Hydroxyquinoline coordinated catalyst, preparation method, composite catalyst and application

Abstract

The invention discloses a hydroxyquinoline coordinated catalyst, a preparation method, a composite catalyst and application, the general formula of the hydroxyquinoline coordinated catalyst is shown as formula (I): # imgabs0 # formula (I), B is selected from one of metal cations, ammonium ions, quaternary ammonium salt cations and quaternary phosphonium salt cations, M is one of Cu, Mo, W, Cr, V, Fe, Mn, Ni and Co, R is C1-C10 alkyl, x is an integer between 1 and 20, and y is an integer between 1 and 40. The hydroxyquinoline coordinated catalyst provided by the invention has high activity and high selectivity, and has high catalytic action and high conversion effect in catalytic oxidation of phenolic compounds to prepare quinone compounds.

Description

Technical Field

[0001] The invention belongs to the technical field of organic chemistry, and in particular relates to a hydroxyquinoline coordinated catalyst, a preparation method, a composite catalyst and applications. Background Art

[0002] Quinone compounds are a class of aromatic organic compounds with a six-carbon cyclic diketone structure containing two double bonds. They have the properties of open-chain diketones and can undergo addition reactions, substitution reactions, and reduction reactions. Common quinone compounds include benzoquinone, naphthoquinone, and phenanthrenequinone. Benzoquinone and its derivatives have antibacterial and anti-inflammatory properties and can be used to treat a variety of diseases. They are widely used in synthetic drugs and dyes. Naphthoquinone has a variety of pharmacological effects such as anti-inflammatory and anti-tumor effects and can be used to treat hepatitis, rheumatoid arthritis and other diseases. Phenanthrenequinone can be used as an intermediate for reducing dyes and can be used in photoconductive materials in electronic photography.

[0003] The common synthesis methods of quinone compounds are as follows: preparing benzoquinone by oxidation reaction of phenol compounds; using naphthalene as raw material to generate naphthoquinone by oxidation reaction; preparing phenanthrenequinone by oxidation reaction of phenanthrene. For example, US Patent US10364231B and European Patent EP2014 / 063425 disclose the oxidation of trimethylphenol based on copper chloride to trimethylbenzoquinone using oxygen-containing gas, wherein a large amount of copper chloride or chloride salt compound with lithium chloride added is used, but there is usually the formation of chlorinated byproducts, which decompose and release HCl during post-treatment, causing equipment corrosion. Another example is that in the prior art, TiSBA-15 molecular sieve is used as a catalyst and hydrogen peroxide is used as an oxidant to oxidize 2-methyl-1-naphthol to quinone, but the preparation of the molecular sieve is relatively cumbersome and the production cost is high; another example is that in the prior art, heteropolyacid is used as a catalyst and hydrogen peroxide is used as an oxidant to oxidize trimethylphenol and naphthol to prepare quinone, but the heteropolyacid used in the technology is relatively complex, difficult to prepare, and difficult to be applied in practice.

[0004] It can be seen that in the above-mentioned methods of preparing quinone compounds using phenolic compounds, there are disadvantages that the amount of catalyst used is large, the number of catalyst applications is small, and the reaction system may corrode the equipment.

[0005] The information disclosed in this background technology section is only intended to enhance the understanding of the overall background of the invention and should not be regarded as an acknowledgment or any form of suggestion that the information constitutes the prior art already known to a person skilled in the art. Summary of the invention

[0006] The purpose of the present invention is to provide a hydroxyquinoline coordinated catalyst, a preparation method, a composite catalyst and an application. The hydroxyquinoline coordinated catalyst of the present invention has high activity and high selectivity, can be repeatedly applied, and can effectively catalyze the oxidation of phenolic compounds to prepare quinone compounds.

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

[0008] A hydroxyquinoline coordinated catalyst, the catalyst general formula is as shown in formula (I):

[0009]

[0010] Wherein, B is selected from one of metal cations, ammonium ions, quaternary ammonium salt cations, and quaternary phosphonium salt cations;

[0011] M is one of Cu, Mo, W, Cr, V, Fe, Mn, Ni, and Co;

[0012] R is C 1 ~C 10 alkyl;

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

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

[0015] In one or more embodiments of the present invention, the quaternary ammonium salt cation is one of tetrabutylammonium ion, tetramethylammonium ion, hexadecyltrimethylammonium ion, dodecyltrimethylammonium ion, and octadecyltrimethylammonium ion.

[0016] In one or more embodiments of the present invention, the metal cation is one of lithium ion, sodium ion, potassium ion, magnesium ion and calcium ion.

[0017] In one or more embodiments of the present invention, the quaternary phosphonium salt cation is benzyltriphenylphosphonium ion.

[0018] Another specific embodiment of the present invention provides a technical solution as follows:

[0019] A method for preparing a hydroxyquinoline coordinated catalyst comprises the following steps:

[0020] Dissolving a metal compound in deionized water and adjusting the pH of the solution to 1-4; then adding peroxide and deionized water to the solution to obtain a metal peroxide solution;

[0021] Add alkyl-substituted 5-chloro-8-hydroxyquinoline and salt to the metal peroxide solution, stir, centrifuge, filter and dry to obtain a hydroxyquinoline-coordinated catalyst of the general formula (I).

[0022] Another specific embodiment of the present invention provides a technical solution as follows:

[0023] A composite catalyst comprises the above-mentioned hydroxyquinoline coordinated catalyst.

