Isoquinoline-5-formic acid coordinated catalyst, composite catalyst, preparation method and application

Abstract

The invention discloses an isoquinoline-5-formic acid coordinated catalyst, a composite catalyst, a preparation method and application, the chemical general formula of the isoquinoline-5-formic acid coordinated catalyst is # imgabs0 #, and the composite catalyst comprises the isoquinoline-5-formic acid coordinated catalyst, a cocatalyst, a regulator, a protective agent and a solvent, by using the isoquinoline-5-formic acid coordinated catalyst or composite catalyst provided by the invention, the selectivity of the oxidation reaction of 4-methyl-1-naphthoic acid can be improved, the reaction activity can be increased, and the catalyst or 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 an isoquinoline-5-carboxylic acid coordinated catalyst, a composite catalyst, a preparation method and an application. Background Art

[0002] 1,4-Naphthalene dicarboxylic acid, also known as 1,4-naphthalene dicarboxylic acid, is widely used in dyes, fluorescent brighteners, high-adhesion coatings and plastics industries. It can be used as an important intermediate in organic synthesis and is used to manufacture high-performance polyester fibers and insulating materials. It is an important monomer for polyethylene naphthalate, liquid crystal polymers and polyurethane resins, and also has certain applications in the medical field.

[0003] The synthesis of 1,4-naphthalene dicarboxylic acid can be divided into the direct oxidation of 1,4-dimethylnaphthalene, the three-step method of naphthalene through bromination, cyano substitution, and hydrolysis to synthesize 1,4-naphthalene dicarboxylic acid, the naphthalene / 1-chloromethylnaphthalene method, the 1-methyl-4-hydroxymethylnaphthalene method, and the three-step method of 1-methylnaphthalene to produce 1,4-naphthalene dicarboxylic acid. Domestic production enterprises produce 1,4-naphthalene dicarboxylic acid by three-step unit reaction of 1-methylnaphthalene, and use 1-methylnaphthalene as raw material to produce 1-methyl-4-acetylnaphthalene through Friedel-Crafts reaction, and then oxidize with sodium hypochlorite to produce 4-methyl-1-naphthalene dicarboxylic acid, and 4-methyl-1-naphthalene dicarboxylic acid is oxidized with potassium permanganate to produce 1,4-naphthalene dicarboxylic acid. Among them, the oxidation of 4-methyl-1-naphthalene dicarboxylic acid adopts the potassium permanganate oxidation method, which requires more than 4 times the potassium permanganate for oxidation, has low reaction efficiency, produces a large amount of waste residue and wastewater, has low production efficiency, and has a huge amount of three wastes.

[0004] Chinese patent CN117820107A discloses a method for obtaining 1,4-naphthalenedicarboxylic acid using dichloromethane, α-methylnaphthalene and aluminum chloride as starting materials through a series of six-step reactions and post-treatment. The method has lengthy steps and complicated operations, and uses acetyl chloride, benzene, sodium hypochlorite and a large amount of acid and alkali in the middle, resulting in high raw material costs or post-treatment costs.

[0005] Chinese patent CN112778116A discloses a method of using 1-bromonaphthalene as a starting material, reacting with acetyl chloride to generate 4-bromo-1-acetylnaphthalene by Friedel-Crafts reaction; then oxidizing with hypochlorite to obtain 4-bromo-1-naphthoic acid; 4-bromo-1-naphthoic acid reacts with cuprous cyanide in a polar aprotic solvent in the presence of potassium iodide and copper sulfate to generate 4-cyanonaphthoic acid copper salt complex; 4-cyanonaphthoic acid copper salt complex is hydrolyzed with alkali to obtain 1,4-naphthalenedicarboxylic acid. This method also has complicated operation steps and uses raw materials with high cost or high post-processing cost such as acetyl chloride, hypochlorite, cuprous cyanide, potassium iodide, etc.

[0006] After experimental investigation, it was found that the above-reported synthesis methods, when used in experiments to prepare 1,4-naphthalene dicarboxylic acid, all had disadvantages such as lengthy reaction steps, complicated operations, and high raw material costs or post-processing costs, and therefore could not be applied to the industrial-scale production of 1,4-naphthalene dicarboxylic acid.

[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 an isoquinoline-5-carboxylic acid coordinated catalyst, a composite catalyst, a preparation method and an application thereof, which are suitable for the industrial production of oxidizing 4-methyl-1-naphthoic acid to prepare 1,4-naphthalenedicarboxylic acid.

[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 catalyst coordinated by isoquinoline-5-carboxylic acid, wherein the catalyst has a general chemical formula as shown in formula (I):

[0011]

[0012] wherein B is selected from the group consisting of lithium ion, sodium ion, potassium ion, magnesium ion, calcium ion, ammonium ion, dodecyldimethylbenzylammonium ion, dodecyltrimethylammonium ion, octadecyltrimethylammonium ion, octadecyldimethylbenzylammonium ion, octyltributylphosphine ion, tetrabutylphosphine ion, tributylethylphosphine ion, tributylhexylphosphine ion, tetramethylammonium ion, tetraethylammonium ion, tetrabutylammonium ion, benzyltrimethylammonium ion, benzyltriphenylphosphine ion and benzyltriethylammonium ion;

[0013] M is selected from Cr, Mo, V, W, Cu, Fe, Co, Ni and Zr;

[0014] R is selected from C1~C 10 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 isoquinoline-5-carboxylic acid coordinated catalyst comprises the following steps:

[0019] Dissolve the metal compound in deionized water, adjust the solution pH to 3-4, and then add peroxide to obtain a metal peroxide solution;

[0020] Alkyl-substituted isoquinoline-5-carboxylic acid and salt are added to the metal peroxide solution, filtered, and dried to obtain an isoquinoline-5-carboxylic acid coordinated catalyst.

[0021] In one or more embodiments of the present invention, the metal compound is selected from sodium tungstate, copper sulfate, iron nitrate, zirconium acetate, sodium molybdate, chromium nitrate, cobalt nitrate, cobalt sulfate, nickel nitrate, nickel sulfate and sodium metavanadate.

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

[0023] In one or more embodiments of the present invention, the alkyl-substituted isoquinoline-5-carboxylic acid is selected from 4-methylisoquinoline-5-carboxylic acid, 4-ethylisoquinoline-5-carboxylic acid, 4-propylisoquinoline-5-carboxylic acid, 4-isopropylisoquinoline-5-carboxylic acid, 4-n-butylisoquinoline-5-carboxylic acid, and 4-tert-butylisoquinoline-5-carboxylic acid.

[0024] 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, magnesium acetate, calcium chloride, ammonium bromide, ammonium acetate, dodecyldimethylbenzylammonium bromide, dodecyltrimethylammonium chloride, octadecyldimethylbenzylammonium bromide, octyltributylphosphonium bromide, tributylethylphosphonium bromide, tetrabutylphosphonium bromide, tributylhexylphosphonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltriphenylphosphonium bromide, benzyltrimethylammonium chloride or benzyltriethylammonium chloride.

