboxylic acid is selected from 8-methylquinoxaline-5-carboxylic acid, 8-ethylquinoxaline-5-carboxylic acid, 8-isopropylquinoxaline-5-carboxylic acid, 8-n-butylquinoxaline-5-carboxylic acid, 8-tert-butylquinoxaline-5-carboxylic acid, 8-n-pentylquinoxaline-5-carboxylic acid or 8-isopentylquinoxaline-5-carboxylic acid. The salt is selected from tetradecyldimethylbenzylammonium bromide, tetradecyltrimethylammonium chloride, tetradecyltrimethylammonium bromide, sodium bromide, magnesium bromide, calcium chloride, aluminum chloride, rubidium bromide, ammonium chloride, hexadecyltrimethylammonium bromide, hexadecyldimethylbenzylammonium ion, tributyloctylphosphonium chloride, tetrapropylphosphonium bromide, dipropyldibutylphosphonium bromide, tetrabenzylphosphonium bromide, tetrabenzylammonium bromide, dimethyldiethylammonium bromide, benzyltrihexylammonium bromide, tribenzylphenylphosphonium bromide and tetraphenylammonium bromide.

[0056] Another specific embodiment of the present invention provides a composite catalyst, comprising the above-mentioned quinoxaline-5-carboxylic acid coordinated catalyst, cocatalyst, regulator, protective agent and solvent in a weight ratio of 100: (1-200): (1-400): (1-600): (20-20000).

[0057] Specifically, the cocatalyst is selected from cerium chloride, cerium nitrate, manganese chloride, manganese sulfate, manganese nitrate, manganese dioxide, vanadium chloride, cobalt nitrate, silver acetate, zirconium nitrate, zirconium sulfate, ferric acetate, ferric nitrate, ferric chloride, copper oxide, copper chloride, copper nitrate, magnesium chloride, magnesium sulfate, zinc acetate, zinc chloride, sodium nitrate, potassium acetate and potassium chloride. The regulator is selected from phosphoric acid, phosphomolybdic acid, tetrabutylammonium fluoride, boric acid, tetrabutylammonium chloride and phosphomolybdic vanadic acid. The protective agent is selected from magnesium acetate, sodium bromide, octadecyltripropylammonium bromide, diphenyldipropylammonium bromide, sodium tungstate and N-hydroxyphthalimide. The solvent is selected from dichloroethane, tetrahydrofuran, methanol, ethanol, ethyl acetate, 1,4-dioxane, acetic acid, n-hexanoic acid and n-heptanoic acid. Selecting the above types of cocatalysts, regulators and protective agents can help improve the reaction selectivity, stabilize the catalyst structure, and improve the efficiency of the catalytic oxidation reaction.

[0058] Preferably, the weight ratio of the catalyst coordinated by quinoxaline-5-carboxylic acid, the cocatalyst, the regulator, the protective agent and the solvent is 100:(20-100):(50-150):(30-80):(200-500). The catalyst coordinated by quinoxaline-5-carboxylic acid is selected from the catalyst coordinated by quinoxaline-5-carboxylic acid with Ti, Mo, Fe, Ni or W as the central metal. The cocatalyst is selected from manganese sulfate, silver acetate, magnesium chloride and zinc acetate. The regulator is selected from tetrabutylammonium chloride, boric acid and phosphomolybdic acid. The protective agent is selected from magnesium acetate, diphenyldipropylammonium bromide, sodium tungstate and N-hydroxyphthalimide. The solvent is selected from ethyl acetate, 1,4-dioxane and acetic acid.

[0059] Another specific embodiment of the present invention provides a method for preparing a composite catalyst, comprising the following steps: preparing all raw materials, including a catalyst coordinated with quinoxaline-5-carboxylic acid, a cocatalyst, a regulator, a protective agent and a solvent;

[0060] Mix the protective agent and the solvent to obtain a solution;

[0061] Add the catalyst coordinated with quinoxaline-5-carboxylic acid to the solution and stir at 0-100° C. for 5-30 minutes;

[0062] Then add the auxiliary catalyst and ultrasonicate at 0-100°C for 10-40 minutes;

[0063] Then add a regulator, stir at 0-100°C for 20-30 minutes to obtain a composite catalyst.

[0064] Another specific embodiment of the present invention provides the use of the above-mentioned quinoxaline-5-carboxylic acid coordinated catalyst, the quinoxaline-5-carboxylic acid coordinated catalyst prepared by the preparation method of the above-mentioned quinoxaline-5-carboxylic acid coordinated catalyst, or the above-mentioned composite catalyst in catalytic oxidation of o-nitrotoluene to prepare o-nitrobenzoic acid.

[0065] Specifically, o-nitrotoluene is dissolved in a solvent, a catalyst coordinated with quinoxaline-5-carboxylic acid or a composite catalyst is added thereto, air is introduced at a rate of 50 to 200 mL / min, and the reaction is stirred at 80 to 180° C. for 0.5 to 5 hours. Taking the composite catalyst as an example, the amount of the composite catalyst added is 0.01% to 10% of the weight of o-nitrotoluene.

