A production method of 10,10-dimethylanthracene

Abstract

The application discloses a preparation method of 10,10-dimethylanthracene for preparing 10,10-dimethylanthracene ketone, which is characterized by the following steps: taking 10,10-dimethylanthracene as raw material, and under the action of a cobalt-based catalyst and an oxygen-containing atmosphere, 10,10-dimethylanthracene ketone is prepared in one step, the conversion rate of the raw material 10,10-dimethylanthracene is greater than 85%, and the selectivity of 10,10-dimethylanthracene ketone is greater than 85%. At present, in the industry, 10,10-dimethylanthracene ketone is prepared from 10,10-dimethylanthracene through the oxidation of chromium trioxide or the bromination under light irradiation and a hydrolysis reaction, but there is a great environmental pollution problem in the reaction process. Compared with the prior art, the catalyst system of the application is cheap and easy to obtain, has high catalytic activity, is safe and environmentally friendly, and is simple in post-treatment, and therefore has great industrial application value.

Description

Technical Field

[0001] This invention relates to the field of 10,10-dimethylanthracene preparation technology, and specifically to a method for producing 10,10-dimethylanthrone from 10,10-dimethylanthracene. Background Technology

[0002] Melitracen hydrochloride, chemically named 3-[10,10-dimethyl-9(10H)-anthraminidyl]-N,N-dimethylpropylamine hydrochloride, possesses strong antipsychotic activity, 4-8 times stronger than chlorprothixol, while having a weaker sedative effect. It also exhibits anti-anxiety and antidepressant effects. It is indicated for acute and chronic schizophrenia, depression, and depressive neurosis. Currently, this active pharmaceutical ingredient is only available overseas, and no domestic manufacturers produce it, thus making it of significant research value. Therefore, research on the preparation of 10,10-dimethylanthraquinone, a crucial intermediate in the preparation of melitracen hydrochloride, is particularly important.

[0003] Current domestic and international literature reports on the preparation of 10,10-dimethylanthrone focus on the multi-step synthesis of 10,10-dimethylanthracene from phthalic anhydride, followed by chromium trioxide oxidation or photobromination, and hydrolysis to prepare 10,10-dimethylanthrone. Both of these methods for preparing 10,10-dimethylanthrone from 10,10-dimethylanthracene suffer from environmental pollution and high costs during the reaction process, making them unsuitable for industrial-scale production. Summary of the Invention

[0004] To address the environmental pollution and high cost associated with the current method of preparing 10,10-dimethylanthrone from 10,10-dimethylanthracene, this invention provides a novel method for preparing 10,10-dimethylanthrone from 10,10-dimethylanthracene. This method uses 10,10-dimethylanthracene as a raw material and, under the action of a cobalt-based catalyst and an oxygen-containing atmosphere, prepares 10,10-dimethylanthrone in one step. The conversion rate of 10,10-dimethylanthracene is >85%, and the selectivity of 10,10-dimethylanthrone is greater than 85%. Compared with traditional processes involving chromium trioxide oxidation or photo-bromination and hydrolysis of 10,10-dimethylanthracene, the catalyst in this invention is inexpensive and readily available, exhibits high catalytic activity, is safe and environmentally friendly, and requires simple post-processing, thus possessing significant industrial application value.

[0005] The present invention is achieved through the following technical solution:

[0006] A method for producing 10,10-dimethylanthrone from 10,10-dimethylanthracene involves preparing 10,10-dimethylanthrone in one step using 10,10-dimethylanthracene as a raw material in the presence of a cobalt-based catalyst and an organic solvent, with oxygen or an oxygen-containing atmosphere as the oxidant, at a reaction temperature of 25-200℃ and a reaction time of 5 min–24 h.

[0007]

[0008] The method for preparing 10,10-dimethylanthrone described above is characterized in that the cobalt-based catalyst is one or more heterogeneous supported catalysts;

[0009] The cobalt-based catalyst comprises one or more of Co / SBA-15, Co / zeolite Y alkali metal salt, Co / ZSM-5, Co / CT (carbon nanotubes), Co / SiO2, and Co / SiO2-MgO-Al2O3, wherein the mass percentage of cobalt in the obtained catalyst is 0.5wt%-5wt% (preferably 0.7wt%-3.5wt%).

[0010] The method for preparing 10,10-dimethylanthrone described above is characterized in that the organic solvent is one or more of benzene, cyclohexane, hexane, tetrahydrofuran, acetonitrile, acetic acid, and 1,4-dioxane; the amount of solvent required per millimole of 10,10-dimethylanthrone is 0.2 mL to 50.0 mL, preferably 1.0 mL to 5.0 mL; the oxygen-containing atmosphere includes one or more of air, oxygen, or other mixtures of nitrogen, argon, carbon dioxide, helium, and oxygen, wherein the oxygen volume content is 10-100%, preferably 20-50%; the reaction temperature is 25-200℃, preferably 80-120℃; and the reaction time is 5 min to 24 h, preferably 3-8 h. The molar ratio of 10,10-dimethylanthracene to cobalt in the catalyst is 1:0.001 to 5, preferably 1:0.1 to 0.5; the molar ratio of 10,10-dimethylanthracene to oxygen is 1:1 to 18, preferably 1:2 to 5.

