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 shown in the specification, and the composite catalyst comprises the isoquinoline-5-formic acid coordinated catalyst, an auxiliary catalyst, 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] This invention belongs to the field of organic catalysis technology, specifically relating to an isoquinoline-5-carboxylic acid coordinated catalyst, a composite catalyst, a preparation method, and its application. Background Technology

[0002] 1,4-Naphthalenedicarboxylic acid, also known as 1,4-naphthalenedicarboxylic acid, is widely used in industries such as dyes, fluorescent whitening agents, high-adhesion coatings, and plastics. 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 some applications in the pharmaceutical field.

[0003] The synthesis of 1,4-naphthalenedicarboxylic acid can be categorized based on the starting material, including: direct oxidation of 1,4-dimethylnaphthalene; a three-step synthesis of 1,4-naphthalenedicarboxylic acid via bromination, cyano substitution, and hydrolysis of naphthalene; the naphthalene / 1-chloromethylnaphthalene method; the 1-methyl-4-hydroxymethylnaphthalene method; and a three-step process from 1-methylnaphthalene to 1,4-naphthalenedicarboxylic acid. Domestic manufacturers produce 1,4-naphthalenedicarboxylic acid through a three-step unit reaction of 1-methylnaphthalene. Using 1-methylnaphthalene as a raw material, a Friedel-Crafts reaction is conducted to generate 1-methyl-4-acetylnaphthalene, which is then oxidized with sodium hypochlorite to produce 4-methyl-1-naphthoic acid. 4-methyl-1-naphthoic acid is then oxidized with potassium permanganate to produce 1,4-naphthalenedicarboxylic acid. However, the oxidation of 4-methyl-1-naphthoic acid using potassium permanganate requires more than four times the amount of potassium permanganate, resulting in low reaction efficiency, large amounts of waste residue and wastewater, low production efficiency, and a huge amount of waste.

[0004] Chinese patent CN117820107A discloses a method for obtaining 1,4-naphthalenedicarboxylic acid by using dichloromethane, α-methylnaphthalene, and aluminum trichloride as starting materials and undergoing a series of six-step reactions and post-treatments. This method is lengthy and complex, and involves the use of acetyl chloride, benzene, sodium hypochlorite, and large amounts of acids and alkalis, resulting in high raw material costs or post-treatment costs.

[0005] Chinese patent CN112778116A discloses a method using 1-bromonaphthalene as a starting material, which undergoes a Friedel-Crafts reaction with acetyl chloride to generate 4-bromo-1-acetylnaphthalene; this is then oxidized 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 a copper 4-cyanonaphthoate complex; the copper 4-cyanonaphthoate complex is then hydrolyzed with an alkaline solution to obtain 1,4-naphthoic acid. This method also involves relatively complex procedures and uses raw materials with high costs or high post-processing costs, such as acetyl chloride, hypochlorite, cuprous cyanide, and potassium iodide.

[0006] Experimental investigation revealed that the reported synthesis methods all suffer from drawbacks such as lengthy reaction steps, complex operation, and high raw material or post-processing costs when used in the preparation of 1,4-naphthalenedicarboxylic acid, and therefore cannot be applied to the industrial-scale production of 1,4-naphthalenedicarboxylic acid.

[0007] The information disclosed in this background section is intended only to enhance the understanding of the overall background of the invention and should not be construed as an admission or in any way implying that the information constitutes prior art known to those skilled in the art. Summary of the Invention

[0008] The purpose of this invention is to provide a catalyst, a composite catalyst, a preparation method, and an application for isoquinoline-5-carboxylic acid coordination, which is suitable for the industrial production of 1,4-naphthalenedicarboxylic acid by oxidizing 4-methyl-1-naphthoic acid.

[0009] To achieve the above objectives, a specific embodiment of the present invention provides the following technical solution:

[0010] A catalyst coordinated with isoquinoline-5-carboxylic acid, the catalyst having the general chemical formula shown in formula (I):

[0011] (I)

[0012] Wherein, B is selected from lithium ion, sodium ion, potassium ion, magnesium ion, calcium ion, ammonium ion, dodecyl dimethyl benzyl ammonium ion, dodecyl trimethyl ammonium ion, octadecyl trimethyl ammonium ion, octadecyl dimethyl benzyl ammonium 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, and W;

[0014] R is selected from C1 to C2. 10 alkyl;

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

[0016] y is selected from integers between 1 and 40.

