CN117142938A - Method for preparing 1, 4-naphthoquinone compound by selectively oxidizing aromatic ketone - Google Patents

Method for preparing 1, 4-naphthoquinone compound by selectively oxidizing aromatic ketone Download PDF

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CN117142938A
CN117142938A CN202310908057.0A CN202310908057A CN117142938A CN 117142938 A CN117142938 A CN 117142938A CN 202310908057 A CN202310908057 A CN 202310908057A CN 117142938 A CN117142938 A CN 117142938A
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aromatic ketone
preparing
naphthoquinone
catalyst
naphthoquinone compounds
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杜中田
郭忠旭
梁长海
申小雨
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Dalian University of Technology
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Dalian University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C46/00—Preparation of quinones
    • C07C46/02—Preparation of quinones by oxidation giving rise to quinoid structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C07B41/06—Formation or introduction of functional groups containing oxygen of carbonyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/24—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings
    • C07C225/26—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings having amino groups bound to carbon atoms of quinone rings or of condensed ring systems containing quinone rings
    • C07C225/30—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings having amino groups bound to carbon atoms of quinone rings or of condensed ring systems containing quinone rings of condensed quinone ring systems formed by two rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C50/00—Quinones
    • C07C50/10—Quinones the quinoid structure being part of a condensed ring system containing two rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C50/00—Quinones
    • C07C50/10—Quinones the quinoid structure being part of a condensed ring system containing two rings
    • C07C50/12—Naphthoquinones, i.e. C10H6O2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C50/00—Quinones
    • C07C50/26—Quinones containing groups having oxygen atoms singly bound to carbon atoms
    • C07C50/32—Quinones containing groups having oxygen atoms singly bound to carbon atoms the quinoid structure being part of a condensed ring system having two rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/12—Acetic acid esters
    • C07C69/14—Acetic acid esters of monohydroxylic compounds
    • C07C69/145—Acetic acid esters of monohydroxylic compounds of unsaturated alcohols
    • C07C69/157—Acetic acid esters of monohydroxylic compounds of unsaturated alcohols containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline

Abstract

The invention provides a method for preparing 1, 4-naphthoquinone compounds by selectively oxidizing aromatic ketone, which is a novel method for preparing 1, 4-naphthoquinone compounds by catalyzing and oxidizing aromatic ketone by using a copper-based and vanadium-based multi-phase catalytic material, and belongs to the technical field of fine chemicals. The method takes molecular oxygen as an oxidant, uses multiphase copper-based and vanadium-based catalytic materials, and prepares the 1, 4-naphthoquinone compounds by liquid phase selective oxidation of aromatic ketone under mild conditions. Wherein the Cu-N-C and V-N-C composite material is obtained by mixing inorganic metal salt and organic nitrogen-containing compound to obtain a precursor and calcining at 300-800 ℃ for 0.5-10h in inert atmosphere. The method provided by the invention adopts aromatic ketone as a raw material and molecular oxygen as an oxidant, has mild catalytic reaction conditions and less pollutants, is a new route for preparing the 1, 4-naphthoquinone compounds, and has strong practicability and wide application prospect.

Description

Method for preparing 1, 4-naphthoquinone compound by selectively oxidizing aromatic ketone
Technical Field
The invention belongs to the field of fine chemical industry, and in particular relates to a novel method for preparing a 1, 4-naphthoquinone compound by using aromatic ketone as a raw material and using molecular oxygen as an oxidant through a liquid phase catalytic selective oxidation reaction.
Background
The naphthoquinone compounds are small molecular compounds widely existing in the nature and have important application value in production and life. For example, 1, 4-naphthoquinone is an important fine chemical intermediate, and has wide application in the industries of pesticides, bactericides, dyes, synthetic rubber, resins and the like. 2-methyl-1, 4-naphthoquinone is a key intermediate for synthesizing vitamin K.