[0066] Preferably, the solvent is n-heptanoic acid. The reaction temperature is 100-130° C., the reaction time is 1-3 hours, the air introduction rate is 100-120 mL / min, and the amount of the composite catalyst added is 0.05%-0.5% of the weight of o-nitrotoluene.

[0067] The present invention is further described in detail below in conjunction with specific embodiments.

[0068] Quinoxaline-5-carboxylic acid coordinated catalyst example

[0069] Example 1

[0070] Step 1: Add 200 mL of deionized water to solid magnesium sulfate (12.04 g, 0.1 mol) at 0°C, and after the solid is completely dissolved, obtain solution a. Add dilute hydrochloric acid dropwise to solution a until the pH of the solution is 3 to obtain solution b. Continue stirring for about 90 minutes, then slowly add 150 mL of 30% hydrogen peroxide solution to solution b to obtain solution c. Add deionized water to solution c until the total liquid volume is 1000 mL to obtain solution d.

[0071] Step 2: Reduce the temperature of solution d to 5°C, add 8-methylquinoxaline-5-carboxylic acid (28.21 g, 0.12 mol) and tetradecyl dimethyl benzyl ammonium bromide (90.75 g, 0.22 mol) to solution d, heat and stir for about 1 hour, and then centrifuge for 20 minutes. Filter, and place the solid obtained after filtration in a vacuum drying oven to dry to obtain 88.75 g of yellow solid, which is the catalyst YG-58-01-001 coordinated with quinoxaline-5-carboxylic acid, and the catalyst yield reaches 90.21%. The nuclear magnetic characterization data are as follows:

[0072] 1 H NMR: δ0.86(3H,t,J=7.0Hz),1.16-1.40(22H,m)),1.88(2H,tt,J=7.7,7.4Hz), δ2.44(3H,s),2.88(6H,s),3.10(2H, t,J=7.7Hz),4.38(2H,s),7.31-7.52(5H,m),7.64-7.78(2H,m),8.07(1H,s),8.85-9.00(2H,m),8.94(d,J=6.8Hz).

[0073] Example 2

[0074] Step 1: Add 200 mL of deionized water to solid magnesium sulfate (12.04 g, 0.1 mol) at 0°C, and after the solid is completely dissolved, obtain solution a. Add dilute hydrochloric acid dropwise to solution a until the pH of the solution is 4 to obtain solution b. Continue stirring for about 60 minutes, then slowly add 150 mL of 30% hydrogen peroxide solution to solution b to obtain solution c. Add deionized water to solution c until the total liquid volume is 1000 mL to obtain solution d.

[0075] Step 2: Heat solution d to 25°C, add 8-ethylquinoxaline-5-carboxylic acid (30.31 g, 0.12 mol) and aluminum chloride (29.27 g, 0.22 mol) to solution d, stir while heating for about 1.5 hours, and centrifuge for 20 minutes. Filter, and place the solid obtained after filtration in a vacuum drying oven to dry to obtain 40.15 g of yellow solid, which is the catalyst YG-58-01-002 coordinated with quinoxaline-5-carboxylic acid, and the catalyst yield reaches 89.58%. The nuclear magnetic characterization data are as follows:

[0076] 1 H NMR: δ1.14(3H,t,J=7.1Hz), 3.02(2H,q,J=7.1Hz), 7.55(1H,s), 7.72(1H,s), 8.08(1H,s), 8.85-9.00(2H,m).

[0077] Example 3

[0078] Step 1: Add 200 mL of deionized water to solid magnesium sulfate (24.07 g, 0.2 mol) at 0°C, and after the solid is completely dissolved, obtain solution a. Add dilute sulfuric acid dropwise to solution a until the pH of the solution is 1 to obtain solution b. Continue stirring for about 100 min, then slowly add 150 mL of 30% hydrogen peroxide solution to solution b to obtain solution c. Add deionized water to solution c until the total liquid volume is 1000 mL to obtain solution d.

[0079] Step 2: Heat solution d to 50°C, add 8-butylquinoxaline-5-carboxylic acid (34.52 g, 0.12 mol) and calcium chloride (12.21 g, 0.11 mol) to solution d, stir while heating for about 1 hour, and centrifuge for 15 minutes. Filter, and place the solid obtained after filtration in a vacuum drying oven to dry to obtain a 68.65 yellow solid, which is the metal peroxide catalyst YG-58-01-003 coordinated with quinoxaline-5-carboxylic acid, and the catalyst yield reaches 89.14%. The nuclear magnetic characterization data are as follows:

[0080] 1 H NMR: δ0.88(3H,t,J=6.5Hz), 1.31(2H,tq,J=6.6,6.5Hz), 1.71(2H,tt,J=7.1 ,6.6Hz),3.08(2H,t,J=7.1Hz),7.92-8.14(2H,m),8.95(1H,s),9.26(1H,s).