[0017] Another specific embodiment of the present invention provides the following technical solution:

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

[0019] The metal compound is dissolved in deionized water, the pH of the solution is adjusted to 3-4, and then peroxide is added to obtain a metal peroxide solution.

[0020] An alkyl-substituted isoquinoline-5-carboxylic acid and its salt were added to a metal peroxide solution, filtered, and dried to obtain a catalyst coordinated with isoquinoline-5-carboxylic acid.

[0021] In one or more embodiments of the present invention, the metal compound is selected from sodium tungstate, sodium molybdate, and sodium chromate.

[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, dodecyl dimethyl benzyl ammonium bromide, dodecyltrimethylammonium chloride, octadecyl dimethyl benzyl ammonium bromide, octyltributylphosphine bromide, tributylethylphosphine bromide, tetrabutylphosphine bromide, tributylhexylphosphine bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltriphenylphosphine bromide, benzyltrimethylammonium chloride, or benzyltriethylammonium chloride.

[0025] Another specific embodiment of the present invention provides the following technical solution:

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

[0027] In one or more embodiments of the present invention, a co-catalyst is further included, wherein the weight ratio of the isoquinoline-5-carboxylic acid-coordinated catalyst to the co-catalyst is 100:(1-200).

[0028] The co-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, wherein the weight ratio of the catalyst coordinated with 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 vanadate.

[0031] In one or more embodiments of the present invention, a protective agent is further included, wherein the weight ratio of the isoquinoline-5-carboxylic acid coordinated catalyst 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, wherein the weight ratio of the isoquinoline-5-carboxylic acid coordinated catalyst to the solvent is 100:(5-1000).

[0034] The solvent is selected from 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 the following technical solution:

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

[0037] Mix the protective agent and solvent thoroughly 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 min;

[0039] Add a co-catalyst and sonicate at 40–90°C for 20–60 min;

[0040] Add a regulator and stir at 40–90°C for 30–60 min to obtain a composite catalyst.

[0041] Another specific embodiment of the present invention provides the following technical solution:

[0042] Application of a catalyst coordinated with isoquinoline-5-carboxylic acid or a composite catalyst thereof in the oxidation of 4-methyl-1-naphthoic acid to prepare 1,4-naphthoic 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 high selectivity, can be reused repeatedly, have low cost, and can effectively catalyze the oxidation of 4-methyl-1-naphthoic acid to prepare 1,4-naphthoic acid. Detailed Implementation

[0044] To enable those skilled in the art to better understand the technical solutions of this invention, the technical solutions in the embodiments of this invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of this invention.

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

[0046] (I)

[0047] Wherein, B is selected from lithium ion, sodium ion, potassium ion, magnesium ion, calcium ion, ammonium ion, dodecyl dimethyl benzyl ammonium ion, dodecyl trimethyl ammonium ion, octadecyl trimethyl ammonium ion, octadecyl dimethyl benzyl ammonium 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, and W; R is selected from C1 to C2. 10 Alkyl; x is an integer selected from 1 to 20; y is an integer selected from 1 to 40.

[0048] More 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 and Mo; R is selected from C1 to 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 and Mo; R is selected from methyl, ethyl and isopropyl; x is 1; y is 1 or 2.

[0050] By selecting the above types of B, M, and R, and simultaneously limiting the values ​​of x and y, the obtained isoquinoline-5-carboxylic acid coordinated catalyst can selectively catalyze the oxidation of 4-methyl-1-naphthoic acid to 1,4-naphthoic acid. It exhibits high selectivity, high activity, and can be reused repeatedly 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, including steps 1-2.

[0052] Step 1: Add the metal compound to deionized water. After the metal compound is completely dissolved, the solution is obtained. Adjust the pH of the solution to 3-4, and then add the peroxide to obtain a metal peroxide solution.