Taking 1, 4-naphthoquinone as an example, typical preparation methods thereof include two methods of a gas-phase oxidation method and a liquid-phase oxidation method. The gas phase oxidation method is to directly oxidize naphthalene to prepare 1, 4-naphthoquinone by using oxygen in air under the action of a catalyst, but the yield of the 1, 4-naphthoquinone is low and is only between 15 and 30 percent. The traditional liquid phase oxidation method comprises the steps of oxidizing naphthalene, naphthylamine and naphthol compounds by using high-valence heavy metal salt, nitric acid, peroxy acid and other oxidants to prepare naphthoquinone substances, and has serious environmental pollution. Chinese patent (CN 102976915A) is to mix 1-naphthylamine with sulfuric acid and stir to generate ammonium sulfate salt, the ammonium sulfate salt mixture is prepared by mixing MnO 2 And oxidizing the suspension obtained by mixing and pulping with sulfuric acid to generate 1, 4-naphthoquinone. Chinese patent (CN 102391091A) is to mix hydrogen peroxide and acetic anhydride in a certain proportion, generate peracetic acid under the condition of no acid catalyst, and oxidize alpha-naphthol by the peracetic acid to prepare 1, 4-naphthoquinone. Yamazaki et al uses chromium trioxide as a catalystAs a catalyst, periodic acid is used as an oxidant, naphthalene is oxidized to 1, 4-naphthoquinone in acetonitrile, which is an organic solvent, wherein the stoichiometric ratio of substrate, catalyst and oxidant is 1:0.1:4.2 (Tetrahedron Letters,2001,42,3355-3357). Researchers such as Shi developed a catalytic system of ruthenium complex and dodecane-1-sulfonic acid sodium salt, and naphthalene and its halogenated substituents can be converted into 1, 4-naphthoquinone in water under the oxidation of hydrogen peroxide (Journal of Molecular Catalysis A: chemical,2007,270,68-75). The tanue researchers found that silver oxide and nitric acid as oxidants can catalyze naphthol and its derivatives to 1, 4-naphthoquinone in acetone solvents, but this system readily produced a dimer byproduct of 1, 4-naphthoquinone, which was difficult to isolate (Tetrahedron, 2002,58,99-104). The method has the problems of equipment corrosion, serious pollution, high raw material cost and the like. The industrial preparation of 2-methyl-1, 4-naphthoquinone is carried out by oxidizing 2-methylnaphthalene in glacial acetic acid by taking chromic anhydride as oxidant, and the process has the problems of large pollution of chromium wastewater and waste residue, corrosion of equipment of glacial acetic acid and the like. Therefore, the development of a green and efficient new route and a new process for preparing the 1, 4-naphthoquinone compounds has important application background.
The invention takes molecular oxygen as an oxygen source, and catalytically and selectively oxidizes aromatic ketone into 1, 4-naphthoquinone compounds under the condition of mild liquid phase oxidation reaction, thereby developing a new route for preparing the 1, 4-naphthoquinone compounds.
Disclosure of Invention
Aiming at the problems, the invention provides a novel method for preparing the 1, 4-naphthoquinone compound by oxidizing aromatic ketone by using a heterogeneous catalyst in a liquid phase system. The method is a novel method for preparing the 1, 4-naphthoquinone compound under mild conditions by taking aromatic ketone as a raw material and molecular oxygen as an oxidant.
In order to achieve the above purpose, the specific technical scheme of the invention is as follows:
a method for preparing 1, 4-naphthoquinone compounds by selectively oxidizing aromatic ketone is a novel method for preparing 1, 4-naphthoquinone compounds by selectively oxidizing aromatic ketone in a liquid phase by using copper-based and vanadium-based multi-phase catalysts. According to the method, aromatic ketone is used as a raw material, molecular oxygen is used as an oxygen source, the aromatic ketone is selectively oxidized into 1, 4-naphthoquinone compounds in an organic solvent through liquid phase catalysis, and the conversion rate (%) of the aromatic ketone can reach more than 62%; the selectivity (%) of naphthoquinone compounds can reach more than 70%.
