3-(3-pyridine)-5-R-ylbenzoic acid coordinated catalyst, composite catalyst, preparation method and application

Abstract

The invention discloses a 3-(3-pyridine)-5-R-group benzoic acid coordinated catalyst, a compound catalyst, a preparation method and application. The chemical general formula of the 3-(3-pyridine)-5-R-group benzoic acid coordinated catalyst is # imgabs0 #, and the compound catalyst comprises the 3-(3-pyridine)-5-R-group benzoic acid coordinated catalyst, a cocatalyst, a regulator, a protective agent and a solvent. By using the composite catalyst disclosed by the invention, the selectivity of mesitylene oxidation reaction can be improved, the reaction activity is increased, and the composite catalyst can be used repeatedly and has a relatively high utilization rate.

Description

Technical Field

[0001] The invention belongs to the technical field of organic catalysis, and specifically relates to a 3-(3-pyridine)-5-R-ylbenzoic acid coordinated catalyst, a composite catalyst, a preparation method and an application. Background Art

[0002] Trimesic acid, also known as 1,3,5-benzenetricarboxylic acid, is an important chemical raw material used as a pharmaceutical intermediate. It is also widely used in plastics, artificial fibers, water-soluble alkyl resins, mildew inhibitors and cross-linking agents, and is also an intermediate for special polymers and resins.

[0003] Trimellitic acid is an emerging important chemical raw material. There are many studies on its preparation methods at home and abroad, but none of them are ideal. At present, the synthesis of trimesic acid usually adopts three methods: potassium permanganate oxidation of mesitylene, nitric acid oxidation of mesitylene and liquid-phase oxygen oxidation of mesitylene. Among them, the potassium permanganate oxidation method produces a large amount of wastewater and waste residue during the reaction, which is difficult to post-process, has a low conversion rate and is more complicated to purify; the nitric acid method has high raw material cost, poor selectivity for the target product, and is difficult to purify the product, seriously pollutes the environment and has a high risk of reaction process; the oxygen oxidation method uses glacial acetic acid as a solvent. Due to the strong activity of mesitylene, a large amount of tar is produced during the reaction, which is costly and difficult to separate and purify.

[0004] Therefore, it is particularly important to provide a catalyst for preparing trimesic acid with low cost, good quality and applicability so that the product can be produced on a large scale and further development and application of trimesic acid.

[0005] 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

[0006] The object of the present invention is to provide a 3-(3-pyridine)-5-R-ylbenzoic acid coordinated catalyst, a composite catalyst, a preparation method and an application, which can effectively improve the selectivity of the mesitylene oxidation reaction.

[0007] In order to achieve the above object, a technical solution provided by a specific embodiment of the present invention is as follows:

[0008] A catalyst coordinated by 3-(3-pyridine)-5-R-benzoic acid, wherein the catalyst has a general chemical formula as shown in formula (I):

[0009]

[0010] Wherein, B is octyltributylphosphonium ion, tetrabutylphosphonium ion, tributylethylphosphonium ion, tributylhexylphosphonium ion, tetramethylammonium ion, tetraethylammonium ion, tetrabutylammonium ion, benzyltrimethylammonium ion, lithium ion, sodium ion, potassium ion, magnesium ion, calcium ion, ammonium ion, dodecyldimethylbenzylammonium ion, dodecyltrimethylammonium ion, octadecyltrimethylammonium ion, octadecyldimethylbenzylammonium ion, benzyltriphenylphosphonium ion or benzyltriethylammonium ion;

[0011] M is Cu, Fe, Cr, Mo, V, W, Co, Ni or Zr;

[0012] R is C1~C 10 alkyl;

[0013] x is an integer between 1 and 20;

[0014] y is an integer between 1 and 40.

[0015] Another specific embodiment of the present invention provides a technical solution as follows:

[0016] A method for preparing the above-mentioned 3-(3-pyridine)-5-R-benzoic acid coordinated catalyst comprises the following steps:

[0017] Dissolve the metal compound in deionized water, adjust the solution pH to 1-4, and then add peroxide to obtain a metal peroxide solution;

[0018] Add alkyl-substituted 3-(3-pyridine)-5-R-ylbenzoic acid and salt to the metal peroxide solution, filter, and dry to obtain a catalyst coordinated with 3-(3-pyridine)-5-R-ylbenzoic acid.

[0019] In one or more embodiments of the present invention, the metal compound is selected from sodium molybdate, chromium nitrate, cobalt nitrate, sodium tungstate, copper nitrate, iron nitrate, zirconium acetate, cobalt sulfate, nickel nitrate, nickel sulfate, nickel acetate and sodium metavanadate.

[0020] In one or more embodiments of the present invention, the peroxide is selected from hydrogen peroxide, meta-chloroperbenzoic acid and urea peroxide.

[0021] In one or more embodiments of the present invention, the alkyl-substituted 3-(3-pyridine)-5-R-benzoic acid is selected from 3-(3-pyridine)-5-methylbenzoic acid, 3-(3-pyridine)-5-ethylbenzoic acid, 3-(3-pyridine)-5-butylbenzoic acid and 3-(3-pyridine)-5-isopropylbenzoic acid.

[0022] In one or more embodiments of the present invention, the salt is selected from octadecyltrimethylammonium chloride, octadecyltrimethylammonium bromide, lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, ammonium bromide, dodecyldimethylbenzylammonium bromide, dodecyltrimethylammonium chloride, octadecyldimethylbenzylammonium bromide, octyltributylphosphonium bromide, tetrabutylphosphonium bromide, tributylethylphosphonium bromide, tributylhexylphosphonium bromide, benzyltriphenylphosphonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltrimethylammonium chloride or benzyltriethylammonium chloride.

[0023] Another specific embodiment of the present invention provides a technical solution as follows:

[0024] A composite catalyst comprises the above-mentioned 3-(3-pyridine)-5-R-benzoic acid acid coordinated catalyst.

[0025] In one or more embodiments of the present invention, a cocatalyst is further included, and the weight ratio of the catalyst coordinated by 3-(3-pyridine)-5-R-ylbenzoic acid to the cocatalyst is 80:(1-500);

[0026] The cocatalyst is selected from cerium nitrate, cerium sulfate, cerium acetate, manganese acetate, manganese nitrate, manganese sulfate, vanadium oxide, cobalt oxide, silver nitrate, zirconium oxide, zirconium acetate, ferric nitrate, ferric sulfate, ferric chloride, magnesium chloride, copper sulfate, ammonium acetate, copper acetate, copper nitrate, magnesium sulfate, magnesium acetate, zinc acetate, zinc sulfate, sodium molybdate, potassium acetate, nickel acetate, chromium acetate, calcium acetate and potassium sulfate.

[0027] In one or more embodiments of the present invention, a regulator is further included, and the weight ratio of the catalyst coordinated by 3-(3-pyridine)-5-R-ylbenzoic acid to the regulator is 100:(1-500);

[0028] The regulator is selected from phosphomolybdic acid, phosphotungstic acid, tetrabutylammonium bromide, boric acid, silicotungstic acid, sodium tungstate, sodium chloride, magnesium chloride, copper chloride and phosphomolybdicvanadic acid.

[0029] In one or more embodiments of the present invention, a protective agent is further included, and the weight ratio of the catalyst coordinated by 3-(3-pyridine)-5-R-ylbenzoic acid to the protective agent is 100:(1-500);

[0030] The protective agent is selected from sodium acetate, ammonium bromide, sodium bromide, hexadecyltrimethylammonium bromide, phenyltrimethylammonium bromide, sodium molybdate, ammonium molybdate, sodium sulfate and N-hydroxyphthalimide.

[0031] In one or more embodiments of the present invention, a solvent is further included, and the weight ratio of the catalyst coordinated by 3-(3-pyridine)-5-R-ylbenzoic acid to the solvent is 100:(50-10000);

[0032] The solvent is selected from the group consisting of dichloromethane, 1,4-dioxane, acetonitrile, methanol, ethanol, formic acid, acetic acid, propionic acid and ethyl acetate.

[0033] Another specific embodiment of the present invention provides a technical solution as follows:

[0034] A method for preparing a composite catalyst comprises the following steps:

[0035] Mix the protective agent and the solvent to obtain a solution;

[0036] Add the 3-(3-pyridine)-5-R-ylbenzoic acid acid-coordinated catalyst of claim 1 to the solution, and stir at 20 to 100° C. for 10 to 60 minutes;

[0037] Then add the auxiliary catalyst and ultrasonicate at 20-120°C for 20-60min;

[0038] Then add a regulator and stir at 20-110°C for 10-60 minutes to obtain a composite catalyst.

[0039] Another specific embodiment of the present invention provides a technical solution as follows:

[0040] An application of the above 3-(3-pyridine)-5-R-benzoic acid acid coordinated catalyst or the above composite catalyst in the reaction of preparing trimesic acid.