[0053] Specifically, the metal compounds are selected from sodium chromate and sodium molybdate, the peroxides are selected from hydrogen peroxide and urea peroxide, and the pH of the solution is adjusted using hydrochloric acid or sulfuric acid.

[0054] In this step, the purpose of adding peroxide is to keep the metal in a high valence state and prevent it from being reduced by other substances, and the purpose of adding deionized water is to prevent crystallization in subsequent operations, which would cause the reaction solution to become viscous.

[0055] Step 2: Add alkyl-substituted isoquinoline-5-carboxylic acid and salt to the metal peroxide solution, filter, and dry to obtain the catalyst coordinated with isoquinoline-5-carboxylic acid.

[0056] 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, octyltributylphosphine bromide, tetrabutylphosphine bromide, hexyltributylphosphine bromide, tributylethylphosphine bromide, tetrabutylphosphine bromide, tributylhexylphosphine bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltriphenylphosphine bromide, benzyltrimethylammonium chloride, or benzyltriethylammonium chloride.

[0057] In this step, alkyl-substituted isoquinoline-5-carboxylic acid and a quaternary ammonium salt are added. The quaternary ammonium salt first reacts with the alkyl-substituted isoquinoline-5-carboxylic acid to obtain the corresponding coordination structure. The purpose of stirring, centrifugation, and other operations is to induce crystallization and obtain the coordinated catalyst structure.

[0058] Another specific embodiment of the present invention provides a composite catalyst, comprising the above-mentioned isoquinoline-5-carboxylic acid coordinated catalyst, co-catalyst, regulator, protectant and solvent, wherein the weight ratio of the isoquinoline-5-carboxylic acid coordinated catalyst, co-catalyst, regulator, protectant and solvent is 100:(1-200):(1-200):(5-200):(5-1000).

[0059] Specifically, the co-catalysts are 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 regulators are selected from phosphomolybdic acid, phosphotungstic acid, tetrabutylammonium bromide, boric acid, silicotungstic acid, and phosphomolybdic vanadate. The protecting agents are selected from sodium acetate, ammonium bromide, hexadecyltrimethylammonium bromide, phenyltrimethylammonium bromide, sodium molybdate, and N-hydroxyphthalimide. The solvents are 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, protecting agents, and solvents, while simultaneously controlling their weight ratios, helps to improve catalyst activity, optimize reaction conditions, and enhance reaction efficiency and selectivity.

[0060] Preferably, the weight ratio of the catalyst, co-catalyst, regulator, protective agent, and solvent coordinated with isoquinoline-5-carboxylic acid is 100:(1-50):(1-50):(10-100):(100-500). The catalyst coordinated with isoquinoline-5-carboxylic acid is selected from alkyl-substituted catalysts coordinated with isoquinoline-5-carboxylic acid with Cr or Mo as the central metal. The co-catalyst 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. The solvent is selected from methanol, ethanol, and acetonitrile.

[0061] Another specific embodiment of the present invention provides a method for preparing the above-mentioned composite catalyst, comprising the following steps: preparing raw materials, including a catalyst coordinated with isoquinoline-5-carboxylic acid, a co-catalyst, a regulator, a protective agent, and a solvent;

[0062] Add the protective agent to the organic solvent, mix well, and you will get solution 1;

[0063] Add the catalyst coordinated with isoquinoline-5-carboxylic acid to solution 1, and stir at 40-90 °C for 20-60 minutes to obtain solution 2;

[0064] Add a co-catalyst to solution 2 and sonicate at 40–90 °C for 20–60 minutes to obtain solution 3;

[0065] Add a regulator to solution 3 and stir at 40–90 °C for 30–60 minutes to obtain a composite catalyst.

[0066] Another specific embodiment of the present invention provides the application of the above-mentioned isoquinoline-5-carboxylic acid coordinated catalyst or composite catalyst in the reaction of oxidizing 4-methyl-1-naphthoic acid to prepare 1,4-naphthoic acid.

[0067] Specifically, 4-methyl-1-naphthoic acid is dissolved in a solvent, and a catalyst or composite catalyst coordinated with isoquinoline-5-carboxylic acid is added to it. Air is introduced at a rate of 200-1000 ml / s, and the reaction is stirred at 80-150°C for 2-8 hours.