The method comprises the following specific steps: adding a catalyst, an aromatic ketone raw material and an organic solvent into a high-pressure reactor, wherein the dosage of the catalyst is 5-40wt% of the dosage of the aromatic ketone, and the dosage of the organic solvent is 1-40 times of the mass of the aromatic ketone. Molecular oxygen is used as an oxygen source, the mixture is heated and stirred at the temperature of 60-150 ℃, the partial pressure of the oxygen is 0.1-2MPa, the reaction time is 0.2-12h, the mixture is cooled to room temperature after the reaction is finished, the pressure is reduced to normal pressure, and the 1, 4-naphthoquinone compounds are obtained through separation.
Further, the aromatic ketone has a structure in the following reaction formula, and the 1, 4-naphthoquinone compound has a structure in the following reaction formula:
wherein R is 1 Is hydrogen, alkyl, phenyl, -Cl, -Br, -F, -NO 2 One or more of methoxy, ethoxy, cyano, amino, acetoxy and acetamido; r is R 2 Is hydrogen, alkyl, phenyl, -Cl, -Br, -F, -NO 2 One or more of methoxy, ethoxy, cyano, amino, acetoxy and acetamido; r is R 1 、R 2 May be the same or different.
Further, the organic solvent used in the catalytic oxidation reaction is one or more of gamma-valerolactone, delta-valerolactone, gamma-butyrolactone and epsilon-caprolactone.
Further, the molecular oxygen in the catalytic oxidation reaction is from air, oxygen or gas containing oxygen, and the partial pressure of oxygen is 0.1-2MPa.
Further, the catalyst is one or more of vanadium pentoxide, vanadium dioxide, vanadium trioxide, vanadium nitride, V-N-C composite material, copper oxide, cuprous oxide and Cu-N-C composite material, preferably V-N-C composite material and Cu-N-C composite material; wherein the preparation method of the V-N-C, cu-N-C composite material catalyst comprises the following steps: dissolving a metal source and a nitrogen-containing organic ligand in a solvent, wherein the molar ratio of the metal source to the nitrogen-containing organic ligand is 1:1-1:10, heating and stirring at 30-100 ℃ for 1-12 hours, cooling to room temperature, removing the solvent by rotary evaporation, drying at 30-80 ℃ for 1-24 hours in a vacuum drying oven, fully grinding the obtained precursor, pyrolyzing at 300-800 ℃ in an inert gas atmosphere for 0.5-10 hours, cooling, and fully grinding to obtain the Cu-N-C or V-N-C composite material. The copper source used in the preparation process of the V-N-C and Cu-N-C composite material is one or more of copper nitrate, copper chloride, copper acetate, copper sulfate and hydrates thereof, and the vanadium salt is one or more of ammonium metavanadate, ammonium vanadate, sodium metavanadate, sodium vanadate and hydrates thereof.
The nitrogen-containing organic ligand is one or more of melamine, dicyandiamide, 1, 10-phenanthroline, 2' -bipyridine, phthalocyanine, porphyrin, cyanuric acid, hydroxylamine hydrochloride, triethylene diamine, 2-methylimidazole, imidazole, 2-pyridine formamide, 2, 6-bipyridine formic acid, chitosan and urea.
In the preparation process of the V-N-C and Cu-N-C composite materials, the solvent is one or more of water, ethanol, methanol, N-propanol and isopropanol. The inert atmosphere is one or more than one mixture of nitrogen, argon and helium
The beneficial effects of the invention are as follows:
(1) The invention adopts multiphase copper-based and vanadium-based catalytic materials, can catalyze molecular oxygen to oxidize aromatic ketone to obtain corresponding 1, 4-naphthoquinone compounds, and has strong practicability and wide application prospect.
(2) Unlike the gas phase oxidation process with naphthalene as material, the present invention has liquid phase catalytic oxidation reaction system and high 1, 4-naphthoquinone compound yield.
(3) Unlike the process of producing 1, 4-naphthoquinone with naphthalene, naphthol, 1-naphthylamine, etc. as material in liquid phase system, the present invention uses aromatic ketone as material to prepare naphthoquinone, expands material channel and is one new path for preparing 1, 4-naphthoquinone.
Drawings
FIG. 1 (a) is a scanning electron microscope image of the catalyst A in example 1; fig. 1 (b) is a partial enlarged view of fig. 1 (a).
FIG. 2 is a GC analysis chart of the oxidation product of α -tetralone of example 1.