[0011] In the above-described method for preparing 10,10-dimethylanthrone, the heterogeneous supported catalyst in the system is a cobalt salt that is immobilized on a support. The cobalt salt includes one or more of cobalt chloride, cobalt bromide, cobalt sulfate, cobalt(II) acetylacetonate, cobalt acetate, cobalt nitrate, cobalt oxide, cobalt tetroxide, and cobalt trioxide.

[0012] The heterogeneous supported catalyst is prepared by organic solvent impregnation or vacuum impregnation.

[0013] Organic solvent impregnation method:

[0014] Weigh out the cobalt salt catalyst and organic solvent and mix them. Sonicate or stir for 5-120 min to fully disperse them to obtain a cobalt salt mixture. Then, quickly add one or more of SBA-15, zeolite Y alkali metal salt, ZSM-5, CT (carbon nanotubes), SiO2 and SiO2-MgO-Al2O3 (the support is pre-dried under vacuum at 50-100℃ for 3-8 hours) to the cobalt salt mixture. Impregnate at room temperature for 1-24 hours, filter and wash, vacuum dry at 30-60℃, and calcine in a muffle furnace at 400-600℃ for 1-12 h, preferably 2-8 h. The mass percentage of cobalt in the obtained catalyst is 0.5wt%-5wt%.

[0015] Vacuum impregnation method:

[0016] One or more of the following supports—SBA-15, zeolite Y alkali metal salt, ZSM-5, CT (carbon nanotubes), SiO2, and SiO2-MgO-Al2O3—are vacuum dried at 50-100℃ for 3-8 hours. After cooling to room temperature, an aqueous solution of cobalt salt (0.001-0.10M, preferably 0.003-0.05M) is added under vacuum (<0.04MPa). The mixture is stirred and impregnated for 1-24 hours, filtered and washed, vacuum dried at 30-60℃, and calcined in a muffle furnace at 400-600℃ for 1-12 hours, preferably 2-8 hours. The resulting catalyst has a cobalt mass percentage of 0.5wt%-5wt%.

[0017] The organic solvent used in the above-described organic solvent impregnation method is one or more of ethanol, methanol, ethylene glycol, glycerol, isopropanol, tert-butanol, tert-amyl alcohol, acetonitrile, and tetrahydrofuran; the cobalt salt concentration is 0.001-0.10M, preferably 0.003-0.05M; the zeolite Y alkali metal salt is one or more of zeolite Y sodium salt, zeolite Y potassium salt, and zeolite Y cesium salt; and SiO2 is one or more of various forms of silica sol, silica gel, silica balls, and fumed silica.

[0018] In both the organic solvent impregnation method and the vacuum impregnation method, the impregnation time for metallic cobalt is 1-24 h, preferably 3-8 h. In both the organic solvent impregnation method and the vacuum impregnation method, the calcination temperature of the obtained catalyst precursor is 400-600 °C, preferably 450-550 °C.

[0019] Currently, the industrial preparation of 10,10-dimethylanthrene from 10,10-dimethylanthracene involves chromium trioxide oxidation or photo-bromination followed by hydrolysis. However, this process causes significant environmental pollution. In contrast, the catalyst in this invention is inexpensive, readily available, highly active, safe, environmentally friendly, and requires simple post-processing, making it highly valuable for industrial applications. Detailed Implementation

[0020] The present invention will be further described in detail below with reference to specific embodiments. The scope of protection of the present invention includes, but is not limited to, the following embodiments. Any modifications to the details and form of the technical solution of the present invention without departing from the meaning and scope of this application shall fall within the scope of protection of the present invention.

[0021] Example 1

[0022] Organic solvent impregnation method:

[0023] Weigh 0.03 g of cobalt acetate and mix with 30 mL of isopropanol. Sonicate for 15 min to fully disperse the cobalt acetate solution. Then, quickly add 1.0 g of commercially available SBA-15 molecular sieve (with the support pre-dried under vacuum at 100 °C for 3 hours) to the cobalt acetate solution. Impregnate at room temperature for 8 hours. After filtration, wash three times with isopropanol, dry under vacuum at 60 °C for 8 hours, and calcine in a muffle furnace at 500 °C for 5 hours. The mass percentage of cobalt in the obtained catalyst is 1.0 wt%, and the catalyst is labeled as 1.0 wt%-Co / SBA-15-iPrOH-1.

[0024] Vacuum impregnation method:

[0025] 1.0 g of commercially available SBA-15 was vacuum dried at 100 °C for 3 hours. After cooling to room temperature, 30 mL of an aqueous solution containing 0.030 g of cobalt acetate was added to the support under vacuum conditions (<0.04 MPa). The mixture was stirred and impregnated for 8 hours. After filtration, the mixture was washed three times with deionized water, vacuum dried at 60 °C for 8 hours, and calcined in a muffle furnace at 500 °C for 5 hours. The mass percentage of cobalt in the obtained catalyst was 1.0 wt%, and the catalyst was labeled as 1.0 wt%-Co / SBA-15-Vacuum-1.