[0068] Taking the composite catalyst as an example, the amount of composite catalyst added is 0.1 to 5% of the weight of 4-methyl-1-naphthoic acid.

[0069] Preferably, the solvent is acetic acid, the air flow rate is 200-500 ml / s, the reaction temperature is 90-120℃, the reaction time is 3-6 h, and the amount of composite catalyst added is 0.5-2% of the weight of 4-methyl-1-naphthoic acid.

[0070] The present invention will be further described in detail below with reference to specific embodiments.

[0071] Examples of catalysts coordinated with isoquinoline-5-carboxylic acid

[0072] Example 1

[0073] Step 1: At room temperature, add 300 mL of deionized water to sodium chromate (16.2 g, 0.1 mol) solid. After the solid is completely dissolved, obtain solution a. Add dilute sulfuric acid dropwise to solution a until the pH reaches 3, obtaining solution b. Continue stirring for about 30 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 1000 mL, obtaining solution d.

[0074] Step 2: Heat solution d to 50 °C, add 22.46 g (0.12 mol) of 4-methylisoquinoline-5-carboxylic acid and 76.57 g (0.22 mol) of octadecyltrimethylammonium chloride to solution d, and stir while heating for about 2 h. Then centrifuge for 20 min. Filter, and dry the filtered solid in a vacuum drying oven to obtain 52.83 g of purple-red solid. This purple-red solid is the catalyst YG-36-2-001 coordinated with isoquinoline-5-carboxylic acid, with a catalyst yield of 84.62%. NMR characterization data are as follows:

[0075] 1H NMR (400 MHz, 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).

[0076] Example 2

[0077] Step 1: At room temperature, add 300 mL of deionized water to sodium chromate (16.2 g, 0.1 mol) solid. After the solid is completely dissolved, solution a is obtained. Add dilute sulfuric acid dropwise to solution a until the pH reaches 3, obtaining solution b. Continue stirring for about 60 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 1000 mL, obtaining solution d.

[0078] Step 2: Heat solution d to 80 °C, add 24.15 g (0.12 mol) of 4-ethylisoquinoline-5-carboxylic acid and 76.57 g (0.22 mol) of octadecyltrimethylammonium chloride to solution d, and stir while heating for about 1 h, then centrifuge for 20 min. Filter, and dry the filtered solid in a vacuum drying oven to obtain 44.12 g of a purple-red solid. This purple-red solid is the catalyst YG-36-2-002, which is coordinated with isoquinoline-5-carboxylic acid, with a catalyst yield of 90.82%. NMR characterization data are as follows:

[0079] 1H NMR (400 MHz, DMSO-d6) δ 8.84 (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).

[0080] Example 3

[0081] Step 1: At room temperature, add 300 mL of deionized water to sodium chromate (16.2 g, 0.1 mol) solid. After the solid is completely dissolved, solution a is obtained. Add dilute sulfuric acid dropwise to solution a until the pH reaches 3, obtaining solution b. Continue stirring for about 60 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 1000 mL, obtaining solution d.

[0082] Step 2: Heat solution d to 60 °C, add 25.83 g (0.12 mol) of 4-isopropylisoquinoline-5-carboxylic acid and 76.57 g (0.22 mol) of octadecyltrimethylammonium chloride to solution d, and stir while heating for about 1 h, then centrifuge for 20 min. Filter, and dry the filtered solid in a vacuum drying oven to obtain 48.62 g of a purple-red solid. This purple-red solid is the catalyst YG-36-2-003, which is coordinated with isoquinoline-5-carboxylic acid, with a catalyst yield of 88.51%. NMR characterization data are as follows:

[0083] 1H NMR (400 MHz, DMSO-d6) δ 8.84 (s, 1H), 8.65 (s, 1H), 8.54 (d, 1H), 8.17 (d, 1H), 8.03 (s, 1H), 3.61 (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).

[0084] Example 4

[0085] Step 1: At room temperature, add 300 mL of deionized water to sodium molybdate (20.59 g, 0.1 mol) solid. After the solid is completely dissolved, solution a is obtained. Add dilute sulfuric acid dropwise to solution a until the pH reaches 3, obtaining solution b. Continue stirring for about 30 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 1000 mL, obtaining solution d.