[0081] Example 4

[0082] Step 1: Add 200 mL of deionized water to solid ferric nitrate (24.19 g, 0.1 mol) at 5°C, and after the solid is completely dissolved, obtain solution a. Add dilute hydrochloric acid dropwise to solution a until the pH of the solution is 2 to obtain solution b. Continue stirring for about 5 minutes, then slowly add 150 mL of 30% hydrogen peroxide solution to solution b to obtain solution c. Add deionized water to solution c until the total liquid volume is 1000 mL to obtain solution d.

[0083] Step 2: Heat solution d to 100°C, add 8-methylquinoxaline-5-carboxylic acid (28.21 g, 0.12 mol) and tetradecyltrimethylammonium bromide (74.00 g, 0.22 mol) to solution d, stir while heating for about 2 hours, and centrifuge for 15 minutes. Filter, and place the solid obtained after filtration in a vacuum drying oven to dry to obtain 67.76 g of yellow solid, which is the catalyst YG-58-01-004 coordinated with quinoxaline-5-carboxylic acid, and the catalyst yield reaches 94.12%. The nuclear magnetic characterization data are as follows:

[0084] 1 H NMR: δ0.86(3H,t,J=7.0Hz),1.16-1.43(22H,m),1.94(2H,q,J=7.4Hz), δ2.44(3H,s),2.84(9H,s),3 .05(2H,t,J=7.4Hz).),7.64-7.78(2H,m),7.71(dd,J=7.7,2.0Hz)),8.07(1H,s),8.85-9.00(2H,m).

[0085] Example 5

[0086] Step 1: Add 200 mL of deionized water to solid ferric chloride (32.44 g, 0.2 mol) at 0°C, and after the solid is completely dissolved, obtain solution a. Add dilute nitric acid dropwise to solution a until the pH of the solution is 2 to obtain solution b. Continue stirring for about 30 minutes, then slowly add 150 mL of 30% hydrogen peroxide solution to solution b to obtain solution c. Add deionized water to solution c until the total liquid volume is 1000 mL to obtain solution d.

[0087] Step 2: Heat solution d to 80°C, add 8-methylquinoxaline-5-carboxylic acid (34.52 g, 0.12 mol) and rubidium bromide (19.84 g, 0.12 mol) to solution d, stir while heating for about 1 hour, and centrifuge for 20 minutes. Filter, and place the solid obtained after filtration in a vacuum drying oven to dry to obtain 61.70 g of yellow solid, which is the catalyst YG-58-01-005 coordinated with quinoxaline-5-carboxylic acid, and the catalyst yield reaches 86.28%. The nuclear magnetic characterization data are as follows:

[0088] 1 H NMR: δ2.47(3H,s),7.91-8.13(2H,m),8.94(1H,s),9.25(1H,s).

[0089] Example 6

[0090] Step 1: Add 200 mL of deionized water to solid ferric sulfate (17.19 g, 0.1 mol) at 0°C, and after the solid is completely dissolved, obtain solution a. Add dilute hydrochloric acid dropwise to solution a until the pH of the solution is 3 to obtain solution b. Continue stirring for about 10 minutes, then slowly add 200 mL of 30% m-chloroperbenzoic acid solution to solution b to obtain solution c. Add deionized water to solution c until the total liquid volume is 1000 mL to obtain solution d.

[0091] Step 2: Heat solution d to 60°C, add 8-ethylquinoxaline-5-carboxylic acid (30.31 g, 0.12 mol) and tetraphenylammonium bromide (79.10 g, 0.22 mol) to solution d, stir while heating for about 6 hours, and centrifuge for 15 minutes. Filter, and place the solid obtained after filtration in a vacuum drying oven to dry to obtain 63.01 g of yellow solid, which is the catalyst YG-58-01-006 coordinated with quinoxaline-5-carboxylic acid, and the catalyst yield reaches 91.48%. The nuclear magnetic characterization data are as follows:

[0092] 1 H NMR: δ1.22-1.34(3H,m),2.93-3.05(2H,m),7.46-7.65(12H,m),7.92-8.13(2H,m),8.18-8.31(8H,m),8.94(1H,s),9.26(1H,s).

[0093] Example 7

[0094] Step 1: Add 200 mL of deionized water to solid chromium nitrate (40.01 g, 0.1 mol) at 0°C, and after the solid is completely dissolved, obtain solution a. Add dilute hydrochloric acid dropwise to solution a until the pH of the solution is 3 to obtain solution b. Continue stirring for about 30 minutes, then slowly add 200 mL of 30% urea peroxide solution to solution b to obtain solution c. Add deionized water to solution c until the total liquid volume is 1000 mL to obtain solution d.

[0095] Step 2: Heat solution d to 50°C, add 8-methylquinoxaline-5-carboxylic acid (28.21 g, 0.12 mol) and tetrabenzylphosphonium bromide (86.94 g, 0.22 mol) to solution d, stir while heating for about 1 hour, and centrifuge for 10 minutes. Filter, and dry the solid obtained after filtration in a vacuum drying oven to obtain 60.55 g of yellow solid, which is the catalyst YG-58-01-007 coordinated with quinoxaline-5-carboxylic acid, and the catalyst yield reaches 86.15%. The nuclear magnetic characterization data are as follows:

[0096] 1 H NMR: δ2.42-2.52(3H,s),3.67-3.76(8H,s),7.13-7.46(20H,m),7.91-8.13(2H,m),9.10(2H,d,J=6.7Hz).