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

[0026] A composite catalyst comprises the catalyst coordinated by isoquinoline-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 isoquinoline-5-carboxylic acid to the cocatalyst is 100:(1-200);

[0028] 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, copper sulfate, copper acetate, copper nitrate, magnesium sulfate, magnesium acetate, zinc acetate, zinc sulfate, sodium molybdate, potassium acetate and potassium sulfate.

[0029] In one or more embodiments of the present invention, a regulator is further included, and the weight ratio of the catalyst coordinated by isoquinoline-5-carboxylic acid to the regulator is 100:(1-200);

[0030] The regulator is selected from phosphomolybdic acid, phosphotungstic acid, tetrabutylammonium bromide, boric acid, silicotungstic acid 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 isoquinoline-5-carboxylic acid to the protective agent is 100:(5-200);

[0032] The protective agent is selected from sodium acetate, ammonium bromide, hexadecyltrimethylammonium bromide, phenyltrimethylammonium bromide, sodium molybdate 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 isoquinoline-5-carboxylic acid to the solvent is 100:(5-1000);

[0034] 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.

[0035] Another specific embodiment of the present invention provides a technical solution 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 isoquinoline-5-carboxylic acid to the solution and stir at 40-90°C for 20-60 minutes;

[0039] Then add the auxiliary catalyst and ultrasonicate at 40-90°C for 20-60min;

[0040] Then add a regulator and stir at 40-90°C for 30-60 minutes to obtain a composite catalyst.

[0041] Another specific embodiment of the present invention provides a technical solution as follows:

[0042] Application of the isoquinoline-5-carboxylic acid coordinated catalyst or the composite catalyst in the reaction of oxidizing 4-methyl-1-naphthoic acid to prepare 1,4-naphthalenedicarboxylic acid.

[0043] Compared with the prior art, the isoquinoline-5-carboxylic acid coordinated catalyst and composite catalyst of the present invention have high activity and selectivity, can be repeatedly applied, have low cost, and can effectively catalyze and oxidize 4-methyl-1-naphthoic acid to prepare 1,4-naphthalenedicarboxylic acid. DETAILED DESCRIPTION

[0044] 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.

[0045] A specific embodiment of the present invention provides a catalyst coordinated by isoquinoline-5-carboxylic acid, and its general chemical formula is as shown in formula (I):

[0046]

[0047] Wherein, B is selected from lithium ion, sodium ion, potassium ion, magnesium ion, calcium ion, ammonium ion, dodecyldimethylbenzylammonium ion, dodecyltrimethylammonium ion, octadecyltrimethylammonium ion, octadecyldimethylbenzylammonium ion, octyltributylphosphine ion, tetrabutylphosphine ion, tributylethylphosphine ion, tributylhexylphosphine ion, tetramethylammonium ion, tetraethylammonium ion, tetrabutylammonium ion, benzyltrimethylammonium ion, benzyltriphenylphosphine ion and benzyltriethylammonium ion; M is selected from Cr, Mo, V, W, Cu, Fe, Co, Ni and Zr; R is selected from Cl~C 10 alkyl; x is selected from an integer between 1 and 20; y is selected from an integer between 1 and 40.

[0048] Further preferably, B is selected from dodecyltrimethylammonium ion, octadecyltrimethylammonium ion, lithium ion, sodium ion, potassium ion, magnesium ion, calcium ion, ammonium ion and benzyltriphenylphosphine ion; M is selected from Cr, Mo, Co, Ni, V, Cu and 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.

[0049] More preferably, B is selected from octadecyltrimethylammonium ion, sodium ion, magnesium ion, ammonium ion and benzyltriphenylphosphine ion; M is selected from Cr, Mo, Co, Ni and V; R is selected from methyl, ethyl and isopropyl; x is 1; and y is 1 or 2.

[0050] By selecting the above types of B, M, and R and limiting the values ​​of x and y, the obtained catalyst coordinated with isoquinoline-5-carboxylic acid can selectively catalyze the oxidation of 4-methyl-1-naphthoic acid to generate 1,4-naphthalenedicarboxylic acid, with high selectivity and activity, and can be repeatedly applied at low cost.

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

[0052] Step 1, adding a metal compound into deionized water, and obtaining a solution after the metal compound is completely dissolved, adjusting the pH of the solution to 3-4, and then adding peroxide to obtain a metal peroxide solution.

[0053] Specifically, the metal compound is selected from sodium tungstate, copper sulfate, iron nitrate, zirconium acetate, sodium molybdate, chromium nitrate, cobalt nitrate, cobalt sulfate, nickel nitrate, nickel sulfate and sodium metavanadate, the peroxide is selected from hydrogen peroxide and urea peroxide, and hydrochloric acid or sulfuric acid is used to adjust the pH of the solution.

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

[0055] Specifically, the alkyl-substituted isoquinoline-5-carboxylic acid is selected from 4-methylisoquinoline-5-carboxylic acid, 4-ethylisoquinoline-5-carboxylic acid, 4-propylisoquinoline-5-carboxylic acid, 4-isopropylisoquinoline-5-carboxylic acid, 4-n-butylisoquinoline-5-carboxylic acid, 4-tert-butylisoquinoline-5-carboxylic 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, hexyltributylphosphonium bromide, tributylethylphosphonium bromide, tetrabutylphosphonium bromide, tributylhexylphosphonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltriphenylphosphonium bromide, benzyltrimethylammonium chloride or benzyltriethylammonium chloride.

[0056] Another specific embodiment of the present invention provides a composite catalyst, including the above-mentioned isoquinoline-5-carboxylic acid coordinated catalyst, cocatalyst, regulator, protective agent and solvent, the weight ratio of the isoquinoline-5-carboxylic acid coordinated catalyst, cocatalyst, regulator, protective agent and solvent is 100: (1 to 200): (1 to 200): (5 to 200): (5 to 1000).

[0057] Specifically, 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, copper sulfate, copper acetate, copper nitrate, magnesium sulfate, magnesium acetate, zinc acetate, zinc sulfate, sodium molybdate, potassium acetate and potassium sulfate. 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. Selecting the above types of cocatalysts, regulators, protective agents and solvents and controlling the weight ratio at the same time helps to improve the catalyst activity, optimize the reaction conditions, and improve the reaction efficiency and selectivity.

[0058] Preferably, the weight ratio of the catalyst coordinated by isoquinoline-5-carboxylic acid, the cocatalyst, the regulator, the protective agent and the solvent is 100:(1-50):(1-50):(10-100):(100-500), the catalyst coordinated by isoquinoline-5-carboxylic acid is selected from the catalyst coordinated by isoquinoline-5-carboxylic acid with alkyl substituted with Cr, Mo, V, Co or Zr 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, hexadecyltrimethylammonium bromide, phenyltrimethylammonium bromide and N-hydroxyphthalimide, and the solvent is selected from methanol, ethanol and acetonitrile.

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

[0060] Add the protective agent to the organic solvent and mix well to obtain solution 1;

[0061] Add a catalyst coordinated with isoquinoline-5-carboxylic acid to solution 1, stir at 40 to 90° C. for 20 to 60 minutes to obtain solution 2;

[0062] Add a cocatalyst to solution 2, and perform ultrasonic treatment at 40-90°C for 20-60 minutes to obtain solution 3;

[0063] Add a regulator to solution 3, stir at 40-90° C. for 30-60 minutes to obtain a composite catalyst.