[0024] In one or more embodiments of the present invention, the composite catalyst further comprises a cocatalyst, and the weight ratio of the hydroxyquinoline-coordinated catalyst to the cocatalyst is 100:(1-500);

[0025] The auxiliary catalyst is one or more of cerium nitrate, cerium sulfate, cerium acetate, manganese acetate, manganese nitrate, manganese sulfate, vanadium oxide, cobalt oxide, silver nitrate, zirconium oxide, zirconium acetate, ferric nitrate, ferric sulfate, ferric chloride, copper sulfate, copper acetate, copper nitrate, magnesium sulfate, magnesium acetate, zinc acetate, zinc sulfate, sodium molybdate, potassium acetate and potassium sulfate.

[0026] In one or more embodiments of the present invention, the composite catalyst further comprises a regulator, and the weight ratio of the hydroxyquinoline-coordinated catalyst to the regulator is 100:(1-500);

[0027] The regulator is one or more of phosphomolybdic acid, phosphotungstic acid, tetrabutylammonium bromide, boric acid, silicotungstic acid and phosphomolybdic vanadic acid.

[0028] In one or more embodiments of the present invention, the composite catalyst further comprises a protective agent, and the weight ratio of the hydroxyquinoline-coordinated catalyst to the protective agent is 100:(1-500);

[0029] The protective agent is one or more of sodium acetate, ammonium bromide, hexadecyltrimethylammonium bromide, phenyltrimethylammonium bromide, sodium molybdate and N-hydroxyphthalimide.

[0030] In one or more embodiments of the present invention, the composite catalyst is dissolved in an organic solvent before use, and the weight ratio of the hydroxyquinoline-coordinated catalyst to the organic solvent is 100:(50-50000);

[0031] The organic solvent is one or more of 1,4-dioxane, acetonitrile, methanol, ethanol, n-butanol, isobutanol and n-pentanol.

[0032] Another specific embodiment of the present invention provides a technical solution as follows:

[0033] The invention discloses an application of a hydroxyquinoline coordinated catalyst or a composite catalyst in oxidizing a phenol compound to prepare a quinone compound.

[0034] In one or more embodiments of the present invention, the method for oxidizing a phenolic compound to prepare a quinone compound is:

[0035] Phenolic compounds and reaction solvents are added to a reactor, and then a hydroxyquinoline-coordinated catalyst or a composite catalyst is added, air is introduced into the reactor at a rate of 1 to 10 mL / s, and the reaction is stirred at 50 to 110° C. for 1 to 10 hours.

[0036] Compared with the prior art, the catalyst coordinated by hydroxyquinoline of the present invention has a bidentate structure, can effectively coordinate with metal, and the chlorine at the 5-position of the quinoline ring can effectively improve the activation of the phenol at the para-position, thereby effectively enhancing the activity and selectivity of the catalyst. In addition, B in the catalyst selects cations, has both hydrophilic and hydrophobic effects, can effectively improve the lipophilicity and hydrophilicity of the catalyst, promote the contact between the catalyst and the substrate, and ultimately improve the conversion effect. DETAILED DESCRIPTION

[0037] 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.

[0038] A specific embodiment of the present invention provides a hydroxyquinoline coordinated catalyst, the catalyst structure is shown in formula (I): In formula (I), B is selected from one of metal cations, ammonium ions, quaternary ammonium salt cations, and quaternary phosphonium salt cations; M is one of Cu, Mo, W, Cr, V, Fe, Mn, Ni, and Co; and R is C 1 ~C 10 Alkyl, x is an integer between 1 and 20, and y is an integer between 1 and 40.

[0039] Specifically, the chemical structure in formula (I) contains a bidentate structure, and the oxygen atom and nitrogen atom substituted at the 8th position of the quinoline ring coordinate with the metal M at the same time, effectively forming a stable complex and effectively ensuring the catalytic activity and selectivity. The chlorine atom substituted at the 5th position of the quinoline ring further enhances the catalytic activity and selectivity of the catalyst, and can effectively improve the activation of the phenolic compound when catalyzing the generation of quinone compounds from phenolic compounds, thereby promoting the reaction. The alkyl substituted at the 2nd position of the quinoline ring can affect the selectivity and catalytic activity of the catalyst. The present invention selects C 1 ~C 10 Alkyl groups as R groups can improve the selectivity and catalytic activity of the catalyst, making it more suitable for catalyzing phenolic compounds to generate quinone compounds.

[0040] In addition, the present invention selects the above-mentioned types of B to improve the lipophilicity and hydrophilicity of the catalyst, promotes the contact between the catalyst and the reaction substrate, and improves the conversion effect. At the same time, the present invention limits the values ​​of x and y to improve the stability of the catalyst structure and improve the interaction between the catalyst and the reaction substrate, thereby effectively improving the catalytic activity, selectivity and stability of the catalyst.

[0041] In a specific embodiment, the quaternary ammonium salt cation is one of tetrabutylammonium ion, tetramethylammonium ion, hexadecyltrimethylammonium ion, dodecyltrimethylammonium ion, and octadecyltrimethylammonium ion; the metal cation is one of lithium ion, sodium ion, potassium ion, magnesium ion, and calcium ion; and the quaternary phosphonium salt cation is benzyltriphenylphosphonium ion.