[0097] Example 8

[0098] Step 1: Add 200 mL of deionized water to solid ferric sulfate (17.19 g, 0.1 mol) at 0°C, and after the solid is completely dissolved, obtain solution a. Add dilute hydrochloric acid dropwise to solution a until the pH of the solution is 3 to obtain solution b. Continue stirring for about 30 minutes, then slowly add 200 mL of 30% tert-butyl hydroperoxide solution to solution b to obtain solution c. Add deionized water to solution c until the total liquid volume is 1000 mL to obtain solution d.

[0099] Step 2: Heat solution d to 25°C, add 8-butylquinoxaline-5-carboxylic acid (34.52 g, 0.12 mol) and aluminum chloride (29.27 g, 0.22 mol) to solution d, stir while heating for about 5 hours, and centrifuge for 20 minutes. Filter, and place the solid obtained after filtration in a vacuum drying oven to dry to obtain 52.83 g of purple-red solid, which is the catalyst YG-58-01-008 coordinated with quinoxaline-5-carboxylic acid, and the catalyst yield reaches 83.76%. The nuclear magnetic characterization data are as follows:

[0100] 1H NMR: δ0.88(3H,t,J=6.5Hz), 1.31(2H,tq,J=6.6,6.5Hz), 1.71(2H,tt,J=7.1,6.6Hz), 3.08(2H,t,J=7.1 Hz), 7.92-8.14 (2H, 7.98 (d, J = 8.5Hz), 8.08 (d, J = 8.5Hz)), 8.95 (1H, d, J = 6.7Hz), 9.26 (1H, d, J = 6.7Hz).

[0101] Composite Catalyst Example

[0102] Example 9

[0103] Step (1): adding 20.0 g of acetic acid to 1.0 g of magnesium acetate, and stirring at room temperature until the solid is completely dissolved to obtain a mixture A;

[0104] Step (2): add 1.0 g of quinoxaline-5-carboxylic acid coordinated catalyst YG-58-01-001 to the mixed solution of step (1), and heat with stirring at 80° C. for 15 min to obtain a mixture B;

[0105] Step (3): add 0.1 g of cerium chloride to the mixture B formed in step (2), and ultrasonicate at 80° C. for 15 min to obtain a mixture C;

[0106] Step (4): Add 0.2 g of phosphomolybdic acid to the mixture C formed in step (3), and stir at 80° C. for 15 minutes to obtain a total of 22.3 g of the composite catalyst 1.

[0107] Example 10

[0108] Step (1): add 100.0 g of ethyl acetate to 5.0 g of diphenyldipropylammonium bromide, and stir at room temperature until the solid is completely dissolved to obtain a mixture A;

[0109] Step (2): add 1.0 g of quinoxaline-5-carboxylic acid coordinated catalyst YG-58-01-002 to the mixed solution of step (1), and heat at 75° C. with stirring for 30 min to obtain a mixture B;

[0110] Step (3): adding 0.5 g of manganese sulfate to the mixture B formed in step (2), and ultrasonicating at 75° C. for 10 min to obtain a mixture C;

[0111] Step (4): Add 0.3 g of tetrabutylammonium fluoride to the mixture C formed in step (3), and stir at 75° C. for 20 minutes to obtain a total of 106.8 g of composite catalyst 2.

[0112] Embodiment 11

[0113] Step (1): adding 50.0 g of acetic acid to 2.0 g of octadecyltripropylammonium bromide, and stirring at room temperature until the solid is completely dissolved to obtain a mixture A;

[0114] Step (2): add 1.0 g of quinoxaline-5-carboxylic acid coordinated catalyst YG-58-01-003 to the mixed solution of step (1), and heat at 60° C. with stirring for 5 min to obtain a mixture B;

[0115] Step (3): add 1.1 g of silver acetate to the mixture B formed in step (2), and ultrasonicate at 60° C. for 10 min to obtain a mixture C;

[0116] Step (4): Add 0.8 g of phosphomolybdic acid to the mixture C formed in step (3), and stir at 60° C. for 25 minutes to obtain a total of 54.9 g of composite catalyst 3.

[0117] Example 12

[0118] Step (1): add 20.0 g of ethyl acetate to 1.5 g of octadecyltripropylammonium bromide, and stir at room temperature until the solid is completely dissolved to obtain a mixture A;

[0119] Step (2): add 1.0 g of quinoxaline-5-carboxylic acid coordinated catalyst YG-58-01-004 to the mixed solution of step (1), and heat at 70° C. with stirring for 15 min to obtain a mixture B;

[0120] Step (3): add 0.2 g of copper oxide to the mixture B formed in step (2), and ultrasonicate at 70° C. for 10 min to obtain a mixture C;

[0121] Step (4): Add 0.2 g of boric acid to the mixture C formed in step (3), and stir at 70° C. for 60 minutes to obtain a total of 22.9 g of composite catalyst 4.