[0064] Another specific embodiment of the present invention provides the use of the above-mentioned catalyst coordinated with isoquinoline-5-carboxylic acid or composite catalyst in the reaction of oxidizing 4-methyl-1-naphthoic acid to prepare 1,4-naphthalenedicarboxylic acid.

[0065] Specifically, 4-methyl-1-naphthoic acid is dissolved in a solvent, a catalyst or a composite catalyst coordinated with isoquinoline-5-carboxylic acid is added thereto, air is introduced at a speed of 200 to 1000 ml / s, and the reaction is stirred at 80 to 150° C. for 2 to 8 hours.

[0066] Taking the composite catalyst as an example, the added amount of the composite catalyst is 0.1-5% of the weight of 4-methyl-1-naphthoic acid.

[0067] Preferably, the solvent is acetic acid, the air introduction rate is 200-500 ml / s, the reaction temperature is 90-120° C., the reaction time is 3-6 hours, and the amount of the composite catalyst added is 0.5-2% of the weight of 4-methyl-1-naphthoic acid.

[0068] The present invention is further described in detail below in conjunction with specific embodiments.

[0069] Isoquinoline-5-carboxylic acid coordinated catalyst example

[0070] Example 1

[0071] Step 1: Add 300 mL of deionized water to solid cobalt sulfate (15.50 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 60 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 1000 mL to obtain solution d.

[0072] Step 2: Heat solution d to 80°C, add 4-methylisoquinoline-5-carboxylic acid (22.46 g, 0.12 mol) and octadecyltrimethylammonium chloride (76.57 g, 0.22 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 59.31 g of yellow solid, which is the catalyst YG-36-2-001 coordinated with isoquinoline-5-carboxylic acid, and the catalyst yield reaches 92.12%. The nuclear magnetic characterization data are as follows:

[0073] 1H NMR(400MHz,DMSO-d6)δ8.81(s,1H),8.62(s,1H),8.52(d,1H),8.17(d,1H),8.05(s,1H),3 .62(t,2H),3.48(s,9H),2.49(s,3H),1.77-1.69(m,2H),1.53-1.10(m,30H),0.92(t,3H).

[0074] Example 2

[0075] Step 1: Add 300 mL of deionized water to solid cobalt sulfate (15.50 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 60 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 1000 mL to obtain solution d.

[0076] Step 2: Heat solution d to 50°C, add 4-methylisoquinoline-5-carboxylic acid (22.46 g, 0.12 mol) and sodium chloride (12.86 g, 0.22 mol) to solution d, stir while heating for about 2 hours, and centrifuge for 20 minutes. Filter, and place the solid obtained after filtration in a vacuum drying oven to dry to obtain 31.10 g of yellow solid, which is the catalyst YG-36-2-002 coordinated with isoquinoline-5-carboxylic acid, and the catalyst yield reaches 88.23%. The NMR characterization data are as follows:

[0077] 1H NMR (400MHz, DMSO-d6) δ 8.86 (s, 1H), 8.64 (s, 1H), 8.53 (d, 1H), 8.19 (d, 1H), 8.08 (s, 1H), 2.50 (s, 3H).

[0078] Example 3

[0079] Step 1: Add 600 mL of deionized water to solid cobalt sulfate (31.00 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 3 to obtain solution b. Continue stirring for about 60 minutes, then slowly add 400 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.

[0080] Step 2: Heat solution d to 50°C, add 4-methylisoquinoline-5-carboxylic acid (44.92g, 0.24mol) and magnesium acetate (15.66g, 0.22mol) 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 72.70g of yellow solid, which is the catalyst YG-36-2-003 coordinated with isoquinoline-5-carboxylic acid, and the catalyst yield reaches 90.66%. The NMR characterization data are as follows:

[0081] 1H NMR (400MHz, DMSO-d6) δ 8.89 (s, 1H), 8.67 (s, 1H), 8.54 (d, 1H), 8.21 (d, 1H), 8.09 (s, 1H), 2.52 (s, 3H).

[0082] Example 4

[0083] Step 1: Add 300 mL of deionized water to solid cobalt sulfate (15.50 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 3 to obtain solution b. Continue stirring for about 40 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 1000 mL to obtain solution d.

[0084] Step 2: Heat solution d to 80°C, add 4-methylisoquinoline-5-carboxylic acid (22.46 g, 0.12 mol) and ammonium acetate (8.41 g, 0.12 mol) to solution d, stir while heating for about 2 hours, and centrifuge for 20 minutes. Filter, and place the solid obtained after filtration in a vacuum drying oven to dry to obtain 36.21 g of yellow solid, which is the catalyst YG-36-2-004 coordinated with isoquinoline-5-carboxylic acid, and the catalyst yield reaches 92.68%. The NMR characterization data are as follows:

[0085] 1H NMR (400MHz, DMSO-d6) δ8.85(s,1H),8.63(s,1H),8.51(d,1H),8.17(d,1H),8.07(s,1H),7.24(t,4H),2.51(s,3H).

[0086] Example 5

[0087] Step 1: Add 300 mL of deionized water to solid cobalt sulfate (15.50 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 3 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 1000 mL to obtain solution d.

[0088] Step 2: Heat solution d to 80°C, add 4-methylisoquinoline-5-carboxylic acid (22.46 g, 0.12 mol) and benzyltriphenylphosphonium bromide (53.20 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 63.12 g of yellow solid, which is the catalyst YG-36-2-005 coordinated with isoquinoline-5-carboxylic acid, and the catalyst yield reaches 89.21%. The nuclear magnetic characterization data are as follows:

[0089] 1H NMR(400MHz,DMSO-d6)δ8.83(s,1H),8.60(s,1H),8.50(d,1H),8.15(d,1H),8.05(s,1H),7.87-7.73(m ,3H),7.65-7.59(m,12H),7.35-7.23(m,1H),7.19-7.10(m,2H),6.97(d,2H),5.15(d,2H),2.49(s,3H).

[0090] Example 6

[0091] Step 1: Add 300 mL of deionized water to solid cobalt sulfate (15.50 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% 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.

[0092] Step 2: Heat solution d to 60°C, add 4-ethylisoquinoline-5-carboxylic acid (24.15 g, 0.12 mol) and octadecyltrimethylammonium chloride (76.57 g, 0.22 mol) to solution d, stir while heating for about 2 hours, and centrifuge for 20 minutes. Filter, and place the solid obtained after filtration in a vacuum drying oven to dry to obtain 47.23 g of yellow solid, which is the catalyst YG-36-2-006 coordinated with isoquinoline-5-carboxylic acid, and the catalyst yield reaches 89.21%. The nuclear magnetic characterization data are as follows:

[0093] 1H NMR(400MHz,DMSO-d6)δ8.82(s,1H),8.64(s,1H),8.53(d,1H),8.16(d,1H),8.04(s,1H),3 .60(t,2H),3.48(s,9H),2.74(q,2H),1.76-1.72(m,2H),1.55-1.06(m,33H),0.88(t,3H).