[0026] Comparative Example 1

[0027] Organic solvent impregnation method:

[0028] 0.03 g of nickel acetate and 30 mL of isopropanol were weighed and mixed, and sonicated for 15 min to fully disperse them to obtain a cobalt acetate solution. Then, 1.0 g of commercially available SBA-15 molecular sieve (with the support pre-dried under vacuum at 100 °C for 3 hours) was quickly added to the above cobalt acetate solution and impregnated at room temperature for 8 hours. After filtration, it was washed three times with isopropanol, dried under vacuum at 60 °C for 8 hours, and calcined in a muffle furnace at 500 °C for 5 hours. The mass percentage of nickel in the obtained catalyst was 1.0 wt%, and the catalyst was labeled as 1.0 wt%-Ni / SBA-15-iPrOH-1A.

[0029] Vacuum impregnation method:

[0030] 1.0 g of commercially available SBA-15 was vacuum dried at 100 °C for 3 hours. After cooling to room temperature, 30 mL of an aqueous solution containing 0.030 g of nickel acetate was added to the support under vacuum conditions (<0.04 MPa). The mixture was stirred and impregnated for 8 hours. After filtration, the mixture was washed three times with deionized water, vacuum dried at 60 °C for 8 hours, and calcined in a muffle furnace at 500 °C for 5 hours. The resulting catalyst had a nickel mass percentage of 1.0 wt% and was labeled as 1.0 wt%-Ni / SBA-15-Vacuum-1A.

[0031] Comparative Example 2

[0032] Organic solvent impregnation method:

[0033] 0.03 g of cobalt acetate and 300 mL of isopropanol were weighed and mixed, and sonicated for 15 min to fully disperse them to obtain a cobalt acetate solution. Then, 1.0 g of commercially available SBA-15 molecular sieve (with the support pre-dried under vacuum at 100 °C for 3 hours) was quickly added to the above cobalt acetate solution and impregnated at room temperature for 8 hours. After filtration, the solution was washed three times with isopropanol, dried under vacuum at 60 °C for 8 hours, and calcined in a muffle furnace at 500 °C for 5 hours. The mass percentage of cobalt in the obtained catalyst was 0.71 wt%, and the catalyst was labeled as 0.71 wt%-Co / SBA-15-iPrOH-1B.

[0034] Vacuum impregnation method:

[0035] 1.0 g of commercially available SBA-15 was vacuum dried at 100 °C for 3 hours. After cooling to room temperature, 300 mL of an aqueous solution containing 0.030 g of cobalt acetate was added to the support under vacuum conditions (<0.04 MPa). The mixture was stirred and impregnated for 8 hours. After filtration, the mixture was washed three times with deionized water, vacuum dried at 60 °C for 8 hours, and calcined in a muffle furnace at 500 °C for 5 hours. The resulting catalyst had a cobalt mass percentage of 0.75 wt% and was labeled as 0.75 wt%-Co / SBA-15-Vacuum-1B.

[0036] Comparative Example 3

[0037] Organic solvent impregnation method:

[0038] Weigh 0.03 g of cobalt acetate and mix with 30 mL of isopropanol. Sonicate for 15 min to fully disperse the cobalt acetate solution. Then, quickly add 1.0 g of commercially available SBA-15 molecular sieve (with the support pre-dried under vacuum at 100 °C for 3 hours) to the cobalt acetate solution. Impregnate at room temperature for 0.5 hours. After filtration, wash three times with isopropanol, dry under vacuum at 60 °C for 8 hours, and calcine in a muffle furnace at 500 °C for 5 hours. The mass percentage of cobalt in the obtained catalyst is 0.42 wt%, and the catalyst is labeled as 0.42 wt%-Co / SBA-15-iPrOH-1C.

[0039] Vacuum impregnation method:

[0040] 1.0 g of commercially available SBA-15 was vacuum dried at 100 °C for 3 hours. After cooling to room temperature, 30 mL of an aqueous solution containing 0.030 g of cobalt acetate was added to the support under vacuum conditions (<0.04 MPa). The mixture was stirred and impregnated for 0.5 hours. After filtration, the mixture was washed three times with deionized water, vacuum dried at 60 °C for 8 hours, and calcined in a muffle furnace at 500 °C for 5 hours. The resulting catalyst had a cobalt mass percentage of 0.47 wt% and was labeled as 0.47 wt%-Co / SBA-15-Vacuum-1C.

[0041] Comparative Example 4

[0042] Organic solvent impregnation method:

[0043] Weigh 0.03 g of cobalt acetate and mix with 30 mL of isopropanol. Sonicate for 15 min to fully disperse the cobalt acetate solution. Then, quickly add 1.0 g of commercially available SBA-15 molecular sieve (with the support pre-dried under vacuum at 100 °C for 1 hour) to the cobalt acetate solution. Impregnate at room temperature for 8 hours. After filtration, wash three times with isopropanol, dry under vacuum at 60 °C for 8 hours, and calcine in a muffle furnace at 300 °C for 5 hours. The mass percentage of cobalt in the obtained catalyst is 0.97 wt%, and the catalyst is labeled as 0.97 wt%-Co / SBA-15-iPrOH-1D.

[0044] Vacuum impregnation method:

[0045] 1.0 g of commercially available SBA-15 was vacuum dried at 100 °C for 1 hour. After cooling to room temperature, 30 mL of an aqueous solution containing 0.030 g of cobalt acetate was added to the support under vacuum conditions (<0.04 MPa). The mixture was stirred and impregnated for 8 hours. After filtration, the mixture was washed three times with deionized water, vacuum dried at 60 °C for 0.5 h, and calcined in a muffle furnace at 300 °C for 5 h. The resulting catalyst had a cobalt mass percentage of 0.97 wt% and was labeled as 0.97 wt%-Co / SBA-15-Vacuum-1D.