[0122] Example 13

[0123] Step (1): add 100.0 g of n-hexanoic acid to 5.0 g of sodium tungstate, and stir at room temperature until the solid is completely dissolved to obtain a mixture A;

[0124] Step (2): add 1.0 g of quinoxaline-5-carboxylic acid coordinated catalyst YG-58-01-005 to the mixed solution of step (1), and heat at 100° C. with stirring for 30 min to obtain a mixture B;

[0125] Step (3): adding 1.0 g of cerium chloride to the mixture B formed in step (2), and ultrasonicating at 100° C. for 10 min to obtain a mixture C;

[0126] Step (4): Add 0.5 g of phosphomolybdic vanadic acid to the mixture C formed in step (3), and stir at 100° C. for 30 minutes to obtain a total of 107.5 g of composite catalyst 5.

[0127] Embodiment 14

[0128] Step (1): adding 30.0 g of acetic acid to a solid mixture of 1.0 g of magnesium acetate and 0.5 g of octadecyltripropylammonium bromide, and stirring at room temperature until the solid is completely dissolved to obtain a mixture A;

[0129] Step (2): add 1.0 g of quinoxaline-5-carboxylic acid coordinated catalyst YG-58-01-006 to the mixed solution of step (1), and heat at 50° C. with stirring for 10 min to obtain a mixture B;

[0130] Step (3): Add 2.0 g of magnesium chloride to the mixture B formed in step (2), and ultrasonicate at 50° C. for 10 min to obtain a mixture C;

[0131] Step (4): Add 1.0 g of phosphoric acid to the mixture C formed in step (3), and stir at 50° C. for 30 minutes to obtain a total of 35.5 g of composite catalyst 6.

[0132] Embodiment 15

[0133] Step (1): adding 50.0 g of n-hexanoic acid to a solid mixture of 2.0 g of octadecyltripropylammonium bromide and 1.0 g of diphenyldipropylammonium bromide, and stirring at room temperature until the solid is completely dissolved to obtain a mixture A;

[0134] Step (2): add 1.0 g of quinoxaline-5-carboxylic acid coordinated catalyst YG-58-01-007 to the mixed solution of step (1), and heat at 80° C. with stirring for 5 min to obtain a mixture B;

[0135] Step (3): add 0.1 g of zinc acetate to the mixture B formed in step (2), and ultrasonicate at 80° C. for 10 min to obtain a mixture C;

[0136] Step (4): Add 0.1 g of tetrabutylammonium fluoride to the mixture C formed in step (3), and stir at 80° C. for 20 minutes to obtain 54.2 g of composite catalyst 7.

[0137] Example 16

[0138] Step (1): adding 200.0 g of ethyl acetate to a solid mixture of 5.0 g of diphenyldipropylammonium bromide and 1.0 g of sodium tungstate, and stirring at room temperature until the solid is completely dissolved to obtain a mixture A;

[0139] Step (2): add 1.0 g of quinoxaline-5-carboxylic acid coordinated catalyst YG-58-01-008 to the mixed solution of step (1), and heat with stirring at 25° C. for 10 min to obtain a mixture B;

[0140] Step (3): Add 2.0 g of potassium chloride to the mixture B formed in step (2), and ultrasonicate at 25° C. for 40 min to obtain a mixture C;

[0141] Step (4): Add 4.0 g of tetrabutylammonium chloride to the mixture C formed in step (3), and stir at 25° C. for 120 minutes to obtain a total of 213.0 g of the composite catalyst 8.

[0142] Application Examples

[0143] Embodiment 17

[0144] Composite catalyst 1 (0.05 g) and o-nitrotoluene (100 g) were added to a 250 mL titanium autoclave in sequence. After the autoclave was installed, nitrogen was filled in until the pressure inside the autoclave was 0.5 MPa and maintained for 15 minutes. If the pressure drop did not exceed 5%, the air tightness of the autoclave was considered good. After the nitrogen was discharged, the temperature was raised to 100 ° C, and air was passed until the pressure inside the autoclave was 0.3 MPa. The air was passed continuously, and the flow rate was controlled to be 100-120 mL / min. The reaction was terminated after 3 hours. The reaction solution was dark green, and the total weight of the reaction solution was weighed to be 133.29 g. Take 0.1 g of the reaction solution, toluene as the internal standard, take 0.1 g of toluene, add 30 g of acetonitrile to dilute, and then inject the sample for testing. Substituting the test data into the internal standard curve, the o-nitrotoluene conversion rate was calculated to be 71.60%, and the o-nitrobenzoic acid selectivity was 94.41%.

[0145] Embodiment 18

[0146] Composite catalyst 2 (0.10 g) and o-nitrotoluene (100 g) were added to a 250 mL titanium autoclave in sequence. After the autoclave was installed, nitrogen was filled until the pressure inside the autoclave was 0.5 MPa and maintained for 15 minutes. If the pressure drop did not exceed 5%, the air tightness of the autoclave was considered good. After the nitrogen was discharged, the temperature was raised to 105 ° C, and air was passed until the pressure inside the autoclave was 0.3 MPa. The air was passed continuously, and the flow rate was controlled to be 100-120 mL / min. The reaction was terminated after 2 hours. The reaction solution was dark green, and the total weight of the reaction solution was weighed to be 134.18 g. Take 0.1 g of the reaction solution, toluene as the internal standard, take 0.1 g of toluene, add 30 g of acetonitrile to dilute, and then inject the sample for testing. Substituting the test data into the internal standard curve, the o-nitrotoluene conversion rate was calculated to be 62.62%, and the o-nitrobenzoic acid selectivity was 91.19%.