[0042] More preferably, B is one of dodecyltrimethylammonium ion, octadecyltrimethylammonium ion, lithium ion, sodium ion, potassium ion, magnesium ion, calcium ion, ammonium ion, benzyltriphenylphosphonium ion; M is one of Cu, Mo, Cr, V, Fe, Ni, Co; R is C 1 ~C 5 Alkyl; x is an integer between 1 and 5; y is an integer between 1 and 5.

[0043] More preferably, B is one of octadecyltrimethylammonium ion, sodium ion, magnesium ion, ammonium ion, benzyltriphenylphosphonium ion; M is one of Cu, Mo, Cr, V, Ni, Co; R is methyl, ethyl or isopropyl; x is 1, and y is 1 or 2.

[0044] Specifically, by selecting specific types of B and M and limiting the values ​​of x and y, the hydroxyquinoline-coordinated catalyst has higher selectivity and catalytic activity in catalyzing the preparation of quinone compounds from phenolic compounds.

[0045] Another specific embodiment of the present invention provides a method for preparing a hydroxyquinoline coordinated catalyst, comprising steps 1-2.

[0046] Step 1, dissolving a metal compound in deionized water, and adjusting the pH value of the solution to 1-4; and then adding peroxide and deionized water to the solution to obtain a metal peroxide solution.

[0047] Specifically, the metal compound is dissolved in deionized water at room temperature, and then sulfuric acid, phosphoric acid, hydrochloric acid or nitric acid is used to adjust the pH of the solution. The metal compound is one of copper nitrate, sodium molybdate, chromium nitrate, chromium nitrate nonahydrate, cobalt nitrate, cobalt sulfate, nickel nitrate, nickel sulfate, sodium metavanadate, manganese nitrate, and iron nitrate, and the peroxide is one or more of hydrogen peroxide, m-chloroperbenzoic acid, tert-butyl hydroperoxide, and urea peroxide.

[0048] Step 2, adding alkyl-substituted 5-chloro-8-hydroxyquinoline and salt to the metal peroxide solution, stirring, centrifuging, filtering, and drying to obtain a hydroxyquinoline-coordinated catalyst having a chemical structure as shown in formula (I).

[0049] Specifically, the metal peroxide solution is first heated to 25-100° C., and then the hydroxyquinoline compound and the salt are added. The alkyl-substituted 5-chloro-8-hydroxyquinoline is 3-methyl-5-chloro-8-hydroxyquinoline, 3-ethyl-5-chloro-8-hydroxyquinoline, 3-propyl-5-chloro-8-hydroxyquinoline, 3-isopropyl-5-chloro-8-hydroxyquinoline, 3-n-butyl-5-chloro-8-hydroxyquinoline, 3-tert-butyl-5-chloro-8-hydroxyquinoline or 3-isobutyl-5-chloro-8-hydroxyquinoline, and the salt is octadecyltrimethylammonium chloride, octadecyltrimethylammonium bromide, or chloride. One of lithium, 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, benzyltrimethylammonium chloride, benzyltriphenylphosphonium bromide and benzyltriethylammonium chloride.

[0050] Another specific embodiment of the present invention provides a composite catalyst, including a hydroxyquinoline-coordinated catalyst shown in formula (I).

[0051] Preferably, the composite catalyst further comprises a cocatalyst, a regulator and a protective agent, and the weight ratio of the hydroxyquinoline coordinated catalyst, the cocatalyst, the regulator and the protective agent is 100:(1-500):(1-500):(1-500).

[0052] Specifically, the cocatalyst is one or more of cerium nitrate, cerium sulfate, cerium acetate, manganese acetate, manganese nitrate, manganese sulfate, vanadium oxide, cobalt oxide, silver nitrate, zirconium oxide, zirconium acetate, ferric nitrate, ferric sulfate, ferric chloride, copper sulfate, copper acetate, copper nitrate, magnesium sulfate, magnesium acetate, zinc acetate, zinc sulfate, sodium molybdate, potassium acetate and potassium sulfate; the regulator is one or more of phosphomolybdic acid, phosphotungstic acid, tetrabutylammonium bromide, boric acid, silicotungstic acid and phosphomolybdicvanadic acid; the protective agent is one or more of sodium acetate, ammonium bromide, hexadecyltrimethylammonium bromide, phenyltrimethylammonium bromide, sodium molybdate and N-hydroxyphthalimide.

[0053] Specifically, the selection of the above-mentioned cocatalyst can improve the reaction selectivity, promote the oxidation of specific phenolic hydroxyl groups into quinones, and activate phenolic compounds to accelerate the reaction rate. The above-mentioned regulators can affect the reaction rate and process during the reaction. Adding them to the reaction system in a certain proportion can effectively promote the reaction and improve the reaction efficiency. The protective agent can reduce the occurrence of side reactions in the reaction system, improve the product and purity of the target product, activate the phenolic hydroxyl group to a certain extent, promote it to be more easily oxidized, and prevent it from being over-oxidized.

[0054] In a specific embodiment, the composite catalyst is dissolved in an organic solvent before use, and the weight ratio of the hydroxyquinoline-coordinated catalyst to the organic solvent is 100:(50-10000).

[0055] Specifically, the organic solvent is one or more of 1,4-dioxane, acetonitrile, methanol, ethanol, n-butanol, isobutanol and n-pentanol. Selecting the above organic solvents to dissolve the composite catalyst first can promote the uniform dispersion of the composite catalyst in the reaction system, increase the reaction rate, and reduce the occurrence of side reactions.