[0046] Comparative Example 5

[0047] Organic solvent impregnation method:

[0048] Weigh 0.03 g of cobalt acetate and mix with 30 mL of isopropanol. Sonicate for 15 min to fully disperse the cobalt acetate solution. Then, quickly add 1.0 g of commercially available SBA-15 molecular sieve (with the support pre-dried under vacuum at 40 °C for 2 hours) to the cobalt acetate solution. Impregnate at room temperature for 8 hours. After filtration, wash three times with isopropanol, dry under vacuum at 60 °C for 8 hours, and calcine in a muffle furnace at 800 °C for 2 hours. The mass percentage of cobalt in the obtained catalyst is 1.0 wt%, and the catalyst is labeled as 1.0 wt%-Co / SBA-15-iPrOH-1E.

[0049] Vacuum impregnation method:

[0050] 1.0 g of commercially available SBA-15 was vacuum dried at 40 °C for 1 hour. After cooling to room temperature, 30 mL of an aqueous solution containing 0.030 g of cobalt acetate was added to the support under vacuum conditions (<0.04 MPa). The mixture was stirred and impregnated for 8 hours. After filtration, the mixture was washed three times with deionized water, vacuum dried at 60 °C for 0.5 h, and calcined in a muffle furnace at 800 °C for 3 h. The resulting catalyst had a cobalt mass percentage of 1.0 wt% and was labeled as 1.0 wt%-Co / SBA-15-Vacuum-1E.

[0051] Example 2

[0052] Organic solvent impregnation method:

[0053] Weigh 0.06 g of cobalt acetate and 30 mL of ethanol and mix them. Sonicate for 15 min to fully disperse the cobalt acetate solution. Then, quickly add 1.0 g of commercially available SBA-15 molecular sieve (with the support pre-dried under vacuum at 100 °C for 3 hours) to the cobalt acetate solution. Impregnate at room temperature for 3 hours. After filtration, wash three times with ethanol, keep at 60 °C under vacuum for 8 hours, and calcine in a muffle furnace at 500 °C for 5 hours. The mass percentage of cobalt in the obtained catalyst is 2.0 wt%, and the catalyst is labeled as 2.0 wt%-Co / SBA-15-EtOH-2.

[0054] Vacuum impregnation method:

[0055] 1.0 g of commercially available SBA-15 was vacuum dried at 100 °C for 3 hours. After cooling to room temperature, 30 mL of an aqueous solution containing 0.060 g of cobalt acetate was added to the support under vacuum conditions (<0.04 MPa). The mixture was stirred and impregnated for 8 hours. After filtration, the mixture was washed three times with deionized water, vacuum dried at 60 °C for 8 hours, and calcined in a muffle furnace at 500 °C for 5 hours. The resulting catalyst had a cobalt mass percentage of 2.0 wt% and was labeled as 2.0 wt%-Co / SBA-15-Vacuum-2.

[0056] Example 3

[0057] Organic solvent impregnation method:

[0058] Weigh 0.06 g of cobalt acetate and 30 mL of ethanol and mix them. Sonicate for 15 min to fully disperse the cobalt acetate solution. Then, quickly add 1.0 g of commercially available sodium zeolite Y molecular sieve (manufacturer: Alfa Aesar, specific surface area 900 m² / g, silicon-aluminum molar ratio 5.1:1; the same raw material is used in the following examples; the support is pre-dried under vacuum at 100°C for 3 hours) to the above cobalt acetate solution. Impregnate at room temperature for 3 hours, filter, wash three times with ethanol, keep at 60°C under vacuum for 8 hours, and calcine in a muffle furnace at 500°C for 5 hours. The mass percentage of cobalt in the obtained catalyst is 2.0 wt%, and the catalyst is labeled as 2.0 wt%-Co / sodium zeolite Y-EtOH-3.

[0059] Vacuum impregnation method:

[0060] 1.0 g of commercially available sodium zeolite Y was vacuum dried at 100 °C for 3 hours. After cooling to room temperature, 30 mL of an aqueous solution containing 0.060 g of cobalt acetate was added to the support under vacuum conditions (<0.04 MPa). The mixture was stirred and impregnated for 8 hours. After filtration, the mixture was washed three times with deionized water, vacuum dried at 60 °C for 8 hours, and calcined in a muffle furnace at 500 °C for 5 hours. The resulting catalyst had a cobalt mass percentage of 2.0 wt% and was labeled as 2.0 wt%-Co / sodium zeolite Y-Vacuum-3.

[0061] Example 4

[0062] Organic solvent impregnation method:

[0063] 0.09 g of cobalt acetate and 30 mL of ethylene glycol were weighed and mixed, and sonicated for 15 min to fully disperse them to obtain a cobalt acetate solution. Then, 1.0 g of commercially available multi-walled carbon nanotubes (Aladdin, purity ≥95%, average diameter 11 nm, average length 10 μm, support pre-dried under vacuum at 100 °C for 3 hours) were quickly added to the above cobalt acetate solution and impregnated at room temperature for 3 hours. After filtration, the catalyst was washed 3 times with ethylene glycol and 2 times with ethanol, dried under vacuum at 60 °C for 8 hours, and calcined in a muffle furnace at 500 °C for 5 hours. The mass percentage of cobalt in the obtained catalyst was 3.0 wt%, and the catalyst was labeled as 3.0 wt%-Co / CT-EG-4.