[0041] Compared with the prior art, the 3-(3-pyridine)-5-R-ylbenzoic acid coordinated catalyst or composite catalyst of the present invention can improve the selectivity of the mesitylene oxidation reaction, increase the reaction activity, and can be applied multiple times with a high utilization rate. DETAILED DESCRIPTION

[0042] 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.

[0043] A specific embodiment of the present invention provides a catalyst coordinated by 3-(3-pyridine)-5-R-benzoic acid, and the general chemical formula of the catalyst is as follows:

[0044]

[0045] Wherein, B is octyltributylphosphonium ion, tetrabutylphosphonium ion, tributylethylphosphonium ion, tributylhexylphosphonium ion, tetramethylammonium ion, tetraethylammonium ion, tetrabutylammonium ion, benzyltrimethylammonium ion, lithium ion, sodium ion, potassium ion, magnesium ion, calcium ion, ammonium ion, dodecyldimethylbenzylammonium ion, dodecyltrimethylammonium ion, octadecyltrimethylammonium ion, octadecyldimethylbenzylammonium ion, benzyltriphenylphosphonium ion or benzyltriethylammonium ion; M is Cu, Fe, Cr, Mo, V, W, Co, Ni or Zr; R is Cl~C 10 Alkyl; x is an integer between 1 and 20; y is an integer between 1 and 40.

[0046] Preferably, B is calcium ion, ammonium ion, benzyltriphenylphosphonium ion, dodecyltrimethylammonium ion, octadecyltrimethylammonium ion, lithium ion, sodium ion, potassium ion or magnesium ion, M is Co, Ni, V, Mo, Cr, Cu or Fe; R is selected from C1-C5 alkyl; x is selected from an integer between 1 and 5; y is selected from an integer between 1 and 5.

[0047] More preferably, B is selected from octadecyltrimethylammonium ion, sodium ion, magnesium ion, ammonium ion or benzyltriphenylphosphonium ion; M is selected from Mo, Cr, Co, Ni or V; R is selected from methyl, ethyl, isopropyl; x is 1; y is 1 or 2.

[0048] Exemplarily, the catalyst coordinated by 3-(3-pyridine)-5-ylbenzoic acid can be:

[0049]

[0050]

[0051] Another specific embodiment of the present invention provides a method for preparing a catalyst coordinated by 3-(3-pyridine)-5-R-benzoic acid, comprising steps 1-2.

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

[0053] Specifically, the metal compound is selected from sodium molybdate, chromium nitrate, chromium nitrate nonahydrate, cobalt nitrate, sodium tungstate, copper nitrate, iron nitrate, zirconium acetate, cobalt sulfate, nickel nitrate, nickel sulfate, nickel acetate and sodium metavanadate, the peroxide is selected from urea peroxide, meta-chloroperbenzoic acid or a 30% hydrogen peroxide solution, and the pH of the solution is adjusted using 2 mol / L dilute hydrochloric acid or 2 mol / L dilute sulfuric acid.

[0054] Step 2, adding alkyl-substituted 3-(3-pyridine)-5-R-ylbenzoic acid and salt to the metal peroxide solution, filtering, and drying to obtain a catalyst coordinated with 3-(3-pyridine)-5-R-ylbenzoic acid.

[0055] Specifically, the alkyl-substituted 3-(3-pyridine)-5-R-ylbenzoic acid is selected from 3-(3-pyridine)-5-methylbenzoic acid, 3-(3-pyridine)-5-ethylbenzoic acid, 3-(3-pyridine)-5-butylbenzoic acid and 3-(3-pyridine)-5-isopropylbenzoic acid, and the salt is selected from octadecyltrimethylammonium chloride, octadecyltrimethylammonium bromide, lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, ammonium bromide, dodecyldimethylbenzylammonium bromide, dodecyltrimethylammonium chloride, octadecyldimethylbenzylammonium bromide, octyltributylphosphonium bromide, tetrabutylphosphonium bromide, tributylethylphosphonium bromide, tributylhexylphosphonium bromide, benzyltriphenylphosphonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltrimethylammonium chloride or benzyltriethylammonium chloride.

[0056] Another specific embodiment of the present invention discloses a composite catalyst, comprising the above-mentioned 3-(3-pyridine)-5-R-ylbenzoic acid coordinated catalyst, co-catalyst, regulator, protective agent and solvent, the weight ratio of the 3-(3-pyridine)-5-R-ylbenzoic acid coordinated catalyst, co-catalyst, regulator, protective agent and solvent is 80:(1~500):(1~500):(1~500):(50~10000).

[0057] Specifically, the auxiliary catalyst is selected from cerium nitrate, cerium sulfate, cerium acetate, manganese acetate, manganese nitrate, manganese sulfate, vanadium oxide, cobalt oxide, silver nitrate, zirconium oxide, zirconium acetate, ferric nitrate, ferric sulfate, ferric chloride, magnesium chloride, copper sulfate, ammonium acetate, copper acetate, copper nitrate, magnesium sulfate, magnesium acetate, zinc acetate, zinc sulfate, sodium molybdate, potassium acetate, nickel acetate, chromium acetate, calcium acetate and potassium sulfate, the regulator is selected from phosphomolybdic acid, phosphotungstic acid, tetrabutylammonium bromide, boric acid, silicotungstic acid, sodium tungstate, sodium chloride, magnesium chloride, copper chloride and phosphomolybdicvanadic acid, the protective agent is selected from sodium acetate, ammonium bromide, sodium bromide, hexadecyltrimethylammonium bromide, phenyltrimethylammonium bromide, sodium molybdate, ammonium molybdate, sodium sulfate and N-hydroxyphthalimide, and the solvent is selected from dichloromethane, 1,4-dioxane, acetonitrile, methanol, ethanol, formic acid, acetic acid, propionic acid and ethyl acetate. Selecting the above types of co-catalysts, regulators, protective agents and solvents can improve the activity of the catalyst and ensure the selectivity and stability of the reaction.

[0058] Preferably, the weight ratio of the catalyst coordinated by 3-(3-pyridine)-5-R-benzoic acid, the cocatalyst, the regulator, the protective agent and the solvent is 100:(1-500):(1-500):(1-500):(50-10000); the cocatalyst is selected from cerium nitrate, manganese acetate, zirconium acetate, ferric nitrate, copper sulfate, magnesium sulfate, magnesium acetate, zinc sulfate and sodium molybdate; the regulator is selected from phosphomolybdic acid, phosphotungstic acid, tetrabutylammonium bromide, boric acid, silicotungstic acid and phosphomolybdic vanadic acid; the protective agent is selected from sodium acetate, ammonium bromide, hexadecyltrimethylammonium bromide, phenyltrimethylammonium bromide, sodium molybdate and N-hydroxyphthalimide; the solvent is selected from dichloromethane, 1,4-dioxane, acetonitrile, methanol, ethanol, formic acid, acetic acid, propionic acid and ethyl acetate.

[0059] Preferably, the weight ratio of the catalyst coordinated by 3-(3-pyridine)-5-R-ylbenzoic acid, the cocatalyst, the regulator, the protective agent and the solvent is 110:(1-60):(10-100):(10-50):(100-1000), the catalyst coordinated by 3-(3-pyridine)-5-R-ylbenzoic acid is a metal coordination catalyst with Cr, Mo, V, Co or Ni as the central metal, the cocatalyst is selected from manganese acetate, zirconium acetate, magnesium acetate and cerium acetate, the regulator is selected from phosphomolybdic acid, phosphotungstic acid and silicotungstic acid, the protective agent is selected from ammonium bromide, dodecyltrimethylammonium bromide, phenyltrimethylammonium bromide and N-hydroxyphthalimide, and the solvent is selected from methanol, ethanol and acetonitrile.

[0060] Another specific embodiment of the present invention provides a method for preparing a composite catalyst, comprising the following steps: preparing raw materials, including a catalyst coordinated by 3-(3-pyridine)-5-R-ylbenzoic acid, a cocatalyst, a regulator, a protective agent and a solvent;

[0061] Add the protective agent to the solvent and mix well to obtain solution 1;

[0062] Add a catalyst coordinated with 3-(3-pyridine)-5-R-benzoic acid to solution 1, stir at 20-100° C. for 10-60 min, and obtain solution 2;

[0063] Add the cocatalyst to solution 2, and perform ultrasonic treatment at 20-120°C for 20-60 minutes to obtain solution 3;

[0064] Add a regulator to solution 3, stir at 20-110°C for 10-60 minutes to obtain a composite catalyst.

[0065] Specifically, the auxiliary catalyst is one or more of cerium nitrate, cerium sulfate, cerium acetate, manganese acetate, manganese nitrate, manganese sulfate, vanadium oxide, cobalt oxide, silver nitrate, zirconium oxide, zirconium acetate, ferric nitrate, ferric sulfate, ferric chloride, copper sulfate, copper acetate, copper nitrate, magnesium sulfate, magnesium acetate, zinc acetate, zinc sulfate, sodium molybdate, potassium acetate and potassium sulfate; the regulator is one or more of phosphomolybdic acid, phosphotungstic acid, tetrabutylammonium bromide, boric acid, silicotungstic acid and phosphomolybdicvanadic acid; the protective agent is one or more of sodium acetate, ammonium bromide, hexadecyltrimethylammonium bromide, phenyltrimethylammonium bromide, sodium molybdate and N-hydroxyphthalimide; the solvent is one or more of dichloromethane, 1,4-dioxane, acetonitrile, methanol, ethanol, formic acid, acetic acid, propionic acid and ethyl acetate.