[0147] Embodiment 19

[0148] Composite catalyst 3 (0.15 g) and o-nitrotoluene (100 g) were added to a 250 mL titanium autoclave in sequence. After the autoclave was installed, nitrogen was filled in until the pressure inside the autoclave was 0.5 MPa and maintained for 15 minutes. If the pressure drop did not exceed 5%, the air tightness of the autoclave was considered good. After the nitrogen was discharged, the temperature was raised to 110 ° C, and air was passed until the pressure inside the autoclave was 0.3 MPa. The air was passed continuously, and the flow rate was controlled to be 100-120 mL / min. The reaction was terminated after 2 hours. The reaction solution was dark green, and the total weight of the reaction solution was weighed to be 133.99 g. Take 0.1 g of the reaction solution, toluene as the internal standard, take 0.1 g of toluene, add 30 g of acetonitrile to dilute, and then inject the sample for testing. Substituting the test data into the internal standard curve, the o-nitrotoluene conversion rate was calculated to be 74.23%, and the o-nitrobenzoic acid selectivity was 89.83%.

[0149] Embodiment 20

[0150] Composite catalyst 4 (0.20 g) and o-nitrotoluene (100 g) were added to a 250 mL titanium autoclave in sequence. After the autoclave was installed, nitrogen was filled until the pressure inside the autoclave was 0.5 MPa and maintained for 15 minutes. If the pressure drop did not exceed 5%, the air tightness of the autoclave was considered good. After the nitrogen was discharged, the temperature was raised to 115 ° C, and air was passed until the pressure inside the autoclave was 0.3 MPa. The air was passed continuously, and the flow rate was controlled to be 100-120 mL / min. The reaction was terminated after 2 hours. The reaction solution was dark green, and the total weight of the reaction solution was weighed to be 131.92 g. Take 0.1 g of the reaction solution, toluene as the internal standard, take 0.1 g of toluene, add 30 g of acetonitrile to dilute, and then inject the sample for testing. Substituting the test data into the internal standard curve, the o-nitrotoluene conversion rate was calculated to be 70.28%, and the o-nitrobenzoic acid selectivity was 93.22%.

[0151] Embodiment 21

[0152] Composite catalyst 5 (0.10 g) and o-nitrotoluene (100 g) were added to a 250 mL titanium autoclave in sequence. After the autoclave was installed, nitrogen was filled until the pressure inside the autoclave was 0.5 MPa and maintained for 15 minutes. If the pressure drop did not exceed 5%, the air tightness of the autoclave was considered good. After the nitrogen was discharged, the temperature was raised to 120 ° C, and air was passed until the pressure inside the autoclave was 0.3 MPa. The air was passed continuously, and the flow rate was controlled to be 100-120 mL / min. The reaction was terminated after 2 hours. The reaction solution was dark green, and the total weight of the reaction solution was weighed to be 137.02 g. Take 0.1 g of the reaction solution, toluene as the internal standard, take 0.1 g of toluene, add 30 g of acetonitrile to dilute, and then inject the sample for testing. Substituting the test data into the internal standard curve, the o-nitrotoluene conversion rate was calculated to be 69.36%, and the o-nitrobenzoic acid selectivity was 93.59%.

[0153] Embodiment 22

[0154] Composite catalyst 6 (0.30 g) and o-nitrotoluene (100 g) were added to a 250 mL titanium autoclave in sequence. After the autoclave was installed, nitrogen was filled until the pressure inside the autoclave was 0.5 MPa and maintained for 15 minutes. If the pressure drop did not exceed 5%, the air tightness of the autoclave was considered good. After the nitrogen was discharged, the temperature was raised to 125 ° C, and air was passed until the pressure inside the autoclave was 0.3 MPa. The air was passed continuously, and the flow rate was controlled to be 100-120 mL / min. The reaction was terminated after 1 hour. The reaction solution was dark green, and the total weight of the reaction solution was weighed to be 135.70 g. Take 0.1 g of the reaction solution, toluene as the internal standard, take 0.1 g of toluene, add 30 g of acetonitrile to dilute, and then inject the sample for testing. Substituting the test data into the internal standard curve, the o-nitrotoluene conversion rate was calculated to be 70.72%, and the o-nitrobenzoic acid selectivity was 87.88%.