FIG. 3 is a flow chart showing the preparation of catalyst B in example 2.
FIG. 4 is a GC analysis chart of the oxidation product of 2-methyl-1-tetralone of example 2.
FIG. 5 is a GC analysis spectrum of the oxidation product of alpha-tetralone of example 12.
Detailed Description
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited to the following description.
Example 1
Preparation of the catalyst
The preparation process of the Cu-N-C catalyst adopts the molar ratio of copper nitrate trihydrate and 1, 10-phenanthroline (1:2) to prepare: 3mmol of copper nitrate trihydrate and 6mmol of 1, 10-phenanthroline are mixed, 150mL of ethanol is added, the mixture is heated to 100 ℃ and stirred for 4 hours, then the mixture is cooled to room temperature, the ethanol is removed by rotary evaporation, the mixture is dried for 12 hours under vacuum at 60 ℃, the mixture is fully ground and then is subjected to heat treatment for 1.5 hours under nitrogen atmosphere at 400 ℃, and then is cooled, and a Cu-N-C catalyst is obtained and is marked as a catalyst A.
Synthesis of 2.1,4-naphthoquinone
2mmol of alpha-tetralone, 10wt% of catalyst A and 4mL of gamma-valerolactone are added into a reaction kettle, 0.4MPa of oxygen is filled, the temperature is raised to 120 ℃ under stirring, and the reaction is carried out for 8 hours. Then cooled to room temperature and the pressure was reduced to normal pressure. The sample was taken for quantitative analysis of the product, the conversion of α -tetralone was 80% and the selectivity of 1, 4-naphthoquinone was 85%. The reaction results are shown in Table 1.
Example 2
Preparation of the catalyst
The Cu-N-C catalyst is prepared by preparing copper nitrate and 1, 10-phenanthroline (1:3) according to the molar ratio of Cheng Caiyong: 3mmol of copper nitrate and 9mmol of 1, 10-phenanthroline are mixed, 150mL of ethanol is added, the mixture is heated to 100 ℃ and stirred for 2 hours, then the mixture is cooled to room temperature, the ethanol is removed by rotary evaporation, the mixture is dried for 12 hours at 60 ℃, the mixture is fully ground and then is subjected to heat treatment for 0.5 hour in a nitrogen atmosphere at 400 ℃, and then the mixture is cooled, so that a Cu-N-C catalyst is obtained and is marked as a catalyst B.
Synthesis of 2, 2-methyl-1, 4-naphthoquinone
2mmol of 2-methyl-1-tetralone, 20wt% of catalyst B and 6mL of gamma-valerolactone are added into a reaction kettle, 0.7MPa of oxygen is filled, the temperature is raised to 120 ℃ under stirring, and the reaction is carried out for 8 hours. Then cooled to room temperature and the pressure was reduced to normal pressure. Samples were taken for quantitative analysis of the product, with a conversion of 72% of 2-methyl-1-tetralone and a selectivity of 79% for 2-methyl-1, 4-naphthoquinone. The reaction results are shown in Table 1.
Example 3
Preparation of the catalyst C
The Cu-N-C catalyst is prepared by Cheng Caiyong mol ratio of copper acetate monohydrate to melamine (1:5): 1mmol of copper acetate monohydrate and 5mmol of melamine are mixed, 250mL of ethanol is added, the mixture is heated to 90 ℃ and stirred for 4 hours, then the mixture is cooled to room temperature, the ethanol is removed by rotary evaporation, the mixture is dried for 12 hours under vacuum at 60 ℃, the mixture is fully ground and then is subjected to heat treatment for 3 hours under nitrogen atmosphere at 600 ℃, and then the mixture is cooled to obtain a Cu-N-C catalyst which is marked as a catalyst C.
Synthesis of 2, 2-methyl-1, 4-naphthoquinone
2mmol of 3-methyl-1-tetralone, 15wt% of catalyst C and 6mL of gamma-valerolactone are added into a reaction kettle, 2.0MPa of oxygen is filled, the temperature is raised to 100 ℃ under stirring, and the reaction is carried out for 6 hours. Then cooled to room temperature and the pressure was reduced to normal pressure. Samples were taken for quantitative analysis of the product, with a conversion of 3-methyl-1-tetralone of 75% and a selectivity of 2-methyl-1, 4-naphthoquinone of 79%. The reaction results are shown in Table 1.