[0064] Vacuum impregnation method:

[0065] 1.0 g of commercially available multi-walled carbon nanotubes (Aladdin, purity ≥95%, average diameter 11 nm, average length 10 μm) were vacuum dried at 100 °C for 3 hours. After cooling to room temperature, 30 mL of an aqueous solution containing 0.090 g of cobalt acetate was added to the support under vacuum conditions (<0.04 MPa). The mixture was stirred and impregnated for 12 hours. After filtration, the mixture was washed three times with deionized water, vacuum dried at 60 °C for 8 hours, and calcined in a muffle furnace at 600 °C for 5 hours. The resulting catalyst had a cobalt mass percentage of 3.0 wt% and was labeled as 3.0 wt%-Co / CT-Vacuum-4.

[0066] Example 5

[0067] Organic solvent impregnation method:

[0068] Weigh 0.03 g of cobalt acetate and 30 mL of ethanol and mix them. Sonicate for 30 min to fully disperse the cobalt acetate solution. Then, quickly add 1.0 g of commercially available SiO2 (200-300 mesh, with the support pre-dried under vacuum at 100 °C for 5 hours) to the cobalt acetate solution. Impregnate at room temperature for 5 hours. After filtration, wash three times with ethanol, keep at 60 °C under vacuum for 8 hours, and calcine in a muffle furnace at 500 °C for 5 hours. The mass percentage of cobalt in the obtained catalyst is 1.0 wt%, and the catalyst is labeled as 1.0 wt%-Co / SiO2-EtOH-5.

[0069] Vacuum impregnation method:

[0070] Commercially available SiO2 (200-300 mesh) was vacuum dried at 100℃ for 3 hours. After cooling to room temperature, 30 mL of an aqueous solution containing 0.030 g of cobalt acetate was added to the support under vacuum conditions (<0.04 MPa). The mixture was stirred and impregnated for 8 hours. After filtration, the mixture was washed three times with deionized water, vacuum dried at 60℃ for 8 hours, and calcined in a muffle furnace at 600℃ for 5 hours. The resulting catalyst had a cobalt mass percentage of 1.0 wt% and was labeled as 1.0 wt%-Co / SiO2-Vacuum-5.

[0071] Example 6

[0072] Organic solvent impregnation method:

[0073] 0.044 g of cobalt(II) acetylacetone was weighed and mixed with 30 mL of ethanol. The mixture was sonicated for 30 min to fully disperse the cobalt acetate solution. Then, 1.0 g of commercially available sodium zeolite Y (with the support pre-dried under vacuum at 100 °C for 5 h) was quickly added to the cobalt acetate solution. The mixture was impregnated at room temperature for 5 h, filtered, washed three times with ethanol, dried under vacuum at 60 °C for 8 h, and calcined in a muffle furnace at 500 °C for 5 h. The mass percentage of cobalt in the resulting catalyst was 1.0 wt%, and the catalyst was labeled as 1.0 wt%-Co / SiO2-EtOH-6.

[0074] Vacuum impregnation method:

[0075] 1.0 g of commercially available sodium zeolite Y was vacuum dried at 100 °C for 3 hours. After cooling to room temperature, 30 mL of water-ethylene glycol solution (V / V = 1:1) containing 0.044 g of cobalt(II) acetylacetonate was added to the support under vacuum conditions (<0.04 MPa). The mixture was stirred and impregnated for 8 hours. After filtration, the mixture was washed three times with deionized water, vacuum dried at 60 °C for 8 hours, and calcined in a muffle furnace at 600 °C for 5 hours. The mass percentage of cobalt in the obtained catalyst was 1.0 wt%, and the catalyst was labeled as 1.0 wt%-Co / SiO2-Vacuum-6.

[0076] Example 7

[0077] The cobalt-based heterogeneous supported catalyst (1,10-dimethylanthracene to cobalt in the catalyst molar ratio of 1:0.2) obtained in the above examples, 2.083 g of 10,10-dimethylanthracene, and 20 mL of acetonitrile were sequentially added to a 100 mL stainless steel reactor. The reactor was sealed, oxygen (0.8 g) was introduced, and the reaction was carried out in an 80 °C water bath for 12 h to produce 10,10-dimethylanthrone. After the reaction, the reactor was cooled to room temperature using an ice-water bath, and the pressure was slowly released to atmospheric pressure. The reactor was then opened, and 1.0 g of naphthalene was added to the reaction solution as an internal standard. The conversion rate of 10,10-dimethylanthracene and the selectivity of 10,10-dimethylanthrone were analyzed by gas chromatography. The catalyst was separated by centrifugation, washed three times with acetonitrile, and dried under vacuum at 50 °C for 8 h. The reaction was then repeated in cycles as described above. After ten cycles, an internal standard was added to the reaction solution, and the conversion rate and selectivity were analyzed by gas chromatography as shown in Table 1.