[0094] Example 7

[0095] Step 1: Add 300 mL of deionized water to solid cobalt sulfate (15.50 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 1000 mL to obtain solution d.

[0096] Step 2: Heat solution d to 50°C, add 4-ethylisoquinoline-5-carboxylic acid (24.15 g, 0.12 mol) and octadecyltrimethylammonium chloride (76.57 g, 0.22 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 60.68 g of yellow solid, which is the catalyst YG-36-2-007 coordinated with isoquinoline-5-carboxylic acid, and the catalyst yield reaches 86.85%. The NMR characterization data are as follows:

[0097] 1H NMR(400MHz,DMSO-d6)δ8.83(s,1H),8.64(s,1H),8.52(d,1H),8.16(d,1H),8.02(s,1H),3.6 1(t,2H),3.48(s,9H),2.91-2.87(m,1H),1.76-1.72(m,2H),1.55-1.06(m,36H),0.88(t,3H).

[0098] Example 8

[0099] Step 1: Add 300 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 3 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 1000 mL to obtain solution d.

[0100] Step 2: Heat solution d to 50°C, add 4-methylisoquinoline-5-carboxylic acid (22.46 g, 0.12 mol) and octadecyltrimethylammonium chloride (76.57 g, 0.22 mol) to solution d, stir while heating for about 2 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-36-2-008 coordinated with isoquinoline-5-carboxylic acid, and the catalyst yield reaches 84.62%. The nuclear magnetic characterization data are as follows:

[0101] 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).

[0102] Example 9

[0103] Step 1: Add 300 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 3 to obtain solution b. Continue stirring for about 60 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 1000 mL to obtain solution d.

[0104] Step 2: Heat solution d to 80°C, add 4-ethylisoquinoline-5-carboxylic acid (24.15 g, 0.12 mol) and octadecyltrimethylammonium chloride (76.57 g, 0.22 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 44.12 g of purple-red solid, which is the catalyst YG-36-2-009 coordinated with isoquinoline-5-carboxylic acid, and the catalyst yield reaches 90.82%. The nuclear magnetic characterization data are as follows:

[0105] 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).

[0106] Example 10

[0107] Step 1: Add 300 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 3 to obtain solution b. Continue stirring for about 60 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 1000 mL to obtain solution d.

[0108] Step 2: Heat solution d to 60°C, add 4-isopropylisoquinoline-5-carboxylic acid (25.83 g, 0.12 mol) and octadecyltrimethylammonium chloride (76.57 g, 0.22 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 48.62 g of purple-red solid, which is the catalyst YG-36-2-010 coordinated with isoquinoline-5-carboxylic acid, and the catalyst yield reaches 88.51%. The nuclear magnetic characterization data are as follows:

[0109] 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).

[0110] Embodiment 11

[0111] Step 1: Add 300 mL of deionized water to a solid of sodium molybdate (20.59 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% 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.

[0112] Step 2: Heat solution d to 60°C, add 4-methylisoquinoline-5-carboxylic acid (22.46 g, 0.12 mol) and octadecyltrimethylammonium chloride (76.57 g, 0.22 mol) to solution d, stir while heating for about 2 hours, and centrifuge for 20 minutes. Filter, and place the solid obtained after filtration in a vacuum drying oven to dry to obtain 52.51 g of blue solid, which is the catalyst YG-36-2-011 coordinated with isoquinoline-5-carboxylic acid, and the catalyst yield reaches 87.21%. The nuclear magnetic characterization data are as follows:

[0113] 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).

[0114] Example 12

[0115] Step 1: Add 300 mL of deionized water to nickel sulfate (15.48 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 3 to obtain solution b. Continue stirring for about 50 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 1000 mL to obtain solution d.

[0116] Step 2: Heat solution d to 60°C, add 4-methylisoquinoline-5-carboxylic acid (22.46 g, 0.12 mol) and octadecyltrimethylammonium chloride (76.57 g, 0.22 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 58.12 g of white solid, which is the catalyst YG-36-2-012 coordinated with isoquinoline-5-carboxylic acid, and the catalyst yield reaches 93.55%. The nuclear magnetic characterization data are as follows:

[0117] 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).

[0118] Embodiment 13

[0119] Step 1: Add 300 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 60 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 1000 mL to obtain solution d.

[0120] Step 2: Heat solution d to 50°C, add 4-methylisoquinoline-5-carboxylic acid (22.46 g, 0.12 mol) and octadecyltrimethylammonium chloride (76.57 g, 0.22 mol) to solution d, stir while heating for about 2 hours, and centrifuge for 20 minutes. Filter, and place the solid obtained after filtration in a vacuum drying oven to dry to obtain 55.24 g of yellow solid, which is the catalyst YG-36-2-013 coordinated with isoquinoline-5-carboxylic acid, and the catalyst yield reaches 89.28%. The NMR characterization data are as follows:

[0121] 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).

[0122] Embodiment 14

[0123] Step 1: Add 300 mL of deionized water to nickel sulfate (15.48 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 3 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 1000 mL to obtain solution d.

[0124] Step 2: Heat solution d to 55°C, add 4-ethylisoquinoline-5-carboxylic acid (24.15 g, 0.12 mol) and octadecyltrimethylammonium chloride (76.57 g, 0.22 mol) to solution d, stir while heating for about 2 hours, and centrifuge for 20 minutes. Filter, and place the solid obtained after filtration in a vacuum drying oven to dry to obtain 57.10 g of yellow solid, which is the catalyst YG-36-2-014 coordinated with isoquinoline-5-carboxylic acid, and the catalyst yield reaches 90.34%. The nuclear magnetic characterization data are as follows:

[0125] 1H NMR(400MHz,DMSO-d6)δ8.83(s,1H),8.64(s,1H),8.52(d,1H),8.14(d,1H),8.01(s,1H),3.6 1(t,2H),3.48(s,9H),2.90-2.86(m,1H),1.76-1.72(m,2H),1.57-1.11(m,36H),0.90(t,3H).

[0126] Composite Catalyst Example

[0127] Embodiment 15

[0128] Step (1): Add 20.0 g of methanol to 10.0 g of ammonium bromide, and stir at room temperature until the solid is completely dissolved to obtain a mixture A;

[0129] Step (2): add 10.0 g of isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-001 to the mixture A of step (1), and heat at 60° C. with stirring for 30 min to obtain a mixture B;

[0130] Step (3): adding 0.5 g of cerium acetate to the mixture B formed in step (2) to obtain a mixture C;

[0131] Step (4): Add 0.1 g of phosphomolybdic acid to the mixture C formed in step (3), stir at 90° C. for 60 min, and obtain a total of 40.4 g of composite catalyst 1.

[0132] Example 16

[0133] Step (1): adding 20.0 g of acetonitrile to 10.0 g of hexadecyltrimethylammonium bromide, and stirring at room temperature until the solid is completely dissolved to obtain a mixture A;

[0134] Step (2): add 10.0 g of isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-002 to the mixture A of step (1), and heat at 60° C. with stirring for 30 min to obtain a mixture B;

[0135] Step (3): adding 0.5 g of cerium acetate to the mixture B formed in step (2) to obtain a mixture C;

[0136] Step (4): Add 0.1 g of phosphomolybdic acid to the mixture C formed in step (3), stir at 90° C. for 60 min, and obtain a total of 40.1 g of composite catalyst 2.