[0056] More preferably, the weight ratio of the hydroxyquinoline-coordinated catalyst, cocatalyst, regulator, protective agent and organic solvent is 100:(1-50):(1-500):(10-100):(100-1000), the cocatalyst is one or more of manganese acetate, zirconium acetate, magnesium acetate and cerium acetate, the regulator is one or more of phosphomolybdic acid, phosphotungstic acid and silicotungstic acid, the protective agent is one or more of ammonium bromide, hexadecyltrimethylammonium bromide, phenyltrimethylammonium bromide and N-hydroxyphthalimide, and the organic solvent is one or more of acetonitrile, ethanol, n-butanol, isobutanol and n-pentanol.

[0057] Another specific embodiment of the present invention provides the use of a hydroxyquinoline-coordinated catalyst or a composite catalyst represented by formula (I) in the oxidation of phenolic compounds to prepare quinone compounds.

[0058] In a specific embodiment, the method for oxidizing phenolic compounds to prepare quinone compounds is: add the phenolic compound and the reaction solvent into a reactor, then add a catalyst or a composite catalyst containing a hydroxyquinoline coordination, introduce air into the reactor at a rate of 1 to 10 mL / s, and stir the reaction at 50 to 110° C. for 1 to 10 hours.

[0059] Specifically, taking the composite catalyst as an example, the dosage of the composite catalyst is 0.01 to 5% of the weight of the phenolic compound, and the composite catalyst includes a hydroxyquinoline-coordinated catalyst, a co-catalyst, a regulator and a protective agent in a weight ratio of 100: (1 to 500): (1 to 500): (1 to 500); the phenolic compound is phenol, methylphenol, p-methylphenol, naphthol or methylnaphthol; and the reaction solvent is ethanol, n-butanol or n-pentanol.

[0060] More preferably, air is introduced into the reactor at a rate of 2 to 5 mL / s, and the reaction is stirred at 60 to 90° C. for 2 to 5 hours; the reaction solvent is n-butanol, and the amount of the composite catalyst is 0.1 to 1% by weight of the phenolic compound.

[0061] Specifically, the hydroxyquinoline-coordinated catalyst represented by formula (I) of the present invention has high selectivity and high catalytic activity in the reaction of oxidizing phenolic compounds to prepare quinones. Adding it to the reaction system in a certain proportion can selectively oxidize phenolic hydroxyl groups to generate quinones with a high conversion rate.

[0062] The present invention is further described in detail below in conjunction with specific embodiments.

[0063] Hydroxyquinoline-coordinated catalyst example

[0064] Example 1

[0065] At room temperature, add 20.60g of sodium molybdate to 500mL of deionized water, stir to completely dissolve the sodium molybdate, then drop dilute sulfuric acid into the solution to adjust the pH of the solution to 2, and continue stirring for 30 minutes. Slowly add 200mL of 30% hydrogen peroxide solution into the solution, and then add deionized water to a total volume of 3000mL to obtain a metal peroxide solution.

[0066] The metal peroxide solution was heated to 50°C, 19.36g of 3-methyl-5-chloro-8-hydroxyquinoline and 76.57g of tetrabutylammonium bromide were added to the metal peroxide solution, and the mixture was stirred for 1h while heating, and then centrifuged for 10min, filtered, and the solid obtained after filtration was placed in a vacuum drying oven for drying to obtain 59.82g of yellow solid, which was the catalyst coordinated by hydroxyquinoline. The NMR characterization data are as follows:

[0067] 1 H NMR: δ2.29-2.39(3H,2.34(s),2.34(s),2.34(s)),2.81(12H,s),7.31(1H,d,J=8.5 Hz), 7.63 (1H, dd, J = 8.5, 0.5 Hz), 8.47 (1H, dd, J = 1.7, 0.5 Hz), 8.62 (1H, d, J = 1.7 Hz).

[0068] Example 2

[0069] At room temperature, add 20.60g of sodium molybdate to 500mL of deionized water, stir to completely dissolve the sodium molybdate, then drop dilute sulfuric acid into the solution to adjust the pH of the solution to 2, and continue stirring for 30 minutes. Slowly add 200mL of 30% urea peroxide solution into the solution, and then add deionized water to a total volume of 3000mL to obtain a metal peroxide solution.

[0070] The metal peroxide solution was heated to 50°C, 22.11 g of 3-isopropyl-5-chloro-8-hydroxyquinoline and 42.25 g of octadecyltrimethylammonium chloride were added to the metal peroxide solution, and the mixture was stirred for 1 h while heating, and then centrifuged for 10 min, filtered, and the solid obtained after filtration was placed in a vacuum drying oven for drying to obtain 58.87 g of a yellow solid, which was the catalyst coordinated with hydroxyquinoline. The NMR characterization data are as follows:

[0071] 1 H NMR: δ0.86(3H,t,J=7.0Hz),1.13-1.43(36H,m),1.94(2H,quint,J=7.4Hz),2.84(9H,s),3.05(2H,t,J=7.4Hz),3.23(1H ,sept,J=6.9Hz),7.31(1H,d,J=8.4Hz),7.63(1H,dd,J=8.4,0.5Hz),8.22(1H,dd,J=1.9,0.5Hz),8.73(1H,d,J=1.9Hz).