[0155] Embodiment 23

[0156] Composite catalyst 7 (0.35 g) and o-nitrotoluene (100 g) were added to a 250 mL titanium autoclave in sequence. After the autoclave was installed, nitrogen was filled until the pressure inside the autoclave was 0.5 MPa and maintained for 15 minutes. If the pressure drop did not exceed 5%, the air tightness of the autoclave was considered good. After the nitrogen was discharged, the temperature was raised to 130 ° C, and air was passed until the pressure inside the autoclave was 0.3 MPa. The air was passed continuously, and the flow rate was controlled to be 100-120 mL / min. The reaction was terminated after 1 hour. The reaction solution was dark green, and the total weight of the reaction solution was weighed to be 137.12 g. Take 0.1 g of the reaction solution, toluene as the internal standard, take 0.1 g of toluene, add 30 g of acetonitrile to dilute, and then inject the sample for testing. Substituting the test data into the internal standard curve, the o-nitrotoluene conversion rate was calculated to be 69.28%, and the o-nitrobenzoic acid selectivity was 91.67%.

[0157] Embodiment 24

[0158] Composite catalyst 8 (0.50 g) and o-nitrotoluene (100 g) were added to a 250 mL titanium autoclave in sequence. After the autoclave was installed, nitrogen was filled until the pressure inside the autoclave was 0.5 MPa and maintained for 15 minutes. If the pressure drop did not exceed 5%, the air tightness of the autoclave was considered good. After the nitrogen was discharged, the temperature was raised to 130 ° C, and air was passed until the pressure inside the autoclave was 0.3 MPa. The air was passed continuously, and the flow rate was controlled to be 100-120 mL / min. The reaction was terminated after 1 hour. The reaction solution was dark green, and the total weight of the reaction solution was weighed to be 134.13 g. Take 0.1 g of the reaction solution, toluene as the internal standard, take 0.1 g of toluene, add 30 g of acetonitrile to dilute, and then inject the sample for testing. Substituting the test data into the internal standard curve, the o-nitrotoluene conversion rate was calculated to be 69.72%, and the o-nitrobenzoic acid selectivity was 92.55%.

[0159] Comparative Example

[0160] The experimental operation methods of the comparative example are consistent with those of Example 17, wherein the material addition amounts of the composite catalyst used during preparation and the experimental results are shown in Table 1.

[0161] Table 1 Comparative Example Material Addition Amount and Experimental Results

[0162]

[0163]

[0164] In Comparative Example 8, no quinoxaline-5-carboxylic acid coordinated catalyst was added. In the experimental results, the conversion rate of o-nitrotoluene was only 9.13%, and the selectivity of o-nitrobenzoic acid was only 60.15%. In Example 17, the conversion rate of o-nitrotoluene was 71.60%, and the selectivity of o-nitrobenzoic acid was 94.41%. The experimental results were significantly better than those of Comparative Example 8, indicating that the quinoxaline-5-carboxylic acid coordinated catalyst disclosed in the present invention can significantly improve the selectivity and conversion rate of the o-nitrotoluene oxidation reaction.

[0165] In Comparative Examples 1-7, the raw materials are free of cocatalysts, regulators or protective agents, and the o-nitrotoluene conversion rate and o-nitrobenzoic acid selectivity in the experimental results are both worse than those in Example 17, indicating that the use of a cocatalyst, a regulator, a protective agent and a catalyst coordinated by quinoxaline-5-carboxylic acid can better promote the oxidation of o-nitrotoluene to o-nitrobenzoic acid. At the same time, in combination with Examples 18-24, it can be seen that the composite catalyst in the present invention has better selectivity and conversion rate in the o-nitrotoluene oxidation reaction, and it is also verified that the use of a cocatalyst, a regulator, a protective agent and a catalyst coordinated by quinoxaline-5-carboxylic acid can obtain excellent reaction results.

[0166] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

[0167] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A quinoxaline-5-carboxylic acid coordinated catalyst, characterized in that: The catalyst general formula is shown as (I): wherein B is a sodium ion, a magnesium ion, a calcium ion, an aluminum ion, a rubidium ion, a cesium ion, an ammonium ion, a tetradecyldimethylbenzylammonium ion, a tetradecyltrimethylammonium ion, a hexadecyltrimethylammonium ion, a hexadecyldimethylbenzylammonium ion, a tributyloctylphosphonium ion, a tetrapropylphosphonium ion, a dipropyldibutylphosphonium ion, a dibutyldihexylphosphonium ion, a tetraheptylphosphonium ion, a tetrabutylphosphonium ion, a tetrabenzylammonium ion, a tetraheptylammonium ion, a dimethyldiethylammonium ion, a benzyltrihexylammonium ion, a tetrabenzylammonium ion, a tribenzylphenylphosphonium ion, or a tetraphenylammonium ion; M is Sc, Ti, Mo, Fe, Ni, Tc, Zn, Zr, Cr, Mg or W; R is selected from C1~C 25 alkyl; x is selected from an integer between 1 and 20; y is an integer selected from 1 to 40.

2. A method for preparing the quinoxaline-5-carboxylic acid coordinated catalyst according to claim 1, characterized in that: The steps include: Dissolve the metal compound in deionized water, adjust the solution pH to 2-4, and then add peroxide to obtain a metal peroxide solution; Add alkyl-substituted quinoxaline-5-carboxylic acid and salt to the metal peroxide solution, filter and dry to obtain a quinoxaline-5-carboxylic acid coordinated catalyst.