[0137] Embodiment 17

[0138] 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;

[0139] Step (2): add 10.0 g of isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-003 to the mixture A of step (1), and heat at 60° C. with stirring for 30 min to obtain a mixture B;

[0140] Step (3): adding 0.5 g of zirconium acetate to the mixture B formed in step (2) to obtain a mixture C;

[0141] Step (4): Add 0.1 g of phosphomolybdic acid to the mixture C formed in step (3), stir at 90° C. for 60 min, and obtain a total of 40.0 g of composite catalyst 3.

[0142] Embodiment 18

[0143] Step (1): Add 20.0 g of acetonitrile to 10.0 g of ammonium bromide, and stir at room temperature until the solid is completely dissolved to obtain a mixture A;

[0144] Step (2): add 10.0 g of isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-004 to the mixture A of step (1), and heat at 60° C. with stirring for 30 min to obtain a mixture B;

[0145] Step (3): adding 0.5 g of zirconium acetate to the mixture B formed in step (2) to obtain a mixture C;

[0146] Step (4): Add 0.1 g of phosphomolybdic acid to the mixture C formed in step (3), stir at 90° C. for 60 min, and obtain a total of 40.4 g of composite catalyst 4.

[0147] Embodiment 19

[0148] Step (1): Add 20.0 g of methanol to 10.0 g of phenyltrimethylammonium bromide, and stir at room temperature until the solid is completely dissolved to obtain a mixture A;

[0149] Step (2): add 10.0 g of isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-005 to the mixture A of step (1), and heat at 60° C. with stirring for 30 min to obtain a mixture B;

[0150] Step (3): adding 0.5 g of cerium acetate to the mixture B formed in step (2) to obtain a mixture C;

[0151] Step (4): Add 0.1 g of phosphomolybdic acid to the mixture C formed in step (3), stir at 90° C. for 60 min, and obtain a total of 39.4 g of composite catalyst 5.

[0152] Embodiment 20

[0153] Step (1): add 20.0 g of methanol to 10.0 g of phenyltrimethylammonium bromide, and stir at room temperature until the solid is completely dissolved to obtain a mixture A;

[0154] Step (2): add 10.0 g of isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-006 to the mixture A of step (1), and heat at 60° C. with stirring for 30 min to obtain a mixture B;

[0155] Step (3): adding 0.5 g of manganese acetate to the mixture B formed in step (2) to obtain a mixture C;

[0156] Step (4): Add 0.1 g of phosphomolybdic acid to the mixture C formed in step (3), stir at 90° C. for 60 min, and obtain a total of 39.7 g of composite catalyst 6.

[0157] Embodiment 21

[0158] Step (1): Add 20.0 g of methanol to 10.0 g of phenyltrimethylammonium bromide, and stir at room temperature until the solid is completely dissolved to obtain a mixture A;

[0159] Step (2): add 10.0 g of isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-007 to the mixture A of step (1), and heat at 60° C. with stirring for 30 min to obtain a mixture B;

[0160] Step (3): adding 0.5 g of magnesium acetate to the mixture B formed in step (2) to obtain a mixture C;

[0161] Step (4): Add 0.1 g of phosphotungstic acid to the mixture C formed in step (3), stir at 90° C. for 60 min, and obtain a total of 39.7 g of composite catalyst 7.

[0162] Embodiment 22

[0163] Step (1): Add 20.0 g of ethanol to 10.0 g of ammonium bromide, and stir at room temperature until the solid is completely dissolved to obtain a mixture A;

[0164] Step (2): add 10.0 g of isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-008 to the mixture A of step (1), and heat at 60° C. with stirring for 30 min to obtain a mixture B;

[0165] Step (3): adding 0.5 g of manganese acetate to the mixture B formed in step (2) to obtain a mixture C;

[0166] Step (4): Add 0.1 g of phosphomolybdic acid to the mixture C formed in step (3), and stir at 90° C. for 60 min to obtain a total of 40.1 g of composite catalyst 8.

[0167] Embodiment 23

[0168] Step (1): Add 20.0 g of ethanol to 10.0 g of ammonium bromide, and stir at room temperature until the solid is completely dissolved to obtain a mixture A;

[0169] Step (2): add 10.0 g of isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-009 to the mixture A of step (1), and heat at 60° C. with stirring for 30 min to obtain a mixture B;

[0170] Step (3): adding 0.5 g of magnesium acetate to the mixture B formed in step (2) to obtain a mixture C;

[0171] Step (4): Add 0.1 g of silicotungstic acid to the mixture C formed in step (3), stir at 90° C. for 60 min, and obtain a total of 40.2 g of composite catalyst 9.

[0172] Embodiment 24

[0173] Step (1): adding 20.0 g of acetonitrile to 10.0 g of N-hydroxyphthalimide, and stirring at room temperature until the solid is completely dissolved to obtain a mixture A;

[0174] Step (2): add 10.0 g of isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-010 to the mixture A of step (1), and heat at 60° C. with stirring for 30 min to obtain a mixture B;

[0175] Step (3): adding 0.5 g of cerium acetate to the mixture B formed in step (2) to obtain a mixture C;

[0176] Step (4): Add 0.1 g of phosphomolybdic acid to the mixture C formed in step (3), stir at 90° C. for 60 min, and obtain a total of 40.5 g of the composite catalyst 10.

[0177] Embodiment 25

[0178] Step (1): adding 20.0 g of methanol to 10.0 g of N-hydroxyphthalimide, and stirring at room temperature until the solid is completely dissolved to obtain a mixture A;

[0179] Step (2): add 10.0 g of isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-011 to the mixture A of step (1), and heat at 60° C. with stirring for 30 min to obtain a mixture B;

[0180] Step (3): adding 0.5 g of manganese acetate to the mixture B formed in step (2) to obtain a mixture C;

[0181] Step (4): Add 0.1 g of phosphomolybdic acid to the mixture C formed in step (3), and stir at 90° C. for 60 min to obtain a total of 40.0 g of composite catalyst 11.

[0182] Embodiment 26

[0183] Step (1): adding 20.0 g of ethanol to 10.0 g of N-hydroxyphthalimide, and stirring at room temperature until the solid is completely dissolved to obtain a mixture A;

[0184] Step (2): add 10.0 g of isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-012 to the mixture A of step (1), and heat at 60° C. with stirring for 30 min to obtain a mixture B;

[0185] Step (3): adding 0.5 g of zirconium acetate to the mixture B formed in step (2) to obtain a mixture C;

[0186] Step (4): Add 0.1 g of phosphotungstic acid to the mixture C formed in step (3), stir at 90° C. for 60 min, and obtain a total of 40.2 g of composite catalyst 12.