[0072] Example 3

[0073] At room temperature, add 40.01 g of chromium nitrate nonahydrate to 500 mL of deionized water, stir until the chromium nitrate nonahydrate is completely dissolved, then add dilute sulfuric acid to the solution to adjust the pH of the solution to 2, and continue stirring for 120 min. Slowly add 200 mL of 30% hydrogen peroxide solution to the solution, and then add deionized water to a total volume of 3000 mL to obtain a metal peroxide solution.

[0074] The metal peroxide solution was heated to 100°C, 19.36g of 3-ethyl-5-chloro-8-hydroxyquinoline and 42.25g of octadecyltrimethylammonium chloride were added to the metal peroxide solution, and the mixture was stirred for 1 hour while heating, and then centrifuged for 30 minutes, filtered, and the solid obtained after filtration was placed in a vacuum drying oven for drying to obtain 56.49g of purple-red solid, which was the catalyst coordinated by hydroxyquinoline. The nuclear magnetic characterization data are as follows:

[0075] 1H NMR: δ0.86 (3H, t, J = 7.0Hz), 1.09-1.43 (33H, m), 1.94 (2H, quint, J = 7.4Hz), 2.78-2.90 (11H, 2.84 (q, J = 6.9Hz), 2.84 (q, J = 6.9Hz), 2. 84(s)), 3.05(2H,t,J=7.4Hz), 7.31(1H,d,J=8.4Hz), 7.63(1H,dd,J=8.4,0.5Hz), 8.25(1H,dd,J=1.8,0.5Hz), 8.73(1H,d,J=1.8Hz).

[0076] Example 4

[0077] At room temperature, add 29.10 g of cobalt nitrate hexahydrate to 500 mL of deionized water, stir to completely dissolve the cobalt nitrate hexahydrate, then drop dilute sulfuric acid into the solution to adjust the pH of the solution to 2, and continue stirring for 30 minutes. Slowly add 200 mL of 30% hydrogen peroxide solution into the solution, and then add deionized water to a total volume of 3000 mL to obtain a metal peroxide solution.

[0078] The metal peroxide solution was heated to 35°C, 19.36g of 3-methyl-5-chloro-8-hydroxyquinoline and 42.25g of octadecyltrimethylammonium chloride were added to the metal peroxide solution, and the mixture was stirred for 10 hours while heating, and then centrifuged for 10 minutes, filtered, and the solid obtained after filtration was placed in a vacuum drying oven for drying to obtain 56.53g of a blue solid, which was a catalyst coordinated with hydroxyquinoline. The NMR characterization data are as follows:

[0079] 1 H NMR: δ0.86(3H,t,J=7.0Hz),1.16-1.43(30H,m),1.94(2H,quint,J=7.4Hz),2.29-2.39(3H,2.34(s),2.34(s),2.34(s)),2.84(9H , s), 3.05 (2H, t, J = 7.4Hz), 7.31 (1H, d, J = 8.5Hz), 7.63 (1H, dd, J = 8.5, 0.5Hz), 8.47 (1H, dd, J = 1.7, 0.5Hz), 8.62 (1H, d, J = 1.7Hz).

[0080] Application examples of hydroxyquinoline-coordinated catalysts

[0081] Application Example 1

[0082] Into 250mL titanium material autoclave, add 0.1g catalyst of hydroxyquinoline coordination in embodiment 1, 0.01g cerium acetate, 0.01g phosphomolybdic acid, 0.01g sodium acetate and 50g ethanol successively, after autoclave is installed, nitrogen is filled into to the pressure in the autoclave to be 0.5MPa and keep 15min, pressure reduction is no more than 5%, then it is considered that the air tightness of the autoclave is good. After nitrogen is discharged, the reactor temperature is raised to 65 ℃, and air is passed to the pressure in the reactor to be 0.3MPa, and air is passed continuously, and the control flow is 400mL / min. After the system is stable, a high-pressure feed pump is used, and a methanol solution of phenol is pumped in at a speed of 1ml / min. In the methanol solution of phenol, phenol weight content is 30%, and pumping in total material is 100mL. After pumping in, the reaction is continued for 1h. After the reaction is completed, the reaction solution is yellow-green, and the reaction solution gross weight is 138.73g.

[0083] 0.1 g of the reaction solution was taken, xylene was used as the internal standard, and 30 g of acetonitrile was added to dilute it and then liquid phase testing was performed. The calculated conversion rate of phenol was 99.3%, and the selectivity for benzoquinone was 92.35%.

[0084] Application Example 2

[0085] Into 250mL titanium material autoclave, add 0.1g catalyst of hydroxyquinoline coordination in embodiment 2, 0.01g cerium acetate, 0.01g phosphomolybdic acid, 0.01g sodium acetate and 50g n-butanol successively, autoclave is filled with nitrogen to 0.5MPa and keeps 15min after installing, pressure reduction is no more than 5%, then thinks that reactor air tightness is good. After nitrogen is discharged, reactor temperature is raised to 70 DEG C, air is passed to reactor pressure is 0.3MPa, air is passed continuously, and control flow is 400mL / min, after system is stable, high pressure feed pump is used, and the methanol solution of o-methylphenol is pumped into at a speed of 1ml / min, in the methanol solution of o-methylphenol, o-methylphenol weight content is 30%, and pumping into total material is 100mL, and pumping into is continued to react 1h after completion, and after reaction ends, reaction solution is yellow-green, and reaction solution gross weight is 134.63g.