Example 4
D catalyst preparation
The V-N-C catalyst is prepared by Cheng Caiyong mol ratio of ammonium metavanadate and hydroxylamine hydrochloride (1:1): 3mmol of ammonium metavanadate and 3mmol of hydroxylamine hydrochloride are mixed, 100mL of isopropanol is added, the mixture is heated to 90 ℃ and stirred for 4 hours, then the mixture is cooled to room temperature, methanol is removed by rotary evaporation, vacuum drying is carried out at 60 ℃ for 12 hours, the mixture is fully ground and then is subjected to heat treatment for 10 hours in a nitrogen atmosphere at 600 ℃, and then the mixture is cooled, thus obtaining a V-N-C catalyst which is denoted as a catalyst D.
Synthesis of 2.1,4-naphthoquinone
4mmol of alpha-tetralone, 25wt% of catalyst D and 8mL of gamma-butyrolactone are added into a reaction kettle, 1.0MPa of oxygen is filled, the temperature is raised to 100 ℃ under stirring, and the reaction is carried out for 10 hours. Then cooled to room temperature and the pressure was reduced to normal pressure. The sample was taken for quantitative analysis of the product, the conversion of α -tetralone was 70% and the selectivity of 1, 4-naphthoquinone was 80%. The reaction results are shown in Table 1.
Example 5
Preparation of the E catalyst
The preparation process of the V-N-C catalyst adopts the molar ratio of sodium vanadate to cyanuric acid (1:4) to prepare: 2mmol of sodium vanadate and 8mmol of cyanuric acid are mixed, and added into 100mL of water, heated to 100 ℃ and stirred for 4 hours, cooled to room temperature, water is removed by rotary evaporation, vacuum drying is carried out at 80 ℃ for 12 hours, the mixture is fully ground, heat treatment is carried out under the condition of 300 ℃ in nitrogen atmosphere for 10 hours, and then the mixture is cooled, thus obtaining the V-N-C catalyst which is denoted as a catalyst E.
Synthesis of 2.1,4-naphthoquinone
3mmol 3-methyl-1-tetralone, 40wt% catalyst E and 5mL delta-butyrolactone are added into a reaction kettle, 0.1MPa oxygen is filled, the temperature is raised to 150 ℃ under stirring, and the reaction is carried out for 10 hours. Then cooled to room temperature and the pressure was reduced to normal pressure. Samples were taken for quantitative analysis of the product, with a conversion of 78% of alpha-tetralone and a selectivity of 80% for 1, 4-naphthoquinone. The reaction results are shown in Table 1.
Example 6
F catalyst preparation
The Cu-N-C catalyst is prepared by Cheng Caiyong mol ratio of copper acetate and 2-pyridine formamide (1:8): 1mmol of copper acetate and 8mmol of 2-pyridine carboxamide are mixed, 200mL of methanol is added, the mixture is heated to 60 ℃ and stirred for 2 hours, then cooled to room temperature, the methanol is removed by rotary evaporation, vacuum drying is carried out at 80 ℃ for 12 hours, the mixture is fully ground and then is subjected to heat treatment for 5 hours in a nitrogen atmosphere at 500 ℃ and then cooled, and a Cu-N-C catalyst is obtained and is marked as a catalyst F.
Synthesis of 2, 2-nitro-1, 4-naphthoquinone
3mmol of 2-methyl-1-tetralone, 10wt% of catalyst F and 5mL of epsilon-caprolactone are added into a reaction kettle, 0.5MPa of oxygen is filled, the temperature is raised to 130 ℃ under stirring, and the reaction is carried out for 10 hours. Then cooled to room temperature and the pressure was reduced to normal pressure. The sample was taken for quantitative analysis of the product, the conversion of 2-nitro-1-tetralone was 77%, and the selectivity of 2-nitro-1, 4-naphthoquinone was 81%. The reaction results are shown in Table 1.