[0187] Embodiment 27

[0188] Step (1): adding 20.0 g of methanol to 10.0 g of N-hydroxyphthalimide, and stirring at room temperature until the solid is completely dissolved to obtain a mixture A;

[0189] Step (2): add 10.0 g of isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-013 to the mixture A of step (1), and heat at 60° C. with stirring for 30 min to obtain a mixture B;

[0190] Step (3): adding 0.5 g of cerium acetate to the mixture B formed in step (2) to obtain a mixture C;

[0191] Step (4): Add 0.1 g of silicotungstic acid to the mixture C formed in step (3), stir at 90° C. for 60 min, and obtain a total of 39.6 g of composite catalyst 13.

[0192] Embodiment 28

[0193] Step (1): Add 20.0 g of methanol to 10.0 g of ammonium bromide, and stir at room temperature until the solid is completely dissolved to obtain a mixture A;

[0194] Step (2): add 10.0 g of isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-014 to the mixture A of step (1), and heat at 60° C. with stirring for 30 min to obtain a mixture B;

[0195] Step (3): adding 0.5 g of manganese acetate to the mixture B formed in step (2) to obtain a mixture C;

[0196] Step (4): Add 0.1 g of silicotungstic acid to the mixture C formed in step (3), stir at 90° C. for 60 min, and obtain a total of 39.8 g of composite catalyst 14.

[0197] Application Examples

[0198] Embodiment 29

[0199] Add ammonium bromide (0.5g), isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-001 (0.5g), cerium acetate (0.25g), phosphomolybdic acid (0.05g), methanol (1.0g), acetic acid (100g), 4-methyl-1-naphthoic acid (50g) 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 100°C, vent it with air until the pressure inside the autoclave is 0.3MPa, vent it continuously, control the flow rate to 200-300mL / min, and end the reaction after three hours. The reaction solution is dark green, and the total weight of the reaction solution is 156.1g. Take 0.1g of the reaction solution, use toluene as the internal standard, take 0.1g of toluene, add 2g of acetonitrile to dilute, and inject the sample for testing. Substitute the test data into the internal standard curve to calculate that the remaining 4-methyl-1-naphthoic acid is 0.8g, and 1,4-naphthalenedicarboxylic acid is 55.8g. The conversion rate of 4-methyl-1-naphthoic acid is calculated to be 98.4%, and the selectivity of 1,4-naphthalenedicarboxylic acid is 97.7%.

[0200] Embodiment 30

[0201] Add hexadecyl trimethylammonium bromide (0.5g), isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-002 (0.5g), cerium acetate (0.25g), phosphomolybdic acid (0.05g), acetonitrile (1.0g), acetic acid (100g), 4-methyl-1-naphthoic acid (50g) 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 100°C, ventilate it with air until the pressure inside the autoclave is 0.3MPa, vent it continuously, control the flow rate to 200-300mL / min, and end the reaction after three hours. The reaction solution is dark green, and the total weight of the reaction solution is 155.4g. Take 0.1g of the reaction solution, use toluene as the internal standard, take 0.1g of toluene, add 2g of acetonitrile to dilute, and inject the sample for testing. Substitute the test data into the internal standard curve to calculate that the remaining 4-methyl-1-naphthoic acid is 1.1g, and 1,4-naphthalenedicarboxylic acid is 55.3g. The conversion rate of 4-methyl-1-naphthoic acid is calculated to be 97.8%, and the selectivity of 1,4-naphthalenedicarboxylic acid is 97.4%.

[0202] Embodiment 31

[0203] Add hexadecyl trimethylammonium bromide (0.5g), isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-003 (0.5g), zirconium acetate (0.25g), phosphomolybdic acid (0.05g), methanol (1.0g), acetic acid (100g), 4-methyl-1-naphthoic acid (50g) 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 100°C, vent it with air until the pressure inside the autoclave is 0.3MPa, vent it continuously, control the flow rate to 200-300mL / min, and end the reaction after three hours. The reaction solution is dark green, and the total weight of the reaction solution is 154.2g. Take 0.1g of the reaction solution, use toluene as the internal standard, take 0.1g of toluene, add 2g of acetonitrile to dilute, and inject the sample for testing. Substitute the test data into the internal standard curve to calculate that the remaining 4-methyl-1-naphthoic acid is 2.3g, and 1,4-naphthalenedicarboxylic acid is 54.1g. The calculated conversion rate of 4-methyl-1-naphthoic acid is 95.4%, and the selectivity of 1,4-naphthalenedicarboxylic acid is 97.7%.

[0204] Embodiment 32

[0205] Add ammonium bromide (0.5g), isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-004 (0.5g), zirconium acetate (0.25g), phosphomolybdic acid (0.05g), acetonitrile (1.0g), acetic acid (100g), 4-methyl-1-naphthoic acid (50g) 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 100°C, ventilate it with air until the pressure inside the autoclave is 0.3MPa, vent it continuously, control the flow rate to 200-300mL / min, and end the reaction after three hours. The reaction solution is dark green, and the total weight of the reaction solution is 154.6g. Take 0.1g of the reaction solution, use toluene as the internal standard, take 0.1g of toluene, add 2g of acetonitrile to dilute, and inject the sample for testing. Substitute the test data into the internal standard curve to calculate that the remaining 4-methyl-1-naphthoic acid is 1.5g, and 1,4-naphthalenedicarboxylic acid is 54.8g. The conversion rate of 4-methyl-1-naphthoic acid is calculated to be 97.0%, and the selectivity of 1,4-naphthalenedicarboxylic acid is 97.3%.

[0206] Embodiment 33

[0207] Add phenyltrimethylammonium bromide (0.5g), isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-005 (0.5g), cerium acetate (0.25g), phosphomolybdic acid (0.05g), methanol (1.0g), acetic acid (100g), 4-methyl-1-naphthoic acid (50g) 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 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 100°C, ventilate it with air until the pressure inside the autoclave is 0.3MPa, vent it continuously, control the flow rate to 200-300mL / min, and end the reaction after three hours. The reaction solution is dark green, and the total weight of the reaction solution is 155.1g. Take 0.1g of the reaction solution, use toluene as the internal standard, take 0.1g of toluene, add 2g of acetonitrile to dilute, and inject the sample for testing. Substitute the test data into the internal standard curve to calculate that the remaining 4-methyl-1-naphthoic acid is 1.4g, and 1,4-naphthalenedicarboxylic acid is 55.1g. The calculated conversion rate of 4-methyl-1-naphthoic acid is 97.2%, and the selectivity of 1,4-naphthalenedicarboxylic acid is 97.7%.

[0208] Embodiment 34

[0209] Add phenyltrimethylammonium bromide (0.5g), isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-006 (0.5g), manganese acetate (0.25g), phosphomolybdic acid (0.05g), methanol (1.0g), acetic acid (100g), 4-methyl-1-naphthoic acid (50g) 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 100°C, ventilate it with air until the pressure inside the autoclave is 0.3MPa, vent it continuously, control the flow rate to 200-300mL / min, and end the reaction after three hours. The reaction solution is dark green, and the total weight of the reaction solution is 154.3g. Take 0.1g of the reaction solution, use toluene as the internal standard, take 0.1g of toluene, add 2g of acetonitrile to dilute, and inject the sample for testing. Substitute the test data into the internal standard curve to calculate that the remaining 4-methyl-1-naphthoic acid is 1.4g, and 1,4-naphthalenedicarboxylic acid is 54.6g. The calculated conversion rate of 4-methyl-1-naphthoic acid is 97.2%, and the selectivity of 1,4-naphthalenedicarboxylic acid is 96.8%.