[0078] Table 1

[0079]

[0080]

[0081] Example 8

[0082] A cobalt-based heterogeneous supported catalyst, consisting of 1.0 wt% Co / SiO2-EtOH-5 (with a molar ratio of 1:0.1 between 10,10-dimethylanthracene and cobalt in the catalyst), 2.083 g of 10,10-dimethylanthracene, and 20 mL of acetic acid, was sequentially added to a 100 mL stainless steel reactor. The reactor was sealed, and oxygen (0.8 g) was introduced. The reaction was carried out in an 80°C water bath for 6 h to produce 10,10-dimethylanthrone. After the reaction, the reactor was cooled to room temperature using an ice-water bath, and the pressure was slowly released to atmospheric pressure. The reactor was then opened, and 1.0 g of naphthalene was added to the reaction solution as an internal standard. The conversion and selectivity were analyzed by gas chromatography. The conversion rate of 10,10-dimethylanthracene was 94.4%, and the selectivity of 10,10-dimethylanthrone was 96.8%. The catalyst was centrifuged, washed three times with acetonitrile, and then vacuum dried at 50°C for 8 h. The process was repeated for recycling. After ten cycles, the conversion of 10,10-dimethylanthracene was 90.4%, and the selectivity of 10,10-dimethylanthrone was 94.2%.

[0083] Example 9

[0084] A cobalt-based heterogeneous supported catalyst, consisting of 1.0 wt% Co / SiO2-EtOH-5 (with a molar ratio of 1:0.1 between 10,10-dimethylanthracene and cobalt in the catalyst), 2.083 g of 10,10-dimethylanthracene, and 20 mL of acetic acid, was sequentially added to a 100 mL stainless steel reactor. The reactor was sealed, and oxygen (0.8 g) was introduced. The reaction was carried out in a 120 °C water bath for 4 h to produce 10,10-dimethylanthrone. After the reaction, the reactor was cooled to room temperature using an ice-water bath, and the pressure was slowly released to atmospheric pressure. The reactor was then opened, and 1.0 g of naphthalene was added to the reaction solution as an internal standard. The conversion and selectivity were analyzed by gas chromatography. The conversion rate of 10,10-dimethylanthracene was 94.4%, and the selectivity of 10,10-dimethylanthrone was 86.8%. The catalyst was centrifuged, washed three times with acetonitrile, and then vacuum dried at 50 °C for 8 h. The catalyst was then recycled using the same process. After ten cycles, the conversion of 10,10-dimethylanthracene was 90.4%, and the selectivity of 10,10-dimethylanthrone was 86.2%.

[0085] Example 10

[0086] A cobalt-based heterogeneous supported catalyst, consisting of 1.0 wt% Co / SiO2-EtOH-5 (with a molar ratio of 1:0.1 between 10,10-dimethylanthracene and cobalt in the catalyst), 2.083 g of 10,10-dimethylanthracene, and 20 mL of acetic acid, was sequentially added to a 100 mL stainless steel reactor. The reactor was sealed, and oxygen (1.2 g) was introduced. The reaction was carried out in a 100°C water bath for 5 h to produce 10,10-dimethylanthrone. After the reaction, the reactor was cooled to room temperature using an ice-water bath, and the pressure was slowly released to atmospheric pressure. The reactor was then opened, and 1.0 g of naphthalene was added to the reaction solution as an internal standard. The conversion and selectivity were analyzed by gas chromatography. The conversion rate of 10,10-dimethylanthracene was 97.4%, and the selectivity of 10,10-dimethylanthrone was 94.8%. The catalyst was centrifuged, washed three times with acetonitrile, and then vacuum dried at 50°C for 8 h. The process was repeated for recycling. After ten cycles, the conversion of 10,10-dimethylanthracene was 96.4%, and the selectivity of 10,10-dimethylanthrone was 94.2%.

[0087] Example 11

[0088] A cobalt-based heterogeneous supported catalyst (2.0 wt% Co / sodium zeolite Y-Vacuum-3, with a molar ratio of 1:0.1 between 10,10-dimethylanthracene and cobalt in the catalyst), 2.52 g of 10,10-dimethylanthracene, and 20 mL of acetic acid were sequentially added to a 100 mL stainless steel reactor. The reactor was sealed, and oxygen (4.0 g) was introduced. The reaction was carried out in a 100 °C water bath for 3 h to produce 10,10-dimethylanthrone. After the reaction, the reactor was cooled to room temperature using an ice-water bath, and the pressure was slowly released to atmospheric pressure. The reactor was then opened, and 1.0 g of naphthalene was added to the reaction solution as an internal standard. The conversion and selectivity were analyzed by gas chromatography. The conversion rate of 10,10-dimethylanthracene was 98.4%, and the selectivity of 10,10-dimethylanthrone was 95.8%. The catalyst was centrifuged, washed three times with acetonitrile, and then vacuum dried at 50 °C for 8 h. The process was repeated for recycling. After ten cycles, the conversion of 10,10-dimethylanthracene was 97.4%, and the selectivity of 10,10-dimethylanthrone was 94.7%.