3. The method for preparing a catalyst coordinated by quinoxaline-5-carboxylic acid according to claim 2, characterized in that: The metal compound is selected from scandium chloride, magnesium sulfate, molybdenum nitrate, magnesium chloride, nickel chloride, potassium titanium oxalate, iron nitrate, zinc sulfate, iron chloride, iron sulfate, tungsten chloride, zirconium acetate and chromium nitrate.

4. The method for preparing a quinoxaline-5-carboxylic acid coordinated catalyst according to claim 2, characterized in that: The peroxide is selected from hydrogen peroxide and meta-chloroperbenzoic acid.

5. The method for preparing a quinoxaline-5-carboxylic acid coordinated catalyst according to claim 2, characterized in that: The alkyl-substituted quinoxaline-5-carboxylic acid is selected from 8-methylquinoxaline-5-carboxylic acid, 8-ethylquinoxaline-5-carboxylic acid, 8-isopropylquinoxaline-5-carboxylic acid, 8-n-butylquinoxaline-5-carboxylic acid, 8-tert-butylquinoxaline-5-carboxylic acid, 8-n-pentylquinoxaline-5-carboxylic acid or 8-isopentylquinoxaline-5-carboxylic acid.

6. The method for preparing a quinoxaline-5-carboxylic acid coordinated catalyst according to claim 2, characterized in that: The salt is selected from the group consisting of tetradecyldimethylbenzylammonium bromide, tetradecyltrimethylammonium chloride, tetradecyltrimethylammonium bromide, sodium bromide, magnesium bromide, calcium chloride, aluminum chloride, rubidium bromide, ammonium chloride, hexadecyltrimethylammonium bromide, hexadecyldimethylbenzylammonium ion, tributyloctylphosphonium chloride, tetrapropylphosphonium bromide, dipropyldibutylphosphonium bromide, tetrabenzylammonium bromide, tetrabenzylammonium bromide, dimethyldiethylammonium bromide, benzyltrihexylammonium bromide, tribenzylphenylphosphonium bromide, tetraheptylammonium bromide and tetraphenylammonium bromide.

7. A composite catalyst, characterized in that The present invention comprises the catalyst coordinated with quinoxaline-5-carboxylic acid as described in claim 1.

8. A composite catalyst according to claim 7, characterized in that: It also includes a cocatalyst, wherein the weight ratio of the catalyst coordinated by quinoxaline-5-carboxylic acid to the cocatalyst is 100:(1-200); The cocatalyst is selected from cerium chloride, cerium nitrate, manganese chloride, manganese sulfate, manganese nitrate, manganese dioxide, vanadium chloride, cobalt nitrate, silver acetate, zirconium nitrate, zirconium sulfate, ferric acetate, ferric nitrate, ferric chloride, copper oxide, copper chloride, copper nitrate, magnesium chloride, magnesium sulfate, zinc acetate, zinc chloride, sodium nitrate, potassium acetate and potassium chloride.

9. A composite catalyst according to claim 7, characterized in that: It also includes a regulator, and the weight ratio of the catalyst coordinated by quinoxaline-5-carboxylic acid to the regulator is 100:(1-400); The regulator is selected from phosphoric acid, phosphomolybdic acid, tetrabutylammonium fluoride, boric acid, tetrabutylammonium chloride and phosphomolybdic vanadic acid.

10. A composite catalyst according to claim 7, characterized in that: It also includes a protective agent, and the weight ratio of the catalyst coordinated by quinoxaline-5-carboxylic acid to the protective agent is 100: (1-600); The protective agent is selected from magnesium acetate, sodium bromide, octadecyltripropylammonium bromide, diphenyldipropylammonium bromide, sodium tungstate and N-hydroxyphthalimide.

11. A composite catalyst according to claim 7, characterized in that: It also includes a solvent, wherein the weight ratio of the catalyst coordinated by quinoxaline-5-carboxylic acid to the solvent is 100:(20-20000); The solvent is selected from the group consisting of ethylene dichloride, tetrahydrofuran, methanol, ethanol, ethyl acetate, 1,4-dioxane, acetic acid, n-hexanoic acid and n-heptanoic acid.

12. A method for preparing a composite catalyst, characterized in that: The following steps are involved: Mix the protective agent and the solvent to obtain a solution; Add the catalyst coordinated with quinoxaline-5-carboxylic acid to the solution and stir at 0-100° C. for 5-30 minutes; Then add the auxiliary catalyst and ultrasonicate at 0-100°C for 10-40 minutes; Then add a regulator, stir at 0-100°C for 20-30 minutes to obtain a composite catalyst.

13. Use of the quinoxaline-5-carboxylic acid coordinated catalyst according to claim 1, the quinoxaline-5-carboxylic acid coordinated catalyst prepared by the preparation method of the quinoxaline-5-carboxylic acid coordinated catalyst according to any one of claims 2 to 6, or the composite catalyst according to any one of claims 7 to 11 in catalytic oxidation of o-nitrotoluene to prepare o-nitrobenzoic acid.

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