Example 7
Preparation of G catalyst
The Cu-N-C catalyst is prepared by Cheng Caiyong molar ratio of copper chloride to urea (1:4): 1mmol of copper sulfate and 4mmol of 2-methylimidazole are mixed, 200mL of methanol is added, the mixture is heated to 60 ℃ and stirred for 12 hours, then the mixture is cooled to room temperature, the methanol is removed by rotary evaporation, the mixture is dried for 12 hours at 50 ℃, the mixture is fully ground and then is subjected to heat treatment for 2 hours in a nitrogen atmosphere at 700 ℃, and then the mixture is cooled to obtain a Cu-N-C catalyst which is denoted as a catalyst G.
Synthesis of 2, 2-chloro-2, 3-dihydro-1, 4 naphthoquinone
1mmol of 2-chloro-1, 2,3, 4-tetrahydronaphthalene-1-one, 20wt% of catalyst G and 2mL of delta-valerolactone are added into a reaction kettle, 0.3MPa of oxygen is filled, and the temperature is raised to 100 ℃ under stirring to react for 8 hours. Then cooled to room temperature and the pressure was reduced to normal pressure. The sample was taken for quantitative analysis of the product, the conversion of 2-chloro-1, 2,3, 4-tetrahydronaphthalen-1-one was 70%, and the selectivity of 2-chloro-2, 3-dihydro-1, 4-naphthoquinone was 74%. The reaction results are shown in Table 1.
Example 8
1.H catalyst preparation
The Cu-N-C catalyst is prepared by Cheng Caiyong mol ratio of copper sulfate and triethylene diamine (1:3): 2mmol of copper sulfate and 6mmol of triethylenediamine are mixed, 150mL of methanol is added, the mixture is heated to 60 ℃ and stirred for 1H, then the mixture is cooled to room temperature, the methanol is removed by rotary evaporation, the mixture is dried for 12H at 50 ℃, the mixture is fully ground and then is subjected to heat treatment for 4H in a nitrogen atmosphere at 300 ℃ and then cooled, and a Cu-N-C catalyst is obtained and is marked as a catalyst H.
Synthesis of 2, 2-methoxy-1, 4-naphthoquinone
8mmol of 2-methoxy-3, 4-dihydronaphthalene-1 (2H) ketone, 15wt% of catalyst H and 20mL of epsilon-caprolactone are added into a reaction kettle, 0.7MPa of oxygen is filled, and the temperature is raised to 140 ℃ under stirring to react for 2 hours. Then cooled to room temperature and the pressure was relieved. The reaction mixture was sampled and quantitatively analyzed to obtain a conversion of 2-methoxy-3, 4-dihydronaphthalene-1 (2H) ketone of 65% and a selectivity of 2-methoxy-1, 4-naphthoquinone of 70%. The reaction results are shown in Table 1.
Example 9
Preparation of the catalyst
The Cu-N-C catalyst is prepared by Cheng Caiyong mol ratio of copper chloride dihydrate to dicyandiamide (1:5): 2mmol of copper sulfate and 10mmol of dicyandiamide are mixed, 200mL of ethanol is added, the mixture is heated to 50 ℃ and stirred for 10 hours, then the mixture is cooled to room temperature, the ethanol is removed by rotary evaporation, the mixture is dried for 12 hours at 50 ℃ in vacuum, the mixture is fully ground and then is subjected to heat treatment for 4 hours in a nitrogen atmosphere at 400 ℃, and then the mixture is cooled, so that a Cu-N-C catalyst is obtained and is marked as a catalyst I.
Synthesis of 2, 2-bromo-2, 3-dihydro-1, 4 naphthoquinone
3mmol of 2-bromo-1-tetralone, 5wt% of catalyst I and 6mL of delta-valerolactone are added into a reaction kettle, 0.5MPa of oxygen is filled, the temperature is raised to 60 ℃ under stirring, and the reaction is carried out for 10 hours. Then cooled to room temperature and the pressure was reduced to normal pressure. The sample was taken for quantitative analysis of the product, the conversion of 2-bromo-1-tetralone was 70%, and the selectivity of 2-bromo-2, 3-dihydro-1, 4-naphthoquinone was 73%. The reaction results are shown in Table 1.