[0066] Preferably, the protective agent is one or more of ammonium bromide, dodecyltrimethylammonium bromide, phenyltrimethylammonium bromide and N-hydroxyphthalimide; the solvent is one or more of formic acid, acetic acid and propionic acid; the catalyst coordinated with 3-(3-pyridine)-5-R-ylbenzoic acid is one or more of the catalysts coordinated with 3-(3-pyridine)-5-R-ylbenzoic acid with Cr, Mo, V, Co or Ni as the central metal; the cocatalyst is one or more of copper nitrate, manganese acetate, silver nitrate, ferric nitrate manganese sulfate, cerium sulfate, cerium nitrate, zirconium acetate and magnesium sulfate; the regulator is one or more of phosphomolybdic acid, phosphotungstic acid and silicotungstic acid.

[0067] Another specific embodiment of the present invention provides the use of the above-mentioned 3-(3-pyridine)-5-R-ylbenzoic acid coordinated catalyst or the above-mentioned composite catalyst in the reaction of preparing trimesic acid.

[0068] Specifically, the reaction conditions are as follows: dissolving mesitylene in a solvent, adding a catalyst coordinated with 3-(3-pyridine)-5-R-benzoic acid or a composite catalyst, introducing air at a rate of 1 to 10 mL / s, and stirring the reaction at 50 to 160° C. for 1 to 10 hours.

[0069] Taking the composite catalyst as an example, the amount of the composite catalyst added is 0.05-6% of the weight of mesitylene.

[0070] Preferably, the amount of the composite catalyst added is 0.1-1.5% of the weight of mesitylene, the reaction temperature is 65-100° C., the reaction time is 2-7 h, and the air introduction rate is 2-3 mL / s.

[0071] The present invention is further described in detail below in conjunction with specific embodiments.

[0072] 3-(3-pyridine)-5-R-benzoic acid coordinated catalyst example

[0073] Example 1

[0074] Step 1: Add 450 mL of deionized water to solid cobalt nitrate (36.58 g, 0.2 mol) at room temperature, 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 3 to obtain solution b. Continue stirring for about 14 minutes, then slowly add 210 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 3000 mL to obtain solution d.

[0075] Step 2: Heat solution d to 45°C, add 3-(3-pyridine)-5-ethylbenzoic acid (54.50 g, 0.24 mol) and sodium chloride (12.86 g, 0.22 mol) to solution d, stir while heating for about 1 hour, and centrifuge for 10 minutes. Filter, and place the solid obtained after filtration in a vacuum drying oven to dry to obtain 62.26 g of yellow solid, which is the catalyst YG-31-1-022 coordinated with 3-(3-pyridine)-5-ethylbenzoic acid, and the catalyst yield reaches 88.33%. The nuclear magnetic characterization data are as follows:

[0076] 1H NMR(400MHz,DMSO-d6)δ8.71(s,1H),8.61(s,1H),8.62(d,1H),8.07(d,1H),8.55(s,1H),3 .66(t,2H),3.45(s,9H),2.49(s,3H),1.77-1.49(m,2H),1.55-1.16(m,30H),0.62(t,3H).

[0077] Example 2

[0078] Step 1: Add 550 mL of deionized water to solid cobalt nitrate (18.29 g, 0.1 mol) at room temperature, 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 64 minutes, then slowly add 260 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 3400 mL to obtain solution d.

[0079] Step 2: Heat solution d to 27°C, add 3-(3-pyridine)-5-isopropylbenzoic acid (28.95 g, 0.12 mol) and lithium chloride (8.48 g, 0.2 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 30.06 g of yellow solid, which is the catalyst YG-31-1-023 coordinated with 3-(3-pyridine)-5-isopropylbenzoic acid, and the catalyst yield reaches 87.46%. The nuclear magnetic characterization data are as follows:

[0080] 1H NMR (400MHz, DMSO-d6) δ9.86(s,1H),8.65(s,1H),8.53(d,1H),8.19(d,1H),8.18(s,1H),2.50(s,3H).

[0081] Example 3

[0082] Step 1: Add 600 mL of deionized water to solid cobalt nitrate (36.58 g, 0.2 mol) at room temperature, 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 170 min, then slowly add 250 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 2000 mL to obtain solution d.

[0083] Step 2: Heat solution d to 50°C, add 3-(3-pyridine)-5-methylbenzoic acid (25.59 g, 0.12 mol) and benzyltriphenylphosphonium bromide (51.99 g, 0.12 mol) to solution d, stir while heating for about 1 hour, and centrifuge for 30 minutes. Filter, and place the solid obtained after filtration in a vacuum drying oven to dry to obtain a 65.44 yellow solid, which is the catalyst YG-31-1-025 coordinated with 3-(3-pyridine)-5-methylbenzoic acid, and the catalyst yield reaches 91.14%. The nuclear magnetic characterization data are as follows:

[0084] 1H NMR (400MHz, DMSO-d6) δ8.69(s,1H),8.67(s,1H),8.54(d,1H),8.21(d,1H),8.06(s,1H),2.57(s,3H).

[0085] Example 4

[0086] Step 1: Add 530 mL of deionized water to solid cobalt nitrate (18.29 g, 0.1 mol) at room temperature, and after the solid is completely dissolved, obtain solution a. Add dilute phosphoric acid dropwise to solution a until the pH of the solution is 2 to obtain solution b. Continue stirring for about 6 minutes, then slowly add 200 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 3000 mL to obtain solution d.

[0087] Step 2: Heat solution d to 100°C, add 3-(3-pyridine)-5-ethylbenzoic acid (54.54 g, 0.24 mol) and ammonium bromide (11.75 g, 0.12 mol) to solution d, stir while heating for about 5 hours, and centrifuge for 5 minutes. Filter, and place the solid obtained after filtration in a vacuum drying oven to dry to obtain 35.41 g of yellow solid, which is the catalyst YG-31-1-027 coordinated with 3-(3-pyridine)-5-ethylbenzoic acid, and the catalyst yield reaches 93.15%. The nuclear magnetic characterization data are as follows:

[0088] 1H NMR (400MHz, DMSO-d6) δ8.86(s,1H),8.63(s,1H),8.31(d,1H),8.17(d,1H),8.04(s,1H),5.14(t,4H),1.51(s,3H).

[0089] Example 5

[0090] Step 1: Add 500 mL of deionized water to solid cobalt nitrate (18.29 g, 0.1 mol) at room temperature, 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 20 minutes, then slowly add 290 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.

[0091] Step 2: Heat solution d to 90°C, add 3-(3-pyridine)-5-butylbenzoic acid (30.64g, 0.12mol) and magnesium chloride (10.47g, 0.11mol) to solution d, stir while heating for about 1h, and centrifuge for 20min. Filter, and place the solid obtained after filtration in a vacuum drying oven to dry to obtain 59.66g of yellow solid, which is the catalyst YG-31-1-031 coordinated with 3-(3-pyridine)-5-butylbenzoic acid, and the catalyst yield reaches 83.28%. The NMR characterization data are as follows:

[0092] 1H NMR(400MHz,DMSO-d6)δ8.81(s,1H),8.66(s,1H),8.50(d,1H),8.15(d,1H),8.05(s,1H),7.37-7.73(m ,3H),7.65-7.59(m,12H),7.35-7.23(m,1H),7.15-7.10(m,2H),6.96(d,2H),5.25(d,2H),2.49(s,3H).

[0093] Example 6

[0094] Step 1: Add 500 mL of deionized water to solid cobalt nitrate (18.29 g, 0.1 mol) at room temperature, 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 2 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 3000 mL to obtain solution d.

[0095] Step 2: Heat solution d to 60°C, add 3-(3-pyridine)-5-methylbenzoic acid (25.59 g, 0.12 mol) and benzyltriphenylphosphonium bromide (51.99 g, 0.12 mol) to solution d, stir while heating for about 6 hours, and centrifuge for 13 minutes. Filter, and place the solid obtained after filtration in a vacuum drying oven to dry to obtain 60.01 g of yellow solid, which is the catalyst YG-31-1-032 coordinated with 3-(3-pyridine)-5-methylbenzoic acid, and the catalyst yield reaches 91.58%. The nuclear magnetic characterization data are as follows:

[0096] 1H NMR(400MHz,DMSO-d6)δ8.02(s,1H),8.64(s,1H),8.53(d,1H),8.16(d,1H),7.04(s,1H),3 .30(t,2H),3.48(s,9H),2.64(q,2H),1.76-1.52(m,2H),1.55-1.16(m,33H),0.84(t,3H).

[0097] Example 7

[0098] Step 1: Add 500 mL of deionized water to solid sodium metavanadate (12.19 g, 0.1 mol) at room temperature, 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 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 3000 mL to obtain solution d.