[0086] Step 2: Heat solution d to 60 °C, add 22.46 g (0.12 mol) of 4-methylisoquinoline-5-carboxylic acid and 76.57 g (0.22 mol) of octadecyltrimethylammonium chloride to solution d, and stir while heating for about 2 h. Then centrifuge for 20 min. Filter, and dry the filtered solid in a vacuum drying oven to obtain 52.51 g of blue solid. This blue solid is the isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-004, with a catalyst yield of 87.21%. NMR characterization data are as follows:

[0087] 1H NMR (400 MHz, DMSO-d6) δ 8.88 (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).

[0088] Composite catalyst examples

[0089] Example 5

[0090] 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 mixture A;

[0091] Step (2): Add 10.0 g of isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-001 to mixture A in step (1), stir and heat at 60 ℃ for 30 min to obtain mixture B;

[0092] Step (3): Add 0.5 g of manganese acetate to mixture B formed in step (2) to obtain mixture C;

[0093] 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.

[0094] Example 6

[0095] 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 mixture A;

[0096] Step (2): Add 10.0 g of isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-002 to mixture A in step (1), stir and heat at 60 ℃ for 30 min to obtain mixture B;

[0097] Step (3): Add 0.5 g of magnesium acetate to mixture B formed in step (2) to obtain mixture C;

[0098] Step (4): Add 0.1 g of silicotungstic acid to the mixture C formed in step (3), and stir at 90°C for 60 min to obtain a total of 40.2 g of composite catalyst 9.

[0099] Example 7

[0100] Step (1): Add 20.0 g of acetonitrile to 10.0 g of N-hydroxyphthalimide and stir at room temperature until the solid is completely dissolved to obtain mixture A;

[0101] Step (2): Add 10.0 g of isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-003 to mixture A in step (1), stir and heat at 60 ℃ for 30 min to obtain mixture B;

[0102] Step (3): Add 0.5 g of cerium acetate to mixture B formed in step (2) to obtain mixture C;

[0103] 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 40.5 g of composite catalyst 10.

[0104] Example 8

[0105] Step (1): Add 20.0 g of methanol to 10.0 g of N-hydroxyphthalimide and stir at room temperature until the solid is completely dissolved to obtain mixture A;

[0106] Step (2): Add 10.0 g of isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-004 to mixture A in step (1), stir and heat at 60 ℃ for 30 min to obtain mixture B;

[0107] Step (3): Add 0.5 g of manganese acetate to mixture B formed in step (2) to obtain mixture C;

[0108] 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.

[0109] Application Examples

[0110] Example 9

[0111] Ammonium bromide (0.5 g), isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-001 (0.5 g), manganese acetate (0.25 g), phosphotungstic acid (0.05 g), ethanol (1.0 g), acetic acid (100 g), and 4-methyl-1-naphthoic acid (50 g) were added sequentially to a 250 mL titanium high-pressure reactor. After the reactor was assembled, nitrogen gas was introduced until the internal pressure reached 0.5 MPa and maintained for 15 minutes. A pressure drop of no more than 5% was considered a good airtightness of the reactor. After purging the nitrogen, the temperature was raised to 100 °C, and air was introduced until the internal pressure reached 0.3 MPa. Air was continuously introduced at a flow rate of 200-300 mL / min, and the reaction was stopped after three hours. The reaction solution was dark green, and the total weight of the reaction solution was 152.0 g. 0.1 g of the reaction solution was taken, and toluene was used as an internal standard. 0.1 g of toluene was diluted with 2 g of acetonitrile and injected for analysis. Substituting the test data into the internal standard curve, the remaining 4-methyl-1-naphthoic acid was 2.0 g, and the 1,4-naphthoic acid was 53.6 g. The conversion rate of 4-methyl-1-naphthoic acid was 96.0%, and the selectivity of 1,4-naphthoic acid was 96.2%.