[0210] Embodiment 35

[0211] Add phenyltrimethylammonium bromide (0.5g), isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-007 (0.5g), magnesium acetate (0.25g), phosphotungstic acid (0.05g), methanol (1.0g), acetic acid (100g), 4-methyl-1-naphthoic acid (50g) 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 100°C, vent it with air until the pressure inside the autoclave is 0.3MPa, vent it continuously, control the flow rate to 200-300mL / min, and end the reaction after three hours. The reaction solution is dark green, and the total weight of the reaction solution is 152.1g. Take 0.1g of the reaction solution, use toluene as the internal standard, take 0.1g of toluene, add 2g of acetonitrile to dilute, and inject the sample for testing. Substitute the test data into the internal standard curve to calculate that 1.8g of 4-methyl-1-naphthoic acid remains, 52.1g of 1,4-naphthalenedicarboxylic acid, and the conversion rate of 4-methyl-1-naphthoic acid is calculated to be 96.4%, and the selectivity of 1,4-naphthalenedicarboxylic acid is 93.1%.

[0212] Embodiment 36

[0213] Add ammonium bromide (0.5g), isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-008 (0.5g), manganese acetate (0.25g), phosphotungstic acid (0.05g), ethanol (1.0g), acetic acid (100g), 4-methyl-1-naphthoic acid (50g) 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 100°C, ventilate it with air until the pressure inside the autoclave is 0.3MPa, vent it continuously, control the flow rate to 200-300mL / min, and end the reaction after three hours. The reaction solution is dark green, and the total weight of the reaction solution is 152.0g. Take 0.1g of the reaction solution, use toluene as the internal standard, take 0.1g of toluene, add 2g of acetonitrile to dilute, and inject the sample for testing. Substitute the test data into the internal standard curve to calculate that the remaining 4-methyl-1-naphthoic acid is 2.0g, and 1,4-naphthalenedicarboxylic acid is 53.6g. The calculated conversion rate of 4-methyl-1-naphthoic acid is 96.0%, and the selectivity of 1,4-naphthalenedicarboxylic acid is 96.2%.

[0214] Embodiment 37

[0215] Add ammonium bromide (0.5g), isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-009 (0.5g), magnesium acetate (0.25g), silicotungstic acid (0.05g), ethanol (1.0g), acetic acid (100g), 4-methyl-1-naphthoic acid (50g) 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 100°C, ventilate it with air until the pressure inside the autoclave is 0.3MPa, vent it continuously, control the flow rate to 200-300mL / min, and end the reaction after three hours. The reaction solution is dark green, and the total weight of the reaction solution is 151.6g. Take 0.1g of the reaction solution, use toluene as the internal standard, take 0.1g of toluene, add 2g of acetonitrile to dilute, and inject the sample for testing. Substitute the test data into the internal standard curve to calculate that the remaining 4-methyl-1-naphthoic acid is 0.8g, and 1,4-naphthalenedicarboxylic acid is 54.2g. The conversion rate of 4-methyl-1-naphthoic acid is calculated to be 98.4%, and the selectivity of 1,4-naphthalenedicarboxylic acid is 94.9%.

[0216] Embodiment 38

[0217] N-hydroxyphthalimide (0.5g), catalyst YG-36-2-010 (0.5g) coordinated with isoquinoline-5-carboxylic acid, cerium acetate (0.25g), phosphomolybdic acid (0.05g), acetonitrile (1.0g), acetic acid (100g), 4-methyl-1-naphthoic acid (50g) 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 100°C, and air was passed through until the pressure inside the autoclave was 0.3MPa. The air was passed through continuously, and the flow rate was controlled to be 200-300mL / min. The reaction was terminated after three hours. The reaction solution was dark green, and the total weight of the reaction solution was weighed to be 152.6g. Take 0.1g of the reaction solution, use toluene as the internal standard, take 0.1g of toluene, add 2g of acetonitrile to dilute, and inject the sample for testing. Substitute the test data into the internal standard curve to calculate that the remaining 4-methyl-1-naphthoic acid is 2.5g, and 1,4-naphthalenedicarboxylic acid is 53.8g. The conversion rate of 4-methyl-1-naphthoic acid is calculated to be 95.0%, and the selectivity of 1,4-naphthalenedicarboxylic acid is 97.6%.

[0218] Embodiment 39

[0219] N-hydroxyphthalimide (0.5g), isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-011 (0.5g), manganese acetate (0.25g), phosphomolybdic acid (0.05g), methanol (1.0g), acetic acid (100g), 4-methyl-1-naphthoic acid (50g) 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 100°C, and air was passed through until the pressure inside the autoclave was 0.3MPa. The air was passed through continuously, and the flow rate was controlled to be 200-300mL / min. The reaction was terminated after three hours. The reaction solution was dark green, and the total weight of the reaction solution was weighed to be 154.3g. Take 0.1g of the reaction solution, use toluene as the internal standard, take 0.1g of toluene, add 2g of acetonitrile to dilute, and inject the sample for testing. Substitute the test data into the internal standard curve to calculate that the remaining 4-methyl-1-naphthoic acid is 2.6g, and 1,4-naphthalenedicarboxylic acid is 53.1g. The calculated conversion rate of 4-methyl-1-naphthoic acid is 94.8%, and the selectivity of 1,4-naphthalenedicarboxylic acid is 96.5%.

[0220] Embodiment 40

[0221] N-hydroxyphthalimide (0.5g), isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-012 (0.5g), zirconium acetate (0.25g), silicotungstic acid (0.05g), ethanol (1.0g), acetic acid (100g), 4-methyl-1-naphthoic acid (50g) 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 100°C, and air was passed through until the pressure inside the autoclave was 0.3MPa. The air was passed through continuously, and the flow rate was controlled to be 200-300mL / min. The reaction was terminated after three hours. The reaction solution was dark green, and the total weight of the reaction solution was weighed to be 152.6g. Take 0.1g of the reaction solution, use toluene as the internal standard, take 0.1g of toluene, add 2g of acetonitrile to dilute, and inject the sample for testing. Substitute the test data into the internal standard curve to calculate that 1.8g of 4-methyl-1-naphthoic acid remains, 54.5g of 1,4-naphthalenedicarboxylic acid, and the conversion rate of 4-methyl-1-naphthoic acid is calculated to be 96.4%, and the selectivity of 1,4-naphthalenedicarboxylic acid is 97.4%.