[0099] Step 2: Heat solution d to 50°C, add 3-(3-pyridine)-5-ethylbenzoic acid (54.54 g, 0.24 mol) and sodium chloride (12.86 g, 0.22 mol) to solution d, stir while heating for about 1 hour, and centrifuge for 11 minutes. Filter, and place the solid obtained after filtration in a vacuum drying oven to dry to obtain 62.55 g of yellow solid, which is the catalyst YG-31-1-034 coordinated with 3-(3-pyridine)-5-ethylbenzoic acid, and the catalyst yield reaches 84.15%. The nuclear magnetic characterization data are as follows:

[0100] 1H NMR(400MHz,DMSO-d6)δ8.81(s,1H),8.14(s,1H),1.52(d,1H),8.11(d,1H),8.12(s,1H),3.6 1(t,2H),3.48(s,9H),2.91-2.11(m,1H),1.76-1.72(m,2H),1.15-1.06(m,36H),0.81(t,3H).

[0101] Example 8

[0102] Step 1: Add 500 mL of deionized water to solid chromium nitrate nonahydrate (40.01 g, 0.1 mol) at room temperature, 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 2 to obtain solution b. Continue stirring for about 30 minutes, then slowly add 200 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 3000 mL to obtain solution d.

[0103] Step 2: Heat solution d to 25°C, add 3-(3-pyridine)-5-methylbenzoic acid (25.59 g, 0.12 mol) and ammonium bromide (21.55 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-31-1-035 coordinated with 3-(3-pyridine)-5-methylbenzoic acid, and the catalyst yield reaches 83.76%. The nuclear magnetic characterization data are as follows:

[0104] 1H NMR(400MHz,DMSO-d6)δ8.85(s,1H),8.64(s,1H),8.55(d,1H),8.19(d,1H),8.08(s,1H),3 .62(t,2H),3.48(s,9H),2.51(s,3H),1.77-1.69(m,2H),1.53-1.10(m,30H),0.91(t,3H).

[0105] Example 9

[0106] Step 1: Add 500 mL of deionized water to solid nickel nitrate (18.27 g, 0.1 mol) at room temperature, 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 2 to obtain solution b. Continue stirring for about 110 minutes, then slowly add 230 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 3000 mL to obtain solution d.

[0107] Step 2: Heat solution d to 100°C, add 3-(3-pyridine)-5-ethylbenzoic acid (27.27g, 0.12mol) and dodecyltrimethylammonium chloride (58.06g, 0.22mol) to solution d, stir while heating for about 1h, and centrifuge for 30min. Filter, and place the solid obtained after filtration in a vacuum drying oven to dry to obtain 58.05g of purple-red solid, which is the catalyst YG-31-1-038 coordinated with 3-(3-pyridine)-5-ethylbenzoic acid, and the catalyst yield reaches 90.03%. The nuclear magnetic characterization data are as follows:

[0108] 1H NMR(400MHz,DMSO-d6)δ8.84(s,1H),8.65(s,1H),8.55(d,1H),8.17(d,1H),8.07(s,1H),3 .61(t,2H),3.49(s,9H),2.76(q,2H),1.79-1.75(m,2H),1.56-1.08(m,33H),0.91(t,3H).

[0109] Example 10

[0110] Step 1: Add 500 mL of deionized water to solid chromium nitrate nonahydrate (40.01 g, 0.1 mol) at room temperature, 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 2 to obtain solution b. Continue stirring for about 100 min, then slowly add 200 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 3000 mL to obtain solution d.

[0111] Step 2: Heat solution d to 60°C, add 3-(3-pyridine)-5-methylbenzoic acid (25.59 g, 0.12 mol) and magnesium chloride (20.95 g, 0.22 mol) to solution d, stir while heating for about 1 hour, and centrifuge for 8 minutes. Filter, and place the solid obtained after filtration in a vacuum drying oven to dry to obtain 60.86 g of purple-red solid, which is the catalyst YG-31-1-036 coordinated with 3-(3-pyridine)-5-methylbenzoic acid, and the catalyst yield reaches 92.37%. The nuclear magnetic characterization data are as follows:

[0112] 1H NMR(400MHz,DMSO-d6)δ8.84(s,1H),8.65(s,1H),8.54(d,1H),8.17(d,1H),8.03(s,1H),3.6 1(t,2H),3.49(s,9H),2.92-2.87(m,1H),1.76-1.72(m,2H),1.55-1.09(m,36H),0.90(t,3H).

[0113] Embodiment 11

[0114] Step 1: Add 500 mL of deionized water to solid cobalt nitrate hexahydrate (29.10 g, 0.1 mol) at room temperature, 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 2 to obtain solution b. Continue stirring for about 30 minutes, then slowly add 200 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 3000 mL to obtain solution d.

[0115] Step 2: Heat solution d to 35°C, add 3-(3-pyridine)-5-ethylbenzoic acid (27.27 g, 0.12 mol) and octadecyltrimethylammonium chloride (76.57 g, 0.22 mol) to solution d, stir while heating for about 10 hours, and centrifuge for 5 minutes. Filter, and place the solid obtained after filtration in a vacuum drying oven to dry to obtain 54.93 g of blue solid, which is the catalyst YG-31-1-040 coordinated with 3-(3-pyridine)-5-ethylbenzoic acid, and the catalyst yield reaches 86.13%. The nuclear magnetic characterization data are as follows:

[0116] 1H NMR(400MHz,DMSO-d6)δ8.88(s,1H),8.69(s,1H),8.58(d,1H),8.23(d,1H),8.12(s,1H),3 .62(t,2H),3.49(s,9H),2.55(s,3H),1.77-1.69(m,2H),1.56-1.10(m,30H),0.91(t,3H).

[0117] Example 12

[0118] Step 1: Add 500 mL of deionized water to nickel acetate tetrahydrate (24.88 g, 0.1 mol) solid at room temperature, 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 2 to obtain solution b. Continue stirring for about 80 minutes, then slowly add 200 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 3000 mL to obtain solution d.

[0119] Step 2: Heat solution d to 45°C, add 3-(3-pyridine)-5-methylbenzoic acid (25.59 g, 0.12 mol) and benzyltriphenylphosphonium bromide (51.99 g, 0.12 mol) to solution d, stir while heating for about 3 hours, and then centrifuge for 20 minutes. Filter, and place the solid obtained after filtration in a vacuum drying oven to dry to obtain 59.94 g of white solid, which is the catalyst YG-31-1-042 coordinated with 3-(3-pyridine)-5-methylbenzoic acid, and the catalyst yield reaches 94.03%. The nuclear magnetic characterization data are as follows:

[0120] 1H NMR(400MHz,DMSO-d6)δ8.86(s,1H),8.67(s,1H),8.56(d,1H),8.20(d,1H),8.11(s,1H),3 .62(t,2H),3.49(s,9H),2.53(s,3H),1.77-1.69(m,2H),1.56-1.10(m,30H),0.91(t,3H).

[0121] Embodiment 13

[0122] Step 1: Add 500 mL of deionized water to solid sodium metavanadate (12.19 g, 0.1 mol) at room temperature, 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 2 to obtain solution b. Continue stirring for about 120 min, then slowly add 200 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 3000 mL to obtain solution d.

[0123] Step 2: Heat solution d to 30°C, add 3-(3-pyridine)-5-isopropylbenzoic acid (28.95g, 0.12mol) and lithium chloride (8.48g, 0.2mol) to solution d, stir while heating for about 2h, and centrifuge for 30min. Filter, and place the solid obtained after filtration in a vacuum drying oven to dry to obtain 55.01g of yellow solid, which is the catalyst YG-31-1-053 coordinated with 3-(3-pyridine)-5-isopropylbenzoic acid, and the catalyst yield reaches 87.34%. The nuclear magnetic characterization data are as follows:

[0124] 1H NMR(400MHz,DMSO-d6)δ8.84(s,1H),8.65(s,1H),8.55(d,1H),8.19(d,1H),8.12(s,1H),3 .61(t,2H),3.49(s,9H),2.52(s,3H),1.77-1.69(m,2H),1.57-1.10(m,30H),0.91(t,3H).

[0125] Embodiment 14

[0126] Step 1: Add 500 mL of deionized water to solid cobalt nitrate (18.29 g, 0.1 mol) at room temperature, 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 2 to obtain solution b. Continue stirring for about 30 minutes, then slowly add 200 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 3000 mL to obtain solution d.

[0127] Step 2: Heat solution d to 55°C, add 3-(3-pyridine)-5-methylbenzoic acid (25.59 g, 0.12 mol) and benzyltriphenylphosphonium bromide (51.99 g, 0.12 mol) to solution d, stir while heating for about 10 hours, and then centrifuge for 10 minutes. Filter, and place the solid obtained after filtration in a vacuum drying oven to dry to obtain 55.70 g of yellow solid, which is the catalyst YG-31-1-054 coordinated with 3-(3-pyridine)-5-methylbenzoic acid, and the catalyst yield reaches 90.76%. The nuclear magnetic characterization data are as follows:

[0128] 1H NMR(400MHz,DMSO-d6)δ8.68(s,1H),8.64(s,1H),8.52(d,1H),8.14(d,1H),8.08(s,1H),3.6 1(t,2H),3.48(s,9H),2.10-2.86(m,1H),1.76-1.78(m,2H),1.57-1.11(m,36H),0.98(t,3H).