[0112] Example 10

[0113] Ammonium bromide (0.5 g), isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-002 (0.5 g), magnesium acetate (0.25 g), silicotungstic acid (0.05 g), ethanol (1.0 g), acetic acid (100 g), and 4-methyl-1-naphthoic acid (50 g) were added sequentially to a 250 mL titanium high-pressure reactor. After the reactor was assembled, nitrogen gas was introduced until the internal pressure reached 0.5 MPa and maintained for 15 minutes. If the pressure drop did not exceed 5%, the reactor was considered to have good airtightness. After purging the nitrogen gas, the temperature was raised to 100 °C, and air was introduced until the internal pressure reached 0.3 MPa. Air was continuously introduced at a flow rate of 200-300 mL / min, and the reaction was stopped after three hours. The reaction solution was dark green, and the total weight of the reaction solution was 151.6 g. 0.1 g of the reaction solution was taken, and toluene was used as an internal standard. 0.1 g of toluene was diluted with 2 g of acetonitrile and injected for testing. Substituting the test data into the internal standard curve, the remaining 4-methyl-1-naphthoic acid was 0.8 g, and the 1,4-naphthoic acid was 54.2 g. The conversion rate of 4-methyl-1-naphthoic acid was 98.4%, and the selectivity of 1,4-naphthoic acid was 94.9%.

[0114] Example 11

[0115] N-hydroxyphthalimide (0.5 g), isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-003 (0.5 g), cerium acetate (0.25 g), phosphomolybdic acid (0.05 g), acetonitrile (1.0 g), acetic acid (100 g), and 4-methyl-1-naphthoic acid (50 g) were added sequentially to a 250 mL titanium high-pressure reactor. After the reactor was assembled, nitrogen gas was introduced until the internal pressure reached 0.5 MPa and maintained for 15 minutes. A pressure drop of no more than 5% was considered a good airtightness of the reactor. After purging the nitrogen, the temperature was raised to 100 °C, and air was introduced until the internal pressure reached 0.3 MPa. Air was continuously introduced at a flow rate of 200-300 mL / min, and the reaction was stopped after three hours. The reaction solution was dark green, and the total weight of the reaction solution was 152.6 g. Take 0.1 g of the reaction solution, using toluene as an internal standard. Take 0.1 g of toluene, dilute with 2 g of acetonitrile, and inject for testing. Substituting the test data into the internal standard curve, the remaining 4-methyl-1-naphthoic acid was 2.5 g, and 1,4-naphthoic acid was 53.8 g. The calculated conversion rate of 4-methyl-1-naphthoic acid was 95.0%, and the selectivity of 1,4-naphthoic acid reached 97.6%.

[0116] Example 12

[0117] N-hydroxyphthalimide (0.5 g), isoquinoline-5-carboxylic acid coordinated catalyst YG-36-2-004 (0.5 g), manganese acetate (0.25 g), phosphomolybdic acid (0.05 g), methanol (1.0 g), acetic acid (100 g), and 4-methyl-1-naphthoic acid (50 g) were added sequentially to a 250 mL titanium high-pressure reactor. After the reactor was assembled, nitrogen gas was introduced until the internal pressure reached 0.5 MPa and maintained for 15 minutes. A pressure drop of no more than 5% was considered a good airtightness of the reactor. After purging the nitrogen, the temperature was raised to 100 °C, and air was introduced until the internal pressure reached 0.3 MPa. Air was continuously introduced at a flow rate of 200-300 mL / min, and the reaction was stopped after three hours. The reaction solution was dark green, and the total weight of the reaction solution was 154.3 g. Take 0.1 g of the reaction solution, using toluene as an internal standard. Take 0.1 g of toluene, dilute with 2 g of acetonitrile, and inject for testing. Substituting the test data into the internal standard curve, the remaining 4-methyl-1-naphthoic acid was 2.6 g, and 1,4-naphthoic acid was 53.1 g. The calculated conversion rate of 4-methyl-1-naphthoic acid was 94.8%, and the selectivity of 1,4-naphthoic acid reached 96.5%.

[0118] Comparative Example

[0119] The experimental procedure for the comparative example is the same as that for Example 9, except for the amount of material added. The specific amount of material added and the experimental results are shown in Table 1.

[0120] Table 1. Material addition amounts and experimental results of Example 9 and the comparative example.