[0086] 0.1 g of the reaction solution was taken, xylene was used as the internal standard, and 30 g of acetonitrile was added to dilute it and then liquid phase testing was performed. The conversion rate of o-methylphenol was calculated to be 98.6%, and the selectivity of methylbenzoquinone was 93.38%.

[0087] Application Example 3

[0088] Into 250mL titanium material autoclave, add 0.1g hydroxyquinoline coordinated catalyst in embodiment 3, 0.01g cerium acetate, 0.01g phosphomolybdic acid, 0.01g sodium acetate and 50g n-amyl alcohol successively, after autoclave is installed, nitrogen is filled into to the pressure in the autoclave to be 0.5MPa and keep 15min, pressure reduction is no more than 5%, then think that the air tightness of the autoclave is good. After discharging nitrogen, the reactor temperature is raised to 60 ℃, and air is ventilated to the pressure in the reactor to be 0.3MPa, and air is continuously ventilated, and the control flow is 400mL / min. After the system is stable, use high-pressure feed pump, and the n-amyl alcohol solution of naphthol is pumped into at a speed of 1ml / min. In the n-amyl alcohol solution of naphthol, naphthol weight content is 30%, and pumping into total material is 100mL. After pumping into, continue to react 1h, after reaction ends, reaction solution is yellow-green, and reaction solution gross weight is 134.63g.

[0089] 0.1 g of the reaction solution was taken, xylene was used as the internal standard, and 30 g of acetonitrile was added to dilute it and then liquid phase testing was performed. The calculated conversion rate of naphthol was 98.96%, and the selectivity of naphthoquinone was 91.36%.

[0090] Application Example 4

[0091] Into 250mL titanium material autoclave, add 0.1g catalyst of hydroxyquinoline coordination in embodiment 4, 0.01g cerium acetate, 0.01g phosphomolybdic acid, 0.01g sodium acetate and 50g n-butanol successively, autoclave is filled with nitrogen to 0.5MPa and keeps 15min after installing, pressure reduction is no more than 5%, and it is considered that the air tightness of the reactor is good. After nitrogen is discharged, the reactor temperature is raised to 70 ℃, and air is passed to 0.3MPa in the reactor, and air is passed continuously, and the control flow is 400mL / min. After the system is stable, a high-pressure feed pump is used, and the methanol solution of o-methylphenol is pumped in at a speed of 1ml / min. In the methanol solution of o-methylphenol, the o-methylphenol weight content is 30%, and the total material pumped in is 100mL. After pumping in, the reaction is continued for 1h. After the reaction is completed, the reaction solution is yellow-green, and the reaction solution gross weight is 134.63g.

[0092] 0.1 g of the reaction solution was taken, xylene was used as the internal standard, and 30 g of acetonitrile was added to dilute it and then liquid phase testing was performed. The conversion rate of o-methylphenol was calculated to be 99.2%, and the selectivity of methylbenzoquinone was 92.34%.

[0093] Comparative Example 1

[0094] At room temperature, add 20.60g of sodium molybdate to 500mL of deionized water, stir to completely dissolve the sodium molybdate, then drop dilute sulfuric acid into the solution to adjust the pH of the solution to 2, and continue stirring for 30 minutes. Slowly add 200mL of 30% hydrogen peroxide solution into the solution, and then add deionized water to a total volume of 3000mL to obtain a metal peroxide solution.

[0095] The metal peroxide solution was heated to 50°C, 17.51 ​​g of 3-methyl-8-hydroxyquinoline and 76.57 g of tetrabutylammonium bromide were added to the metal peroxide solution, and the mixture was stirred for 1 h while heating, and then centrifuged for 10 min, filtered, and the solid obtained after filtration was placed in a vacuum drying oven for drying to obtain 53.35 g of a yellow solid, which was the catalyst coordinated with hydroxyquinoline. The NMR characterization data are as follows:

[0096] 1 H NMR: δ2.29-2.39(3H,2.34(s),2.34(s),2.34(s)),2.81(12H,s),7.31(1H,d,J=8.5 Hz), 7.63 (1H, dd, J = 8.5, 0.5 Hz), 8.47 (1H, dd, J = 1.7, 0.5 Hz), 8.62 (1H, d, J = 1.7 Hz).

[0097] 0.1g of hydroxyquinoline coordinated catalyst, 0.01g of cerium acetate, 0.01g of phosphomolybdic acid, 0.01g of sodium acetate and 50g of n-pentanol were added to a 250mL titanium autoclave in sequence. After the autoclave was installed, nitrogen was charged to a pressure of 0.5MPa in the autoclave and maintained for 15min. If the pressure drop did not exceed 5%, the air tightness of the autoclave was considered good. After the nitrogen was discharged, the temperature of the autoclave was raised to 60°C, air was passed to a pressure of 0.3MPa in the autoclave, and air was continuously passed in, with a flow rate of 400mL / min. After the system was stabilized, a high-pressure feed pump was used to pump in a n-pentanol solution of naphthol at a speed of 1ml / min. The weight content of naphthol in the n-pentanol solution of naphthol was 30%, and the total material pumped in was 100mL. After the pumping was completed, the reaction was continued for 1h. After the reaction was completed, the reaction solution was yellow-green, and the total weight of the reaction solution was 134.63g.