[0129] Composite catalyst embodiment

[0130] Embodiment 15

[0131] Step (1): adding 23.0 g of methanol to 15.0 g of N-hydroxyphthalimide, and stirring at room temperature until the solid is completely dissolved to obtain a mixture A;

[0132] Step (2): Add 1.0 g of 3-(3-pyridine)-5-ethylbenzoic acid coordinated catalyst YG-31-1-022 to the mixture A of step (1), and heat at 80° C. with stirring for 36 min to obtain a mixture B;

[0133] Step (3): adding 0.2 g of magnesium acetate to the mixture B formed in step (2) to obtain a mixture C;

[0134] Step (4): Add 0.2 g of phosphomolybdic acid to the mixture C formed in step (3), and stir at 100° C. for 50 minutes to obtain a total of 33.2 g of composite catalyst 1.

[0135] Example 16

[0136] Step (1): Add 25.0 g of methanol to 10.0 g of sodium bromide, and stir at room temperature until the solid is completely dissolved to obtain a mixture A;

[0137] Step (2): Add 1.0 g of 3-(3-pyridine)-5-isopropylbenzoic acid coordinated catalyst YG-31-1-023 to the mixture A of step (1), and heat at 80° C. with stirring for 40 min to obtain a mixture B;

[0138] Step (3): adding 0.1 g of copper acetate to the mixture B formed in step (2) to obtain a mixture C;

[0139] Step (4): Add 0.1 g of phosphomolybdic acid to the mixture C formed in step (3), and stir at 120° C. for 60 minutes to obtain a total of 42.3 g of composite catalyst 2.

[0140] Embodiment 17

[0141] Step (1): Add 25.0 g of methanol to 10.0 g of dodecyltrimethylammonium bromide, and stir at room temperature until the solid is completely dissolved to obtain a mixture A;

[0142] Step (2): Add 2.0 g of 3-(3-pyridine)-5-methylbenzoic acid coordinated catalyst YG-31-1-025 to the mixture A of step (1), and heat at 80° C. with stirring for 60 min to obtain a mixture B;

[0143] Step (3): adding 0.1 g of ammonium acetate to the mixture B formed in step (2) to obtain a mixture C;

[0144] Step (4): Add 0.1 g of phosphomolybdic acid to the mixture C formed in step (3), and stir at 120° C. for 60 minutes to obtain a total of 31.2 g of composite catalyst 3.

[0145] Embodiment 18

[0146] Step (1): adding 20.0 g of methanol to 10.0 g of hexadecyltrimethylammonium bromide, and stirring at room temperature until the solid is completely dissolved to obtain a mixture A;

[0147] Step (2): add 1.0 g of 3-(3-pyridine)-5-ethylbenzoic acid coordinated catalyst YG-31-1-027 to the mixed solution of step (1), and heat with stirring at 40° C. for 30 min to obtain a mixture B;

[0148] Step (3): adding 0.1 g of manganese acetate to the mixture B formed in step (2) to obtain a mixture C;

[0149] Step (4): Add 0.1 g of phosphomolybdic acid to the mixture C formed in step (3), and stir at 80° C. for 60 minutes to obtain a total of 31.2 g of composite catalyst 4.

[0150] Embodiment 19

[0151] Step (1): adding 30.0 g of ethanol to a solid mixture of 5.0 g of ammonium bromide and 5.0 g of octadecyltrimethylammonium bromide, and stirring at room temperature until the solid is completely dissolved to obtain a mixture A;

[0152] Step (2): Add 1.0 g of 3-(3-pyridine)-5-butylbenzoic acid coordinated catalyst YG-31-1-031 to the mixture A of step (1), and heat at 120° C. with stirring for 30 min to obtain a mixture B;

[0153] Step (3): adding 0.1 g of cerium acetate to the mixture B formed in step (2) to obtain a mixture C;

[0154] Step (4): Add 0.1 g of phosphotungstic acid to the mixture C formed in step (3), and stir at 110° C. for 120 minutes to obtain a total of 41.2 g of composite catalyst 5.

[0155] Embodiment 20

[0156] Step (1): adding 35.0 g of methanol to a solid mixture of 5.0 g of N-hydroxyphthalimide and 5.0 g of hexadecyltrimethylammonium bromide, and stirring at room temperature until the solid is completely dissolved to obtain a mixture A;

[0157] Step (2): Add 1.0 g of 3-(3-pyridine)-5-methylbenzoic acid coordinated catalyst YG-31-1-032 to the mixture A of step (1), and heat with stirring at 80° C. for 200 min to obtain a mixture B;

[0158] Step (3): adding 0.1 g of cerium acetate to the mixture B formed in step (2) to obtain a mixture C;

[0159] Step (4): Add 0.1 g of phosphomolybdic acid to the mixture C formed in step (3), and stir at 120° C. for 40 minutes to obtain a total of 41.2 g of the composite catalyst 6.

[0160] Embodiment 21

[0161] Step (1): adding 25.0 g of methanol to a solid mixture of 5.0 g of ammonium bromide and 7.0 g of N-hydroxyphthalimide, and stirring at room temperature until the solid is completely dissolved to obtain a mixture A;

[0162] Step (2): Add 1.0 g of 3-(3-pyridine)-5-ethylbenzoic acid coordinated catalyst YG-31-1-034 to the mixture A of step (1), and heat at 80° C. with stirring for 60 min to obtain a mixture B;

[0163] Step (3): adding 0.1 g of cerium acetate to the mixture B formed in step (2) to obtain a mixture C;

[0164] Step (4): Add 0.1 g of phosphomolybdic acid to the mixture C formed in step (3), and stir at 110° C. for 65 minutes to obtain a total of 42.2 g of composite catalyst 7.

[0165] Embodiment 22

[0166] Step (1): adding 45.0 g of methanol to a solid mixture of 5.0 g of N-hydroxyphthalimide and 10.0 g of hexadecyltrimethylammonium bromide, and stirring at room temperature until the solid is completely dissolved to obtain a mixture A;

[0167] Step (2): Add 1.0 g of 3-(3-pyridine)-5-methylbenzoic acid coordinated catalyst YG-31-1-035 to the mixture A of step (1), and heat with stirring at 60° C. for 100 min to obtain a mixture B;

[0168] Step (3): adding 0.1 g of cerium acetate to the mixture B formed in step (2) to obtain a mixture C;

[0169] Step (4): Add 0.1 g of phosphomolybdic acid to the mixture C formed in step (3), and stir at 100° C. for 120 minutes to obtain a total of 41.2 g of the composite catalyst 8.

[0170] Embodiment 23

[0171] Step (1): adding 30.0 g of methanol to a solid mixture of 5.0 g of N-hydroxyphthalimide and 5.0 g of hexadecyltrimethylammonium bromide, and stirring at room temperature until the solid is completely dissolved to obtain a mixture A;

[0172] Step (2): Add 1.0 g of 3-(3-pyridine)-5-ethylbenzoic acid coordinated catalyst YG-31-1-038 to the mixture A of step (1), and heat at 60° C. with stirring for 60 min to obtain a mixture B;

[0173] Step (3): adding 0.1 g of cerium acetate to the mixture B formed in step (2) to obtain a mixture C;

[0174] Step (4): Add 0.1 g of phosphomolybdic acid to the mixture C formed in step (3), and stir at 120° C. for 60 minutes to obtain a total of 41.2 g of the composite catalyst 9.

[0175] Embodiment 24

[0176] Step (1): adding 30.0 g of methanol to a solid mixture of 5.0 g of N-hydroxyphthalimide and 5.0 g of hexadecyltrimethylammonium bromide, and stirring at room temperature until the solid is completely dissolved to obtain a mixture A;

[0177] Step (2): Add 1.0 g of 3-(3-pyridine)-5-methylbenzoic acid coordinated catalyst YG-31-1-036 to the mixture A of step (1), and heat at 80° C. with stirring for 60 min to obtain a mixture B;

[0178] Step (3): adding 0.1 g of cerium acetate to the mixture B formed in step (2) to obtain a mixture C;

[0179] Step (4): Add 0.1 g of phosphomolybdic acid to the mixture C formed in step (3), and stir at 100° C. for 60 minutes to obtain a total of 41.2 g of the composite catalyst 10.