[0222] Embodiment 41

[0223] N-hydroxyphthalimide (0.5g), isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-013 (0.5g), cerium acetate (0.25g), silicotungstic acid (0.05g), methanol (1.0g), acetic acid (100g), 4-methyl-1-naphthoic acid (50g) 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 100°C, and air was passed through until the pressure inside the autoclave was 0.3MPa. The air was passed through continuously, and the flow rate was controlled to be 200-300mL / min. The reaction was terminated after three hours. The reaction solution was dark green, and the total weight of the reaction solution was weighed to be 153.8g. Take 0.1g of the reaction solution, use toluene as the internal standard, take 0.1g of toluene, add 2g of acetonitrile to dilute, and inject the sample for testing. Substitute the test data into the internal standard curve to calculate that 1.7g of 4-methyl-1-naphthoic acid remains, 54.6g of 1,4-naphthalenedicarboxylic acid, and the conversion rate of 4-methyl-1-naphthoic acid is calculated to be 96.6%, and the selectivity of 1,4-naphthalenedicarboxylic acid is 97.4%.

[0224] Embodiment 42

[0225] Add ammonium bromide (0.5g), isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-014 (0.5g), manganese acetate (0.25g), silicotungstic acid (0.05g), methanol (1.0g), acetic acid (100g), 4-methyl-1-naphthoic acid (50g) 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 100°C, vent it with air until the pressure inside the autoclave is 0.3MPa, vent it continuously, control the flow rate to 200-300mL / min, and end the reaction after three hours. The reaction solution is dark green, and the total weight of the reaction solution is 154.2g. Take 0.1g of the reaction solution, use toluene as the internal standard, take 0.1g of toluene, add 2g of acetonitrile to dilute, and inject the sample for testing. Substitute the test data into the internal standard curve to calculate that the remaining 4-methyl-1-naphthoic acid is 1.5g, and 1,4-naphthalenedicarboxylic acid is 53.9g. The conversion rate of 4-methyl-1-naphthoic acid is calculated to be 97.0%, and the selectivity of 1,4-naphthalenedicarboxylic acid is 95.7%.

[0226] Comparative Example

[0227] The experimental operation method of the comparative example is consistent with that of Example 29, except for the amount of material added. The material addition amount and the experimental results are specifically shown in Table 1.

[0228] Table 1 Material addition amount and experimental results of Example 29 and Comparative Example

[0229]

[0230] Compared with the comparative example 8 in which no isoquinoline-5-carboxylic acid coordinated catalyst was added, the conversion rate of 4-methyl-1-naphthoic acid and the selectivity of 1,4-naphthalenedicarboxylic acid in Example 29 were both optimal, indicating that the isoquinoline-5-carboxylic acid coordinated catalyst disclosed in the present invention can effectively catalyze the oxidation of 4-methyl-1-naphthoic acid to produce 1,4-naphthalenedicarboxylic acid.

[0231] Combined with comparative examples 1-7, it can be seen that after the selective removal of the co-catalyst, regulator, protective agent and solvent, the reaction effect is affected to varying degrees, indicating that the combined use of the above components can have a synergistic effect on catalysis, can better improve the reaction selectivity, and the overall reaction steps are simple and easy to operate, which helps to reduce raw material costs or post-processing costs.

[0232] 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.

[0233] 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 isoquinoline-5-carboxylic acid, characterized in that: The general chemical formula of the catalyst is shown in formula (I): wherein B is selected from the group consisting of lithium ion, sodium ion, potassium ion, magnesium ion, calcium ion, ammonium ion, dodecyldimethylbenzylammonium ion, dodecyltrimethylammonium ion, octadecyltrimethylammonium ion, octadecyldimethylbenzylammonium ion, octyltributylphosphine ion, tetrabutylphosphine ion, tributylethylphosphine ion, tributylhexylphosphine ion, tetramethylammonium ion, tetraethylammonium ion, tetrabutylammonium ion, benzyltrimethylammonium ion, benzyltriphenylphosphine ion and benzyltriethylammonium ion; M is selected from Cr, Mo, V, W, Cu, Fe, Co, Ni and Zr; R is selected from C1~C 10 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 isoquinoline-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 3-4, and then add peroxide to obtain a metal peroxide solution; Alkyl-substituted isoquinoline-5-carboxylic acid and salt are added to the metal peroxide solution, filtered, and dried to obtain an isoquinoline-5-carboxylic acid coordinated catalyst.

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

4. The method for preparing the catalyst coordinated by isoquinoline-5-carboxylic acid according to claim 2, characterized in that: The peroxide is selected from hydrogen peroxide and urea peroxide.

5. The method for preparing the catalyst coordinated by isoquinoline-5-carboxylic acid according to claim 2, characterized in that: The alkyl-substituted isoquinoline-5-carboxylic acid is selected from 4-methylisoquinoline-5-carboxylic acid, 4-ethylisoquinoline-5-carboxylic acid, 4-propylisoquinoline-5-carboxylic acid, 4-isopropylisoquinoline-5-carboxylic acid, 4-n-butylisoquinoline-5-carboxylic acid, and 4-tert-butylisoquinoline-5-carboxylic acid.

6. The method for preparing the catalyst coordinated by isoquinoline-5-carboxylic 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, magnesium acetate, calcium chloride, ammonium bromide, ammonium acetate, dodecyldimethylbenzylammonium bromide, dodecyltrimethylammonium chloride, octadecyldimethylbenzylammonium bromide, octyltributylphosphonium bromide, tributylethylphosphonium bromide, tetrabutylphosphonium bromide, tributylhexylphosphonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltriphenylphosphonium bromide, benzyltrimethylammonium chloride or benzyltriethylammonium chloride.

7. A composite catalyst, characterized in that The invention comprises the catalyst coordinated by isoquinoline-5-carboxylic acid 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 isoquinoline-5-carboxylic acid to the cocatalyst is 100:(1-200); 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, copper sulfate, copper acetate, copper nitrate, magnesium sulfate, magnesium acetate, zinc acetate, zinc sulfate, sodium molybdate, potassium 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 isoquinoline-5-carboxylic acid coordinated catalyst to the regulator is 100: (1-200); The regulator is selected from phosphomolybdic acid, phosphotungstic acid, tetrabutylammonium bromide, boric acid, silicotungstic acid 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 isoquinoline-5-carboxylic acid to the protective agent is 100:(5-200); The protective agent is selected from sodium acetate, ammonium bromide, hexadecyltrimethylammonium bromide, phenyltrimethylammonium bromide, sodium molybdate and N-hydroxyphthalimide.

11. The composite catalyst according to claim 7, characterized in that It also includes a solvent, wherein the weight ratio of the catalyst coordinated by isoquinoline-5-carboxylic acid to the solvent is 100:(5-1000); 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 steps include: Mix the protective agent and the solvent to obtain a solution; Add the isoquinoline-5-carboxylic acid coordinated catalyst according to claim 1 to the solution, and stir at 40 to 90° C. for 20 to 60 minutes; Then add the auxiliary catalyst and ultrasonicate at 40-90°C for 20-60min; Then add a regulator and stir at 40-90°C for 30-60 minutes to obtain a composite catalyst.

13. Use of the isoquinoline-5-carboxylic acid coordinated catalyst according to claim 1 or the composite catalyst according to any one of claims 7 to 11 in the reaction of oxidizing 4-methyl-1-naphthoic acid to prepare 1,4-naphthalenedicarboxylic acid.

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