Example 10
J catalyst preparation
The Cu-N-C catalyst is prepared by adopting copper nitrate trihydrate and trimellitic acid (1:10) in a molar ratio: 1mmol of copper sulfate and 10mmol of chitosan are mixed, 250mL of ethanol is added, the mixture is heated to 70 ℃ and stirred for 6 hours, then the mixture is cooled to room temperature, the ethanol is removed by rotary evaporation, the mixture is dried for 12 hours at 70 ℃ in vacuum, the mixture is fully ground and then is subjected to heat treatment for 4 hours in a nitrogen atmosphere at 800 ℃, and then the mixture is cooled to obtain a Cu-N-C catalyst which is marked as a catalyst J.
Synthesis of 2, 2-aminonaphthalene-1, 4-dione
3mmol of 2-amino-3, 4-dihydro-1 (2H) -naphthalenone, 20wt% of catalyst J and 10mL of gamma-valerolactone are added into a reaction kettle, 0.6MPa of oxygen is filled, the temperature is raised to 110 ℃ under stirring, and the reaction is carried out for 12 hours. Then cooled to room temperature and the pressure was reduced to normal pressure. Samples were taken for quantitative analysis of the product, the conversion of 2-amino-3, 4-dihydro-1 (2H) -naphthalenone was 71% and the selectivity of 2-aminonaphthalene-1, 4-dione was 82%. The reaction results are shown in Table 1.
Example 11
Synthesis of 2-acetoxy-1, 4-naphthoquinone
Using vanadium trioxide as a catalyst, marking the catalyst as a catalyst K, adding 3mmol of 2-acetoxyl-3, 4-dihydronaphthalene-1 (2H) -ketone, 10wt% of the catalyst K and 5mL of gamma-valerolactone into a reaction kettle, charging 0.5MPa of oxygen, heating to 110 ℃ under stirring, and reacting for 12 hours. Then cooled to room temperature and the pressure was reduced to normal pressure. Samples were taken for quantitative analysis of the product, with a conversion of 65% of 2-acetoxy-3, 4-dihydronaphthalene-1 (2H) -one and a selectivity of 80% for 2-acetoxy-1, 4-naphthoquinone. The reaction results are shown in Table 1.
Example 12
Synthesis of 1, 4-naphthoquinone
Cuprous oxide is used as a catalyst and is marked as a catalyst L, 3mmol of 2-nitro-1-tetralone, 15wt% of the catalyst L and 4mL of gamma-valerolactone are added into a reaction kettle, 0.6MPa of oxygen is filled, and the temperature is raised to 120 ℃ under stirring to react for 10 hours. Then cooled to room temperature and the pressure was reduced to normal pressure. Samples were taken for quantitative analysis of the product, with 62% conversion of alpha-tetralone and 71% selectivity of 1, 4-naphthoquinone. The reaction results are shown in Table 1.
TABLE 1 different catalyst compositions and solvents and the respective reaction results
It is noted that the above-described embodiments are only for explaining the present invention, and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications having the same function.

Claims (10)

1.A method for preparing 1, 4-naphthoquinone compounds by selectively oxidizing aromatic ketone is characterized in that the method is a method for preparing 1, 4-naphthoquinone compounds by selectively oxidizing aromatic ketone in a liquid phase by using copper-based and vanadium-based multi-phase catalysts; the method takes aromatic ketone as a raw material, takes molecular oxygen as an oxygen source, and oxidizes the aromatic ketone into 1, 4-naphthoquinone compounds in an organic solvent through liquid phase catalysis and selection.
2. The method for preparing the 1, 4-naphthoquinone compound by selectively oxidizing aromatic ketone according to claim 1, wherein the specific steps are as follows: adding a catalyst, an aromatic ketone raw material and an organic solvent into a high-pressure reactor, wherein the dosage of the catalyst is 5-40wt% of the dosage of the aromatic ketone, and the dosage of the organic solvent is 1-40 times of the mass of the aromatic ketone; molecular oxygen is used as an oxygen source, the mixture is heated and stirred at the temperature of 60-150 ℃, the partial pressure of the oxygen is 0.1-2MPa, the reaction time is 0.2-12h, the mixture is cooled to room temperature after the reaction is finished, the pressure is reduced to normal pressure, and the 1, 4-naphthoquinone compounds are obtained through separation.