[0180] Embodiment 25

[0181] Step (1): adding 30.0 g of methanol to a solid mixture of 5.0 g of N-hydroxyphthalimide and 5.0 g of hexadecyltrimethylammonium bromide, and stirring at room temperature until the solid is completely dissolved to obtain a mixture A;

[0182] Step (2): Add 1.0 g of 3-(3-pyridine)-5-ethylbenzoic acid coordinated catalyst YG-31-1-040 to the mixture A of step (1), and heat at 80° C. with stirring for 60 min to obtain a mixture B;

[0183] Step (3): adding 0.1 g of cerium acetate to the mixture B formed in step (2) to obtain a mixture C;

[0184] Step (4): Add 0.1 g of phosphomolybdic acid to the mixture C formed in step (3), and stir at 100° C. for 60 minutes to obtain a total of 41.2 g of the composite catalyst 11.

[0185] Embodiment 26

[0186] Step (1): adding 30.0 g of methanol to a solid mixture of 5.0 g of N-hydroxyphthalimide and 5.0 g of hexadecyltrimethylammonium bromide, and stirring at room temperature until the solid is completely dissolved to obtain a mixture A;

[0187] Step (2): Add 1.0 g of 3-(3-pyridine)-5-methylbenzoic acid coordinated catalyst YG-31-1-042 to the mixture A of step (1), and heat at 80° C. with stirring for 60 min to obtain a mixture B;

[0188] Step (3): adding 0.1 g of cerium acetate to the mixture B formed in step (2) to obtain a mixture C;

[0189] Step (4): Add 0.1 g of phosphomolybdic acid to the mixture C formed in step (3), and stir at 100° C. for 60 minutes to obtain a total of 41.2 g of the composite catalyst 12.

[0190] Embodiment 27

[0191] Step (1): adding 30.0 g of methanol to a solid mixture of 5.0 g of N-hydroxyphthalimide and 5.0 g of hexadecyltrimethylammonium bromide, and stirring at room temperature until the solid is completely dissolved to obtain a mixture A;

[0192] Step (2): Add 1.0 g of 3-(3-pyridine)-5-isopropylbenzoic acid coordinated catalyst YG-31-1-053 to the mixture A of step (1), and heat at 80° C. with stirring for 60 min to obtain a mixture B;

[0193] Step (3): adding 0.1 g of cerium acetate to the mixture B formed in step (2) to obtain a mixture C;

[0194] Step (4): Add 0.1 g of phosphomolybdic acid to the mixture C formed in step (3), and stir at 100° C. for 60 minutes to obtain a total of 41.2 g of the composite catalyst 13.

[0195] Embodiment 28:

[0196] Step (1): adding 30.0 g of methanol to a solid mixture of 5.0 g of N-hydroxyphthalimide and 5.0 g of hexadecyltrimethylammonium bromide, and stirring at room temperature until the solid is completely dissolved to obtain a mixture A;

[0197] Step (2): Add 1.0 g of 3-(3-pyridine)-5-methylbenzoic acid coordinated catalyst YG-31-1-054 to the mixture A of step (1), and heat at 80° C. with stirring for 60 min to obtain a mixture B;

[0198] Step (3): adding 0.1 g of cerium acetate to the mixture B formed in step (2) to obtain a mixture C;

[0199] Step (4): Add 0.1 g of phosphomolybdic acid to the mixture C formed in step (3), and stir at 100° C. for 60 minutes to obtain a total of 41.2 g of the composite catalyst 14.

[0200] Application Examples

[0201] Embodiment 29

[0202] N-hydroxyphthalimide (0.25g), 3-(3-pyridine)-5-ethylbenzoic acid coordinated catalyst YG-31-1-022 (0.1g), manganese acetate (0.01g), sodium tungstate (0.04g), ethanol (2.0g) solvent, acetic acid (20g), mesitylene (100g) were added to a 250mL titanium autoclave in sequence. After the autoclave was installed, nitrogen was filled in until the pressure in the autoclave was 0.5MPa 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 60°C, and air was passed until the pressure in the autoclave was 0.3MPa. Air was passed continuously, and the flow rate was controlled to be 400-500mL / min. The reaction was terminated after three hours. The reaction solution was dark brown, and the total weight of the reaction solution was weighed to be 220.14g. Take 0.1g of the reaction solution, use toluene as the internal standard, take 0.1g of toluene, add 30g of acetonitrile to dilute, and inject the sample for testing. Substitute the test data into the internal standard curve to calculate that 4.04g of mesitylene remains and 193.47g of trimesic acid. The conversion rate of mesitylene is calculated to be 95.96%, and the selectivity of trimesic acid is 95.41%.

[0203] Embodiment 30

[0204] Add ammonium bromide (0.05g), 3-(3-pyridine)-5-methylbenzoic acid coordinated catalyst YG-31-1-025 (0.2g), manganese acetate (0.01g), sodium tungstate (0.04g), ethanol (2.0g), propionic acid (20g), mesitylene (100g) in sequence to a 250mL titanium autoclave. After the autoclave is installed, fill it with nitrogen until the pressure inside the autoclave is 0.5MPa and keep it for 15 minutes. If the pressure drop does not exceed 5%, it is considered that the air tightness of the autoclave is good. After the nitrogen is discharged, heat it to 60°C, ventilate it with air until the pressure inside the autoclave is 0.6MPa, vent it continuously, control the flow rate to 400-500mL / min, and end the reaction after three hours. The reaction solution is dark brown, and the total weight of the reaction solution is 221.34g. Take 0.1g of the reaction solution, use toluene as the internal standard, take 0.1g of toluene, add 30g of acetonitrile to dilute, and inject the sample for testing. Substitute the test data into the internal standard curve to calculate that the remaining mesitylene is 3.96g, and the trimesic acid is 190.09g. The conversion rate of mesitylene is calculated to be 96.04%, and the selectivity of trimesic acid is 94.21%.

[0205] Embodiment 31

[0206] Add phenyltrimethylammonium bromide (0.05g), 3-(3-pyridine)-5-ethylbenzoic acid coordinated catalyst YG-31-1-027 (0.2g), manganese acetate (0.01g), sodium chloride (0.04g), methanol (2.0g), acetic acid (15g), mesitylene (100g) in sequence to a 250mL titanium autoclave. After the autoclave is installed, fill it with nitrogen until the pressure in the autoclave is 0.5MPa and keep it for 15 minutes. If the pressure decreases by no more than 5%, it is considered that the air tightness of the autoclave is good. After the nitrogen is discharged, heat it to 60°C, ventilate it with air until the pressure in the autoclave is 0.6MPa, vent it continuously, control the flow rate to 400-500mL / min, and end the reaction after three hours. The reaction solution is dark brown, and the total weight of the reaction solution is 219.21g. Take 0.1g of the reaction solution, use toluene as the internal standard, take 0.1g of toluene, add 30g of acetonitrile to dilute, and inject the sample for testing. Substitute the test data into the internal standard curve to calculate that the remaining mesitylene is 7.25g, and trimesic acid is 179.69g. The conversion rate of mesitylene is calculated to be 92.75%, and the selectivity of trimesic acid is 92.21%.

[0207] Embodiment 32

[0208] N-hydroxyphthalimide (0.05g), 3-(3-pyridine)-5-ethylbenzoic acid coordinated catalyst YG-31-1-040 (0.2g), nickel acetate (0.01g), magnesium chloride (0.03g), methanol (2.0g), acetic acid (15g), mesitylene (100g) were added to a 250mL titanium autoclave in sequence. After the autoclave was installed, nitrogen was filled in until the pressure in the autoclave was 0.5MPa 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 60°C, and air was passed through until the pressure in the autoclave was 0.6MPa. The air was passed through continuously, and the flow rate was controlled to be 400-500mL / min. The reaction was terminated after three hours. The reaction solution was dark brown, and the total weight of the reaction solution was weighed to be 219.55g. Take 0.1g of the reaction solution, use toluene as the internal standard, take 0.1g of toluene, add 30g of acetonitrile to dilute, and inject the sample for testing. Substitute the test data into the internal standard curve to calculate that the remaining mesitylene is 4.25g, and the trimesic acid is 193.55g. The conversion rate of mesitylene is calculated to be 95.75%, and the selectivity of trimesic acid is 96.21%.

[0209] Embodiment 33

[0210] Ammonium bromide (0.05g), hexadecyl trimethyl ammonium bromide (0.05g), 3-(3-pyridine)-5-ethylbenzoic acid coordinated catalyst YG-31-1-022 (0.2g), chromium acetate (0.01g), cupric chloride (0.07g), methanol (2.0g), acetic acid (15g), mesitylene (100g) were added to a 250mL titanium autoclave in sequence. After the autoclave was installed, nitrogen was filled in until the pressure in the autoclave was 0.5MPa 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 60°C, and air was passed through until the pressure in the autoclave was 0.6MPa. Air was passed through continuously, and the flow rate was controlled to be 400-500mL / min. The reaction was terminated after three hours. The reaction solution was dark brown, and the total weight of the reaction solution was weighed to be 216.56g. Take 0.1g of the reaction solution, use toluene as the internal standard, take 0.1g of toluene, add 30g of acetonitrile to dilute, and then inject the sample for testing. Substitute the test data into the internal standard curve to calculate that the remaining mesitylene is 9.98g, and the trimesic acid is 168.72g. The conversion rate of mesitylene is calculated to be 90.02%, and the selectivity of trimesic acid is 89.21%.