[0089] Example 12

[0090] A cobalt-based heterogeneous supported catalyst (2.0 wt% Co / sodium zeolite Y-EtOH-3, with a molar ratio of 1:0.5 between 10,10-dimethylanthracene and cobalt in the catalyst), 2.52 g of 10,10-dimethylanthracene, and 30 mL of acetic acid were sequentially added to a 100 mL stainless steel reactor. The reactor was sealed, and oxygen (1.0 g) was introduced. The reaction was carried out in a 100°C water bath for 3 h to produce 10,10-dimethylanthrone. After the reaction, the reactor was cooled to room temperature using an ice-water bath, and the pressure was slowly released to atmospheric pressure. The reactor was then opened, and 1.0 g of naphthalene was added to the reaction solution as an internal standard. The conversion and selectivity were analyzed by gas chromatography. The conversion rate of 10,10-dimethylanthracene was 99.4%, and the selectivity of 10,10-dimethylanthrone was 98.8%. The catalyst was centrifuged, washed three times with acetonitrile, and then vacuum dried at 50°C for 8 h. The process was repeated for recycling. After ten cycles, the conversion of 10,10-dimethylanthracene was 98.7%, and the selectivity of 10,10-dimethylanthrone was 98.1%.

[0091] Example 13

[0092] A cobalt-based heterogeneous supported catalyst (2.0 wt% Co / sodium zeolite Y-EtOH-3, with a molar ratio of 1,10-dimethylanthracene to cobalt in the catalyst of 1:0.3), 3.16 g of 10,10-dimethylanthracene, and 25 mL of acetic acid were sequentially added to a 100 mL stainless steel reactor. The reactor was sealed, and oxygen (1.5 g) was introduced. The reaction was carried out in a 100 °C water bath for 3 h to produce 10,10-dimethylanthrone. After the reaction, the reactor was cooled to room temperature using an ice-water bath, and the pressure was slowly released to atmospheric pressure. The reactor was then opened, and 1.0 g of naphthalene was added to the reaction solution as an internal standard. The conversion and selectivity were analyzed by gas chromatography. The conversion of 10,10-dimethylanthracene was 95.4%, and the selectivity of 10,10-dimethylanthrone was 96.2%. The catalyst was centrifuged, washed three times with acetonitrile, and dried under vacuum at 50 °C for 8 h. The reaction was then recycled using the same process. After ten cycles, the conversion of 10,10-dimethylanthracene was 94.7%, and the selectivity of 10,10-dimethylanthrone was 96.1%.

[0093] Example 14

[0094] A cobalt-based heterogeneous supported catalyst (2.0 wt% Co / sodium zeolite Y-EtOH-3, with a molar ratio of 1:0.2 between 10,10-dimethylanthracene and cobalt in the catalyst), 2.08 g of 10,10-dimethylanthracene, and 25 mL of acetic acid were sequentially added to a 100 mL stainless steel reactor. The reactor was sealed, and air (4.0 g) was introduced. The reaction was carried out in a 120 °C water bath for 5 h to produce 10,10-dimethylanthrone. After the reaction, the reactor was cooled to room temperature using an ice-water bath, and the pressure was slowly released to atmospheric pressure. The reactor was then opened, and 1.0 g of naphthalene was added to the reaction solution as an internal standard. The conversion and selectivity were analyzed by gas chromatography. The conversion of 10,10-dimethylanthracene was 88.4%, and the selectivity of 10,10-dimethylanthrone was 87.2%. The catalyst was centrifuged, washed three times with acetonitrile, and then vacuum dried at 50 °C for 8 h. The reaction was then recycled using the same process. After ten cycles, the conversion of 10,10-dimethylanthracene was 88.1%, and the selectivity of 10,10-dimethylanthrone was 84.9%.

[0095] Example 15

[0096] 2.0 wt% Co / SBA-15-Vacuum-2 cobalt-based heterogeneous supported catalyst (molar ratio of 10,10-dimethylanthracene to cobalt in the catalyst is 1:0.25), 2.08 g of 10,10-dimethylanthracene, and 25 mL of acetic acid were sequentially added to a 100 mL stainless steel reactor. The reactor was sealed and purged with a mixture of carbon dioxide and oxygen (4.0 g) at a volume ratio of V / V = 1:1. The reaction was carried out in an 80 °C water bath for 5 h to produce 10,10-dimethylanthrone. After the reaction was completed, the reactor was cooled to room temperature using an ice-water bath, and the pressure was slowly released to atmospheric pressure. The reactor was then opened, and 1.0 g of naphthalene was added to the reaction solution as an internal standard. The conversion and selectivity were analyzed by gas chromatography. The conversion rate of 10,10-dimethylanthracene was 89.7%, and the selectivity of 10,10-dimethylanthrone was 93.2%. After centrifugation to separate the catalyst, it was washed three times with acetonitrile and then vacuum-dried at 50°C for 8 hours. The catalyst was then recycled according to the above process. After ten cycles, the conversion rate of 10,10-dimethylanthracene was 89.5%, and the selectivity of 10,10-dimethylanthrone was 91.3%.

Claims

1. A method for producing 10,10-dimethylanthrone, characterized in that, In the presence of a cobalt-based catalyst and an organic solvent, using oxygen or an oxygen-containing atmosphere as an oxidant, and 10,10-dimethylanthracene as a raw material, 10,10-dimethylanthrone is prepared in one step at a reaction temperature of 25-200℃ and a reaction time of 5 min–24 h. The cobalt-based catalyst is one or more of heterogeneous supported catalysts; The cobalt-based catalyst comprises one or more of Co / SBA-15, Co / zeolite Y alkali metal salt, Co / ZSM-5, Co / carbon nanotube, and Co / SiO2, and the mass percentage of cobalt in the obtained catalyst is 1.0wt%-3.0wt%.