3. The method for preparing 1, 4-naphthoquinone compounds by selectively oxidizing aromatic ketone according to claim 1, wherein the aromatic ketone has a structure in the following reaction scheme, and the 1, 4-naphthoquinone compound has a structure in the following reaction scheme:
wherein R is 1 Is hydrogen, alkyl, phenyl, -Cl, -Br, -F, -NO 2 One or more of methoxy, ethoxy, cyano, amino, acetoxy and acetamido; r is R 2 Is hydrogen, alkyl, phenyl, -Cl, -Br, -F, -NO 2 Methoxy, ethoxy, cyano, aminoOne or more of an acetoxy group and an acetamido group; r is R 1 、R 2 May be the same or different.
4. The method for preparing 1, 4-naphthoquinone compounds by selectively oxidizing aromatic ketone according to claim 1, wherein the organic solvent used in the catalytic oxidation reaction is one or more of gamma valerolactone, delta valerolactone, gamma butyrolactone, and epsilon caprolactone.
5. The method for preparing 1, 4-naphthoquinone compounds by selectively oxidizing aromatic ketone according to claim 1, wherein the molecular oxygen in the catalytic oxidation reaction is air, oxygen or gas containing oxygen, and the partial pressure of oxygen is 0.1-2MPa.
6. The method for preparing 1, 4-naphthoquinone compounds by selectively oxidizing aromatic ketone according to claim 1, wherein the catalyst is one or more of vanadium pentoxide, vanadium dioxide, vanadium trioxide, vanadium nitride, V-N-C composite material, copper oxide, cuprous oxide and Cu-N-C composite material.
7. The method for preparing 1, 4-naphthoquinone compounds by selectively oxidizing aromatic ketone according to claim 6, wherein the catalyst is preferably a V-N-C composite material or a Cu-N-C composite material.
8. The method for preparing 1, 4-naphthoquinone compounds by selectively oxidizing aromatic ketone according to claim 7, wherein the preparation steps of the V-N-C, cu-N-C composite catalyst are as follows:
dissolving a metal source and a nitrogen-containing organic ligand in a solvent, wherein the molar ratio of the metal source to the nitrogen-containing organic ligand is 1:1-1:10, heating and stirring at 30-100 ℃ for 1-12 hours, cooling to room temperature, removing the solvent by rotary evaporation, fully grinding the obtained precursor, pyrolyzing at 300-800 ℃ in an inert gas atmosphere for 0.5-10 hours, cooling, and fully grinding to obtain the Cu-N-C or V-N-C composite material.
9. The method for preparing 1, 4-naphthoquinone compounds by selectively oxidizing aromatic ketone according to claim 8, wherein the copper source used in the preparation process of the V-N-C and Cu-N-C composite material is one or more of copper nitrate, copper chloride, copper acetate, copper sulfate and their hydrates, and the vanadium salt is one or more of ammonium metavanadate, ammonium vanadate, sodium metavanadate, sodium vanadate and their hydrates; the nitrogen-containing organic ligand is one or more of melamine, dicyandiamide, 1, 10-phenanthroline, 2' -bipyridine, phthalocyanine, porphyrin, cyanuric acid, hydroxylamine hydrochloride, triethylene diamine, 2-methylimidazole, imidazole, 2-pyridine formamide, 2, 6-bipyridine formic acid, chitosan and urea.
10. The method for preparing 1, 4-naphthoquinone compounds by selectively oxidizing aromatic ketone according to claim 1, wherein the conversion rate of aromatic ketone is up to 62%; the selectivity of naphthoquinone compounds can reach more than 70 percent.
CN202310908057.0A 2023-07-24 2023-07-24 Method for preparing 1, 4-naphthoquinone compound by selectively oxidizing aromatic ketone Pending CN117142938A (en)

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