[0098] 0.1 g of the reaction solution was taken, xylene was used as an internal standard, and 30 g of acetonitrile was added to dilute it and then liquid phase testing was performed. The calculated conversion rate of naphthol was 68.76%, and the selectivity of naphthoquinone was 67.65%.

[0099] Comparative Example 2

[0100] At room temperature, add 20.60g of sodium molybdate to 500mL of deionized water, stir to completely dissolve the sodium molybdate, then drop dilute sulfuric acid into the solution to adjust the pH of the solution to 2, and continue stirring for 30 minutes. Slowly add 200mL of 30% urea peroxide solution into the solution, and then add deionized water to a total volume of 3000mL to obtain a metal peroxide solution.

[0101] The metal peroxide solution was heated to 50°C, 18.32g of 3-isopropyl-8-hydroxyquinoline and 42.25g of octadecyltrimethylammonium chloride were added to the metal peroxide solution, and the mixture was stirred for 1h while heating, and then centrifuged for 10min, filtered, and the solid obtained after filtration was placed in a vacuum drying oven for drying to obtain 55.65g of yellow solid, which was the catalyst coordinated by hydroxyquinoline. The NMR characterization data are as follows:

[0102] 1 H NMR: δ0.86(3H,t,J=7.0Hz),1.13-1.43(36H,m),1.94(2H,quint,J=7.4Hz),2.84(9H,s),3.05(2H,t,J=7.4Hz),3.23(1H ,sept,J=6.9Hz),7.31(1H,d,J=8.4Hz),7.63(1H,dd,J=8.4,0.5Hz),8.22(1H,dd,J=1.9,0.5Hz),8.73(1H,d,J=1.9Hz).

[0103] 0.1g of hydroxyquinoline coordinated catalyst, 0.01g of cerium acetate, 0.01g of phosphomolybdic acid, 0.01g of sodium acetate and 50g of ethanol were added to a 250mL titanium autoclave in sequence. After the autoclave was installed, nitrogen was charged to a pressure of 0.5MPa in the autoclave and maintained for 15min. If the pressure drop did not exceed 5%, the air tightness of the autoclave was considered good. After the nitrogen was discharged, the temperature of the autoclave was raised to 65°C, and air was passed to a pressure of 0.3MPa in the autoclave. Air was continuously passed in, and the flow rate was controlled to be 400mL / min. After the system was stabilized, a high-pressure feed pump was used to pump in a methanol solution of phenol at a speed of 1ml / min. The weight content of phenol in the methanol solution of phenol was 30%, and the total material pumped in was 100mL. After the pumping was completed, the reaction was continued for 1h. After the reaction was completed, the reaction solution was yellow-green, and the total weight of the reaction solution was 138.73g.

[0104] 0.1 g of the reaction solution was taken, xylene was used as the internal standard, and 30 g of acetonitrile was added to dilute it and then liquid phase testing was performed. The calculated conversion rate of phenol was 67.3%, and the selectivity for benzoquinone was 72.5%.

[0105] Comparative Example 3

[0106] At room temperature, 24.88 g of nickel acetate tetrahydrate was added to 500 mL of deionized water, and the nickel acetate tetrahydrate was completely dissolved by stirring. Then, dilute sulfuric acid was added dropwise to the solution to adjust the pH of the solution to 2, and stirring was continued for 80 min. 200 mL of a 30% hydrogen peroxide solution was slowly added to the solution, and deionized water was added to the solution until the total volume was 3000 mL to obtain a metal peroxide solution.

[0107] The metal peroxide solution was heated to 45°C, 15.56 g of 3-methyl-8-hydroxyquinoline and 42.25 g of octadecyltrimethylammonium chloride were added to the metal peroxide solution, and the mixture was stirred for 3 h while heating, and then centrifuged for 20 min, filtered, and the solid obtained after filtration was placed in a vacuum drying oven for drying to obtain 57.56 g of a white solid, which was the catalyst coordinated with hydroxyquinoline. The NMR characterization data are as follows:

[0108] 1 H NMR: δ0.86(3H,t,J=7.0Hz),1.16-1.43(30H,m),1.94(2H,quint,J=7.4Hz),2.29-2.39(3H,2.34(s),2.34(s),2.34(s)),2.84(9H , s), 3.05 (2H, t, J = 7.4Hz), 7.31 (1H, d, J = 8.5Hz), 7.63 (1H, dd, J = 8.5, 0.5Hz), 8.47 (1H, dd, J = 1.7, 0.5Hz), 8.62 (1H, d, J = 1.7Hz).

[0109] 0.1g of hydroxyquinoline coordinated catalyst, 0.01g of cerium acetate, 0.01g of phosphomolybdic acid, 0.01g of sodium acetate and 50g of n-butanol were added to a 250mL titanium autoclave in sequence. After the autoclave was installed, nitrogen was charged to a pressure of 0.5MPa in the autoclave and maintained for 15min. If the pressure drop did not exceed 5%, the air tightness of the autoclave was considered good. After the nitrogen was discharged, the temperature of the autoclave was raised to 70°C, and air was passed to a pressure of 0.3MPa in the autoclave. Air was continuously passed in, and the flow rate was controlled to be 400mL / min. After the system was stabilized, a high-pressure feed pump was used to pump in a methanol solution of o-methylphenol at a speed of 1ml / min. The weight content of o-methylphenol in the methyl solution of o-methylphenol was 30%, and the total material pumped in was 100mL. After the pumping was completed, the reaction was continued for 1h. After the reaction was completed, the reaction solution was yellow-green, and the total weight of the reaction solution was 134.63g.