[0211] Embodiment 34

[0212] N-hydroxyphthalimide (0.05g), hexadecyl trimethyl ammonium bromide (0.08g), 3-(3-pyridine)-5-ethylbenzoic acid coordinated catalyst YG-31-1-027 (0.2g), calcium acetate (0.01g), sodium chloride (0.03g), methanol (2.0g), acetic acid (20g), mesitylene (100g) were added to a 250mL titanium autoclave in sequence. After the autoclave was installed, nitrogen was filled in until the pressure in the autoclave was 0.5MPa 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 60°C, and air was passed through until the pressure in the autoclave was 0.6MPa. Air was passed through continuously, and the flow rate was controlled to be 400-500mL / min. The reaction was terminated after three hours. The reaction solution was dark brown, and the total weight of the reaction solution was weighed to be 220.51g. Take 0.1g of the reaction solution, use toluene as the internal standard, take 0.1g of toluene, add 30g of acetonitrile to dilute, and inject the sample for testing. Substitute the test data into the internal standard curve to calculate that the remaining mesitylene is 1.75g, and the trimesic acid is 168.63g. The conversion rate of mesitylene is calculated to be 98.25%, and the selectivity of trimesic acid is 81.69%.

[0213] Embodiment 35

[0214] N-hydroxyphthalimide (0.05g), octadecyl trimethyl ammonium bromide (0.05g), 3-(3-pyridine)-5-isopropylbenzoic acid coordinated catalyst YG-31-1-023 (0.2g), calcium acetate (0.01g), ammonium molybdate (0.03g), methanol (2.0g), acetic acid (20g), mesitylene (100g) were added to a 250mL titanium autoclave in sequence. After the autoclave was installed, nitrogen was filled in until the pressure in the autoclave was 0.5MPa 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 60°C, and air was passed through until the pressure in the autoclave was 0.5MPa. Air was passed through continuously, and the flow rate was controlled to be 400-500mL / min. The reaction was terminated after three hours. The reaction solution was dark brown, and the total weight of the reaction solution was weighed to be 219.43g. Take 0.1g of the reaction solution, use toluene as the internal standard, take 0.1g of toluene, add 30g of acetonitrile to dilute, and inject the sample for testing. Substitute the test data into the internal standard curve to calculate that 4.69g of mesitylene remains and 183.29g of trimesic acid. The conversion rate of mesitylene is calculated to be 95.31%, and the selectivity of trimesic acid is 91.53%.

[0215] Embodiment 36

[0216] N-hydroxyphthalimide (0.5g), hexadecyl trimethyl ammonium bromide (0.5g), 3-(3-pyridine)-5-butylbenzoic acid coordinated catalyst YG-31-1-031 (0.2g), magnesium acetate (0.01g), sodium sulfate (0.03g), methanol (2.0g), acetic acid (20g), mesitylene (100g) were added to a 250mL titanium autoclave in sequence. After the autoclave was installed, nitrogen was filled in until the pressure in the autoclave was 0.5MPa 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 60°C, and air was passed through until the pressure in the autoclave was 0.3MPa. Air was passed through continuously, and the flow rate was controlled to be 400-500mL / min. The reaction was terminated after three hours. The reaction solution was dark brown, and the total weight of the reaction solution was weighed to be 220.43g. Take 0.1g of the reaction solution, use toluene as the internal standard, take 0.1g of toluene, add 30g of acetonitrile to dilute, and inject the sample for testing. Substitute the test data into the internal standard curve to calculate that the remaining mesitylene is 6.44g, and the trimesic acid is 177.52g. The conversion rate of mesitylene is calculated to be 93.56%, and the selectivity of trimesic acid is 90.31%.

[0217] Embodiment 37

[0218] N-hydroxyphthalimide (0.8g), hexadecyl trimethyl ammonium bromide (0.4g), 3-(3-pyridine)-5-methylbenzoic acid coordinated catalyst YG-31-1-032 (0.2g), magnesium chloride (0.01g), sodium tungstate (0.03g), methanol (2.0g), acetic acid (20g), mesitylene (100g) were added to a 250mL titanium autoclave in sequence. After the autoclave was installed, nitrogen was filled in until the pressure inside the autoclave was 0.5MPa 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 60°C, and air was passed through until the pressure inside the autoclave was 0.3MPa. Air was passed through continuously, and the flow rate was controlled to be 400-500mL / min. The reaction was terminated after three hours. The reaction solution was dark brown, and the total weight of the reaction solution was weighed to be 221.15g. Take 0.1g of the reaction solution, use toluene as the internal standard, take 0.1g of toluene, add 30g of acetonitrile to dilute, and inject the sample for testing. Substitute the test data into the internal standard curve to calculate that the remaining mesitylene is 3.77g, and the trimesic acid is 188.21g. The conversion rate of mesitylene is calculated to be 96.23%, and the selectivity of trimesic acid is 93.09%.

[0219] Embodiment 38

[0220] N-hydroxyphthalimide (0.4g), hexadecyl trimethyl ammonium bromide (0.7g), 3-(3-pyridine)-5-isopropylbenzoic acid coordinated catalyst YG-31-1-053 (0.2g), cupric acetate (0.01g), phosphomolybdic acid (0.05g), methanol (2.0g), acetic acid (20g), mesitylene (100g) were added to a 250mL titanium autoclave in sequence. After the autoclave was installed, nitrogen was filled in until the pressure in the autoclave was 0.5MPa 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 60°C, and air was passed through until the pressure in the autoclave was 0.3MPa. Air was passed through continuously, and the flow rate was controlled to be 400-500mL / min. The reaction was terminated after three hours. The reaction solution was dark brown, and the total weight of the reaction solution was weighed to be 217.77g. Take 0.1g of the reaction solution, use toluene as the internal standard, take 0.1g of toluene, add 30g of acetonitrile to dilute, and inject the sample for testing. Substitute the test data into the internal standard curve to calculate that the remaining mesitylene is 7.63g, and the trimesic acid is 182.77g. The conversion rate of mesitylene is calculated to be 92.37%, and the selectivity of trimesic acid is 94.18%.

[0221] Embodiment 39

[0222] N-hydroxyphthalimide (0.5g), hexadecyl trimethyl ammonium bromide (0.5g), 3-(3-pyridine)-5-ethylbenzoic acid coordinated catalyst YG-31-1-034 (0.2g), potassium acetate (0.01g), phosphomolybdic acid (0.05g), methanol (2.0g), acetic acid (20g), mesitylene (100g) were added to a 250mL titanium autoclave in sequence. After the autoclave was installed, nitrogen was filled in until the pressure in the autoclave was 0.5MPa 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 60°C, and air was passed through until the pressure in the autoclave was 0.5MPa. Air was passed through continuously, and the flow rate was controlled to be 400-500mL / min. The reaction was terminated after three hours. The reaction solution was dark brown, and the total weight of the reaction solution was weighed to be 220.68g. Take 0.1g of the reaction solution, use toluene as the internal standard, take 0.1g of toluene, add 30g of acetonitrile to dilute, and inject the sample for testing. Substitute the test data into the internal standard curve to calculate that the remaining mesitylene is 8.61g and trimesic acid is 180.53g. The conversion rate of mesitylene is calculated to be 91.39%, and the selectivity of trimesic acid is 94.02%.

[0223] Embodiment 40

[0224] N-hydroxyphthalimide (0.5g), hexadecyl trimethyl ammonium bromide (0.5g), 3-(3-pyridine)-5-ethylbenzoic acid coordinated catalyst YG-31-1-034 (0.2g), zirconium acetate (0.01g), phosphomolybdic acid (0.15g), methanol (2.0g), acetic acid (20g), mesitylene (100g) were added to a 250mL titanium autoclave in sequence. After the autoclave was installed, nitrogen was filled in until the pressure in the autoclave was 0.5MPa 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 60°C, and air was passed through until the pressure in the autoclave was 0.5MPa. Air was passed through continuously, and the flow rate was controlled to be 400-500mL / min. The reaction was terminated after three hours. The reaction solution was dark brown, and the total weight of the reaction solution was weighed to be 218.12g. Take 0.1g of the reaction solution, use toluene as the internal standard, take 0.1g of toluene, add 30g of acetonitrile to dilute, and inject the sample for testing. Substitute the test data into the internal standard curve to calculate that the remaining mesitylene is 6.44g, and the trimesic acid is 177.78g. The conversion rate of mesitylene is calculated to be 93.56%, and the selectivity of trimesic acid is 90.44%.