2. The method for preparing 10,10-dimethylanthrone according to claim 1, characterized in that, The organic solvent is one or more of benzene, cyclohexane, hexane, tetrahydrofuran, acetonitrile, acetic acid, and 1,4-dioxane; the amount of solvent required per millimole of 10,10-dimethylanthracene is 0.2 mL to 50.0 mL; The oxygen-containing atmosphere includes one or more of air, oxygen, or other nitrogen, argon, carbon dioxide, helium, and oxygen mixed with one or more other gases, wherein the oxygen volume content is 10-100%.

3. The method for preparing 10,10-dimethylanthrone according to claim 2, characterized in that, The amount of solvent required per millimole of 10,10-dimethylanthracene is 1.0 mL to 5.0 mL; the oxygen volume content is 20-50%.

4. The method for preparing 10,10-dimethylanthrone according to claim 1, characterized in that, The reaction temperature is 25-200 °C; the reaction time is 5 min-24 h; the molar ratio of 10,10-dimethylanthracene to cobalt in the catalyst is 1:0.001-5; the molar ratio of 10,10-dimethylanthracene to oxygen in the oxygen-containing atmosphere is 1:1-18.

5. The method for preparing 10,10-dimethylanthrone according to claim 4, characterized in that, The reaction temperature is 80-120℃; the reaction time is 3-8h; the molar ratio of 10,10-dimethylanthracene to cobalt in the catalyst is 1:0.1~0.5; the molar ratio of 10,10-dimethylanthracene to oxygen in the oxygen-containing atmosphere is 1:2~5.

6. The method for preparing 10,10-dimethylanthrone according to any one of claims 1-5, characterized in that, Heterogeneous supported catalysts are cobalt salts immobilized on a support, wherein the cobalt salts include one or more of cobalt chloride, cobalt bromide, cobalt sulfate, cobalt(II) acetylacetonate, cobalt acetate, cobalt nitrate, cobalt oxide, cobalt tetroxide, and cobalt trioxide; The heterogeneous supported catalyst is prepared by organic solvent impregnation or vacuum impregnation. Organic solvent impregnation method: Weigh out cobalt salt and organic solvent and mix them. Sonicate or stir for 5-120 min to fully disperse them into a cobalt salt mixture. Then, quickly add one or more of the following: SBA-15, zeolite Y alkali metal salt, ZSM-5, carbon nanotubes, and SiO2. The support is pre-dried under vacuum at 50-100℃ for 3-8 hours. Add the cobalt salt mixture to the mixture and impregnate at room temperature for 1-24 hours. Filter and wash, then vacuum dry at 30-60℃ and calcine in a muffle furnace at 400-600℃ for 1-12 h. The resulting catalyst has a cobalt mass percentage of 1.0wt%-3.0wt%. Vacuum impregnation method: One or more of the following supports—SBA-15, zeolite Y alkali metal salt, ZSM-5, carbon nanotubes, and SiO2—are vacuum dried at 50-100℃ for 3-8 hours. After cooling to room temperature, a 0.001-0.10 M aqueous solution of cobalt salt is added under a vacuum of less than 0.04 MPa. The mixture is stirred and impregnated for 1-24 hours, filtered and washed, vacuum dried at 30-60℃, and calcined in a muffle furnace at 400-600℃ for 1-12 hours. The resulting catalyst has a cobalt mass percentage of 1.0 wt%-3.0 wt%.

7. The preparation method according to claim 6, characterized in that, The heterogeneous supported catalyst is prepared by organic solvent impregnation or vacuum impregnation. Organic solvent impregnation method: The catalyst was calcined in a muffle furnace at 400–600℃ for 2–8 hours, yielding a cobalt mass percentage of 1.0 wt%–3.0 wt%. Vacuum impregnation method: The catalyst was calcined in a muffle furnace at 400–600℃ for 2–8 hours, and the mass percentage of cobalt obtained was 1.0wt%–3.0wt%.

8. The preparation method according to claim 6, characterized in that, The organic solvent used in the organic solvent impregnation method is one or more of ethanol, methanol, ethylene glycol, glycerol, isopropanol, tert-butanol, tert-amyl alcohol, acetonitrile, and tetrahydrofuran, with the cobalt salt having a concentration of 0.001-0.10 M. Zeolite Y alkali metal salt is one or more of zeolite Y sodium salt, zeolite Y potassium salt, and zeolite Y cesium salt; SiO2 is one or more of various forms of silica sol, silica gel, silica balls, and precipitated silica.

9. The preparation method according to claim 8, characterized in that, The organic solvent used in the organic solvent impregnation method is one or more of ethanol, methanol, ethylene glycol, glycerol, isopropanol, tert-butanol, tert-amyl alcohol, acetonitrile, and tetrahydrofuran, with the cobalt salt having a concentration of 0.003-0.05M.

10. The preparation method according to claim 6, characterized in that, In both the organic solvent impregnation method and the vacuum impregnation method, the impregnation time of metallic cobalt is 1-24 h; in both the organic solvent impregnation method and the vacuum impregnation method, the calcination temperature of the obtained catalyst precursor is 400-600℃.

11. The preparation method according to claim 10, characterized in that, In both the organic solvent impregnation method and the vacuum impregnation method, the impregnation time for metallic cobalt is 3-8 hours; in both the organic solvent impregnation method and the vacuum impregnation method, the calcination temperature of the resulting catalyst precursor is 450-550℃.

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