[0121]

[0122] Compared with the catalyst without isoquinoline-5-carboxylic acid coordination in Comparative Example 8, the conversion rate of 4-methyl-1-naphthoic acid and the selectivity of 1,4-naphthoic acid in Example 9 were the best, indicating that the catalyst with isoquinoline-5-carboxylic acid coordination disclosed in this invention can effectively catalyze the oxidation of 4-methyl-1-naphthoic acid to 1,4-naphthoic acid.

[0123] As can be seen from Comparative Examples 1-7, the reaction effect was affected to varying degrees after selectively removing the co-catalyst, regulator, protectant and solvent. This indicates that using the above components in combination can have a synergistic effect on catalysis, which can better improve the reaction selectivity. Moreover, the overall reaction steps are simple and easy to operate, which helps to reduce the cost of raw materials or post-processing.

[0124] 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 invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0125] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A catalyst coordinated with isoquinoline-5-carboxylic acid, characterized in that, The general chemical formula of the catalyst is shown in formula (Ⅰ): （Ⅰ） Wherein, B is selected from lithium ion, sodium ion, potassium ion, magnesium ion, calcium ion, ammonium ion, dodecyl dimethyl benzyl ammonium ion, dodecyl trimethyl ammonium ion, octadecyl trimethyl ammonium ion, octadecyl dimethyl benzyl ammonium 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, and W; R is selected from C1 to C2. 10 alkyl; x is selected from an integer between 1 and 20; y is selected from integers between 1 and 40.

2. A method for preparing the isoquinoline-5-carboxylic acid coordinated catalyst according to claim 1, characterized in that, Includes the following steps: The metal compound is dissolved in deionized water, the pH of the solution is adjusted to 3-4, and then peroxide is added to obtain a metal peroxide solution. An alkyl-substituted isoquinoline-5-carboxylic acid and its salt were added to a metal peroxide solution, filtered, and dried to obtain a catalyst coordinated with isoquinoline-5-carboxylic acid.

3. The method for preparing the isoquinoline-5-carboxylic acid coordinated catalyst according to claim 2, characterized in that, The metal compound is selected from sodium tungstate, sodium molybdate, and sodium chromate.

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

5. The method for preparing the isoquinoline-5-carboxylic acid coordinated catalyst 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 isoquinoline-5-carboxylic acid coordinated catalyst 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, dodecyl dimethyl benzyl ammonium bromide, dodecyltrimethylammonium chloride, octadecyl dimethyl benzyl ammonium bromide, octyltributylphosphine bromide, tributylethylphosphine bromide, tetrabutylphosphine bromide, tributylhexylphosphine bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltriphenylphosphine bromide, benzyltrimethylammonium chloride, or benzyltriethylammonium chloride.

7. A composite catalyst, characterized in that, The catalyst includes the isoquinoline-5-carboxylic acid coordinated catalyst as described in claim 1.

8. The composite catalyst according to claim 7, characterized in that, It also includes a co-catalyst, wherein the weight ratio of the isoquinoline-5-carboxylic acid-coordinated catalyst to the co-catalyst is 100:(1-200). The co-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, wherein the weight ratio of the catalyst coordinated with isoquinoline-5-carboxylic acid to the regulator is 100:(1-200). The regulator is selected from phosphomolybdic acid, phosphotungstic acid, tetrabutylammonium bromide, boric acid, silicotungstic acid, and phosphomolybdic vanadate.

10. The composite catalyst according to claim 7, characterized in that, It also includes a protective agent, wherein the weight ratio of the isoquinoline-5-carboxylic acid coordinated catalyst 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 isoquinoline-5-carboxylic acid coordinated catalyst to the solvent is 100:(5-1000). The solvent is selected from 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, Includes the following steps: Mix the protective agent and solvent thoroughly to obtain a solution; Add the isoquinoline-5-carboxylic acid coordinated catalyst as described in claim 1 to the solution and stir at 40–90°C for 20–60 min; Add a co-catalyst and sonicate at 40–90°C for 20–60 min; Add a regulator and stir at 40–90°C for 30–60 min to obtain a composite catalyst.

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

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