[0225] Embodiment 41

[0226] N-hydroxyphthalimide (0.5g), hexadecyl trimethyl ammonium bromide (0.5g), 3-(3-pyridine)-5-methylbenzoic acid coordinated catalyst YG-31-1-035 (0.2g), cerium acetate (0.01g), phosphomolybdic acid (0.15g), methanol (2.0g), acetic acid (20g), mesitylene (100g) were added to a 250mL titanium autoclave in sequence. After the autoclave was installed, nitrogen was filled in until the pressure in the autoclave was 0.5MPa 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 60°C, and air was passed through until the pressure in the autoclave was 0.5MPa. Air was passed through continuously, and the flow rate was controlled to be 400-500mL / min. The reaction was terminated after three hours. The reaction solution was dark brown, and the total weight of the reaction solution was weighed to be 135.02g. Take 0.1g of the reaction solution, use toluene as the internal standard, take 0.1g of toluene, add 30g of acetonitrile to dilute, and inject the sample for testing. Substitute the test data into the internal standard curve to calculate that the remaining mesitylene is 9.44g and trimesic acid is 175.69g. The conversion rate of mesitylene is calculated to be 90.56%, and the selectivity of trimesic acid is 92.34%.

[0227] Embodiment 42

[0228] N-hydroxyphthalimide (0.5g), hexadecyl trimethyl ammonium bromide (0.5g), 3-(3-pyridine)-5-methylbenzoic acid coordinated catalyst YG-31-1-042 (0.2g), cerium acetate (0.01g), phosphomolybdic acid (0.15g), methanol (2.0g), acetic acid (20g), mesitylene (100g) were added to a 250mL titanium autoclave in sequence. After the autoclave was installed, nitrogen was filled in until the pressure in the autoclave was 0.5MPa 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 60°C, and air was passed through until the pressure in the autoclave was 0.5MPa. Air was passed through continuously, and the flow rate was controlled to be 400-500mL / min. The reaction was terminated after three hours. The reaction solution was dark brown, and the total weight of the reaction solution was weighed to be 217.38g. Take 0.1g of the reaction solution, use toluene as the internal standard, take 0.1g of toluene, add 30g of acetonitrile to dilute, and then inject the sample for testing. Substitute the test data into the internal standard curve to calculate that the remaining mesitylene is 7.42g and trimesic acid is 179.61g. The conversion rate of mesitylene is calculated to be 92.58%, and the selectivity of trimesic acid is 92.34%.

[0229] Comparative Example

[0230] The experimental operation methods of the comparative example are consistent with those of Example 29, except for the amount of material added. The material addition amount and the experimental results are specifically shown in Table 1.

[0231]

[0232]

[0233] It can be seen from Table 1 that compared with Comparative Example 8 in which no 3-(3-pyridine)-5-ethylbenzoic acid coordinated catalyst is added, Example 29 has the best reaction effect in terms of conversion rate and selectivity, indicating that the 3-(3-pyridine)-5-R-ethylbenzoic acid coordinated catalyst disclosed in the present invention can improve the selectivity and activity of the oxidation reaction of mesitylene.

[0234] Combined with Comparative Examples 1-7, by selectively removing one or more of the cocatalyst, regulator, protective agent and solvent, the conversion rate of mesitylene and the selectivity of trimesic acid were reduced to varying degrees, indicating that the use of a catalyst, cocatalyst, regulator, protective agent and solvent coordinated with 3-(3-pyridine)-5-R-benzoic acid can better promote the oxidation of mesitylene to produce trimesic acid.

[0235] 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.

[0236] 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 catalyst coordinated by 3-(3-pyridine)-5-ylbenzoic acid, characterized in that: The catalyst chemical formula is as follows: Wherein, B is octyltributylphosphonium ion, tetrabutylphosphonium ion, tributylethylphosphonium ion, tributylhexylphosphonium ion, tetramethylammonium ion, tetraethylammonium ion, tetrabutylammonium ion, benzyltrimethylammonium ion, lithium ion, sodium ion, potassium ion, magnesium ion, calcium ion, ammonium ion, dodecyldimethylbenzylammonium ion, dodecyltrimethylammonium ion, octadecyltrimethylammonium ion, octadecyldimethylbenzylammonium ion, benzyltriphenylphosphonium ion or benzyltriethylammonium ion; M is Cu, Fe, Cr, Mo, V, W, Co, Ni or Zr; R is C1~C 10 alkyl; x is an integer between 1 and 20; y is an integer between 1 and 40.

2. A method for preparing the 3-(3-pyridine)-5-R-benzoic 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 1-4, and then add peroxide to obtain a metal peroxide solution; Add alkyl-substituted 3-(3-pyridine)-5-R-ylbenzoic acid and salt to the metal peroxide solution, filter, and dry to obtain a catalyst coordinated with 3-(3-pyridine)-5-R-ylbenzoic acid.

3. The method for preparing a catalyst coordinated by 3-(3-pyridine)-5-R-benzoic acid according to claim 2, characterized in that: The metal compound is selected from sodium molybdate, chromium nitrate, cobalt nitrate, sodium tungstate, copper nitrate, iron nitrate, zirconium acetate, cobalt sulfate, nickel nitrate, nickel sulfate, nickel acetate and sodium metavanadate.

4. The method for preparing a catalyst coordinated by 3-(3-pyridine)-5-R-benzoic acid according to claim 2, characterized in that: The peroxide is selected from hydrogen peroxide, meta-chloroperbenzoic acid and urea peroxide.

5. The method for preparing a catalyst coordinated by 3-(3-pyridine)-5-R-benzoic acid according to claim 2, characterized in that: The alkyl-substituted 3-(3-pyridine)-5-ylbenzoic acid is selected from 3-(3-pyridine)-5-methylbenzoic acid, 3-(3-pyridine)-5-ethylbenzoic acid, 3-(3-pyridine)-5-butylbenzoic acid and 3-(3-pyridine)-5-isopropylbenzoic acid.

6. The method for preparing a catalyst coordinated by 3-(3-pyridine)-5-R-benzoic acid according to claim 2, characterized in that: The salt is selected from octadecyltrimethylammonium chloride, octadecyltrimethylammonium bromide, lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, ammonium bromide, dodecyldimethylbenzylammonium bromide, dodecyltrimethylammonium chloride, octadecyldimethylbenzylammonium bromide, octyltributylphosphonium bromide, tetrabutylphosphonium bromide, tributylethylphosphonium bromide, tributylhexylphosphonium bromide, benzyltriphenylphosphonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltrimethylammonium chloride or benzyltriethylammonium chloride.

7. A composite catalyst, characterized in that: The invention comprises the 3-(3-pyridine)-5-R-benzoic acid acid coordinated catalyst as claimed in claim 1.

8. The composite catalyst according to claim 7, characterized in that It also includes a cocatalyst, wherein the weight ratio of the catalyst coordinated by 3-(3-pyridine)-5-R-ylbenzoic acid to the cocatalyst is 80:(1-500); The cocatalyst is selected from cerium nitrate, cerium sulfate, cerium acetate, manganese acetate, manganese nitrate, manganese sulfate, vanadium oxide, cobalt oxide, silver nitrate, zirconium oxide, zirconium acetate, ferric nitrate, ferric sulfate, ferric chloride, magnesium chloride, copper sulfate, ammonium acetate, copper acetate, copper nitrate, magnesium sulfate, magnesium acetate, zinc acetate, zinc sulfate, sodium molybdate, potassium acetate, nickel acetate, chromium acetate, calcium acetate and potassium sulfate.

9. The composite catalyst according to claim 7, characterized in that: It also includes a regulator, and the weight ratio of the 3-(3-pyridine)-5-R-ylbenzoic acid acid coordinated catalyst to the regulator is 100:(1-500); The regulator is selected from phosphomolybdic acid, phosphotungstic acid, tetrabutylammonium bromide, boric acid, silicotungstic acid, sodium tungstate, sodium chloride, magnesium chloride, copper chloride and phosphomolybdic vanadic acid.

10. The composite catalyst according to claim 7, characterized in that: It also includes a protective agent, and the weight ratio of the catalyst coordinated by 3-(3-pyridine)-5-R-ylbenzoic acid to the protective agent is 100:(1-500); The protective agent is selected from sodium acetate, ammonium bromide, sodium bromide, hexadecyltrimethylammonium bromide, phenyltrimethylammonium bromide, sodium molybdate, ammonium molybdate, sodium sulfate and N-hydroxyphthalimide.

11. The composite catalyst according to claim 7, characterized in that: It also includes a solvent, and the weight ratio of the 3-(3-pyridine)-5-R-ylbenzoic acid acid coordinated catalyst to the solvent is 100:(50-10000); The solvent is selected from the group consisting of dichloromethane, 1,4-dioxane, acetonitrile, methanol, ethanol, formic acid, acetic acid, propionic acid and ethyl acetate.

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 3-(3-pyridine)-5-R-ylbenzoic acid acid-coordinated catalyst of claim 1 to the solution, and stir at 20 to 100° C. for 10 to 60 minutes; Then add the auxiliary catalyst and ultrasonicate at 20-120°C for 20-60min; Then add a regulator and stir at 20-110°C for 10-60 minutes to obtain a composite catalyst.

13. Use of the 3-(3-pyridine)-5-R-benzoic acid acid-coordinated catalyst according to claim 1 or the composite catalyst according to any one of claims 7 to 11 in the reaction of preparing trimesic acid.

Images