[0110] 0.1 g of the reaction solution was taken, xylene was used as the internal standard, and 30 g of acetonitrile was added to dilute it and then liquid phase testing was performed. The conversion rate of o-methylphenol was calculated to be 78.5%, and the selectivity of methylbenzoquinone was 69.4%.

[0111] Compared with Comparative Examples 1-3, when the hydroxyquinoline-coordinated catalyst in the embodiment of the present invention is used to oxidize phenolic compounds to generate quinone compounds, the conversion rate of the phenolic compounds reaches more than 98%, showing a higher conversion effect, while the conversion rates of the phenolic compounds in Comparative Examples 1-3 are all below 80%, which is much lower than the conversion rate in the application example of the present invention, indicating that the present invention selects alkyl-substituted 5-chloro-8-hydroxyquinoline as a raw material to prepare the catalyst, which can effectively enhance the activity and selectivity of the hydroxyquinoline-coordinated catalyst and can effectively improve the conversion effect.

[0112] 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.

[0113] 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 hydroxyquinoline coordinated catalyst, characterized in that: The general formula of the catalyst is shown in formula (I): Wherein, B is selected from one of metal cations, ammonium ions, quaternary ammonium salt cations, and quaternary phosphonium salt cations; M is one of Cu, Mo, W, Cr, V, Fe, Mn, Ni, and Co; R is C1~C 10 alkyl; x is an integer between 1 and 20; y is an integer between 1 and 40.

2. The hydroxyquinoline-coordinated catalyst according to claim 1, characterized in that The quaternary ammonium salt cation is one of tetrabutylammonium ion, tetramethylammonium ion, hexadecyltrimethylammonium ion, dodecyltrimethylammonium ion and octadecyltrimethylammonium ion.

3. The hydroxyquinoline-coordinated catalyst according to claim 1, characterized in that The metal cation is one of lithium ion, sodium ion, potassium ion, magnesium ion and calcium ion.

4. The hydroxyquinoline coordinated catalyst according to claim 1, characterized in that The quaternary phosphonium salt cation is a benzyltriphenylphosphonium ion.

5. A method for preparing a hydroxyquinoline-coordinated catalyst according to any one of claims 1 to 4, characterized in that: The steps include: Dissolving a metal compound in deionized water and adjusting the pH of the solution to 1-4; then adding peroxide and deionized water to the solution to obtain a metal peroxide solution; Add alkyl-substituted 5-chloro-8-hydroxyquinoline and salt to the metal peroxide solution, stir, centrifuge, filter and dry to obtain a hydroxyquinoline-coordinated catalyst of the general formula (I).

6. A composite catalyst, characterized in that: A catalyst comprising the hydroxyquinoline coordination catalyst according to any one of claims 1 to 4.

7. The composite catalyst according to claim 6, characterized in that The composite catalyst also includes a cocatalyst, and the weight ratio of the hydroxyquinoline-coordinated catalyst to the cocatalyst is 100:(1-500); The auxiliary catalyst is one or more of cerium nitrate, cerium sulfate, cerium acetate, manganese acetate, manganese nitrate, manganese sulfate, vanadium oxide, cobalt oxide, silver nitrate, zirconium oxide, zirconium acetate, ferric nitrate, ferric sulfate, ferric chloride, copper sulfate, copper acetate, copper nitrate, magnesium sulfate, magnesium acetate, zinc acetate, zinc sulfate, sodium molybdate, potassium acetate and potassium sulfate.

8. The composite catalyst according to claim 6, characterized in that: The composite catalyst also includes a regulator, and the weight ratio of the hydroxyquinoline-coordinated catalyst to the regulator is 100:(1-500); The regulator is one or more of phosphomolybdic acid, phosphotungstic acid, tetrabutylammonium bromide, boric acid, silicotungstic acid and phosphomolybdic vanadic acid.

9. The composite catalyst according to claim 6, characterized in that: The composite catalyst also includes a protective agent, and the weight ratio of the hydroxyquinoline-coordinated catalyst to the protective agent is 100:(1-500); The protective agent is one or more of sodium acetate, ammonium bromide, hexadecyltrimethylammonium bromide, phenyltrimethylammonium bromide, sodium molybdate and N-hydroxyphthalimide.

10. The composite catalyst according to claim 6, characterized in that: The composite catalyst is dissolved in an organic solvent before use, and the weight ratio of the hydroxyquinoline-coordinated catalyst to the organic solvent is 100:(50-50000); The organic solvent is one or more of 1,4-dioxane, acetonitrile, methanol, ethanol, n-butanol, isobutanol and n-pentanol.

11. Use of the hydroxyquinoline-coordinated catalyst according to any one of claims 1 to 4 or the composite catalyst according to any one of claims 6 to 10 in oxidizing phenolic compounds to prepare quinone compounds.

12. The use of the hydroxyquinoline coordinated catalyst according to claim 11, characterized in that: The method for preparing quinone compounds by oxidizing phenolic compounds is: Phenolic compounds and reaction solvents are added to a reactor, and then a hydroxyquinoline-coordinated catalyst or a composite catalyst is added, air is introduced into the reactor at a rate of 1 to 10 mL / s, and the reaction is stirred at 50 to 110° C. for 1 to 10 hours.

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