CN111848371A - Method for preparing aromatic ketone by oxidizing aromatic hydrocarbon with ozone - Google Patents

Method for preparing aromatic ketone by oxidizing aromatic hydrocarbon with ozone Download PDF

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CN111848371A
CN111848371A CN202010685809.8A CN202010685809A CN111848371A CN 111848371 A CN111848371 A CN 111848371A CN 202010685809 A CN202010685809 A CN 202010685809A CN 111848371 A CN111848371 A CN 111848371A
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aromatic hydrocarbon
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CN111848371B (en
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焦纬洲
高文强
刘有智
祁贵生
袁志国
张巧玲
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North University of China
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/40—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with ozone; by ozonolysis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/79—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/80—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
    • C07C2603/18—Fluorenes; Hydrogenated fluorenes

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Abstract

The invention belongs to the technical field of fine organic synthesis, and provides a method for preparing aromatic ketone by oxidizing aromatic hydrocarbon with ozone, aiming at the defects of harsh reaction conditions, complicated catalyst preparation process, many byproducts, low yield and the like in a method for synthesizing aromatic ketone compounds with aromatic hydrocarbon. In the process of not adding any metal catalyst and under mild reaction conditions, the aromatic hydrocarbon is selectively oxidized to synthesize the aromatic ketone compound. Simple process, high efficiency, environmental protection, mild reaction conditions, high conversion rate, high atom economy and the like. Is favorable for recycling the solvent. Has wide industrial application prospect.

Description

Method for preparing aromatic ketone by oxidizing aromatic hydrocarbon with ozone
Technical Field
The invention belongs to the technical field of fine organic synthesis, and particularly relates to a method for preparing aromatic ketone by oxidizing aromatic hydrocarbon with ozone.
Background
The selective oxidation of aromatic side chains is a research difficulty in organic synthesis and also plays an important role in the field of petrochemical industry. Traditionally, oxidation of aromatic side chains is usually carried out by using heavy metal oxidants such as potassium permanganate, potassium dichromate, chromyl chloride, and the like. These oxidizing agents are costly, generally used in large quantities, and are environmentally harmful, greatly limiting their use in industry. Therefore, research and development of a novel green oxidation method applied to aromatic hydrocarbon synthesis of aromatic ketone compounds become research hotspots of people. The structure of arones exists in many functional structural molecules as well as natural products, however, the simplest arones include acetophenone, benzophenone, and 9-fluorenone.
Acetophenone is an important fine chemical raw material, and is widely used for synthesizing spices, dyes and medicines. Such as alpha-phenylindole, mandelic acid and ibuprofen. In addition, acetophenone also generally acts as a reaction solvent, and has the advantages of good stability, high boiling point and the like. Can dissolve cellulose, coumarone resin, alkyd resin, etc. The synthesis method of the acetophenone comprises the synthesis of the acetophenone by air oxidation of ethylbenzene, the Friedel-crafts acylation of benzene and acetic anhydride or acetyl chloride, the benzoic acid decomposition method and the synthesis of the acetophenone by oxidation of phenethyl alcohol. The synthesis of acetophenone by the catalytic oxidation of ethylbenzene has great practical significance for the development of fine chemical engineering. At present, the method for industrially synthesizing acetophenone by oxidizing ethylbenzene has some defects, such as difficult recycling of the metal catalyst, low conversion rate, more side reactions and the like.
Zhang Qiaoqiao hong et al human bodyForming a series of tetrahalogenated NHPI and DADCAQ (1, 4-diamino-2, 3-dichloroanthraquinone) composite catalysts, oxidizing ethylbenzene to synthesize acetophenone at the reaction temperature of 100 ℃ under the oxygen pressure of 0.3 MPa for 5 h, wherein the conversion rate of ethylbenzene is 82.3%, and the selectivity of acetophenone is 86.9% (A)Journal of Chemical Technology and Biotechnology. 2008, 83: 1364-1369)。
Malong et al combined green heme and NHPI in the synthesis of acetophenone by ethylbenzene oxidationCatalysis Communications2007, 8: 27-30), the reaction temperature is 100 ℃, the oxygen pressure is 0.3 MPa, the reaction time is 9 h, the ethylbenzene conversion rate is 90.32%, and the selectivity is 94.3%.
Preparation of MnO loaded with magnesium-aluminum hydrotalcite (LDHs) by calcination reduction of Wangyiman et al4 -The catalyst is used in the oxidation of ethylbenzene at the reaction temperature of 120 ℃, and the yield of the acetophenone is 57 percent (Application of chemistry. 2012, 29(9):1017-1022)。
Wang Cienxin et al immobilized cobalt porphyrin with different structures on high polymer modified silica gel by coordination method, and prepared catalyst CoTNPP-P (4VP-co-St)/SiO2Applied to the oxidation of ethylbenzene, the reaction is carried out for 12 hours at the reaction temperature of 120 ℃, and the yield of the acetophenone is 25.53%Physical chemistry newspaper. 2009, 25(9): 1791-1798)。
Rogin et al used carbon nanotubes as catalyst, showed high stability in the reaction, oxygen pressure was 1.5MPa, the mass ratio of catalyst to ethylbenzene was 0.2, reaction temperature was 155 deg.C, reaction time was 4 h, conversion of ethylbenzene was 38.2%, selectivity of acetophenone was 60.9%, and after the catalyst was reused for 5 times, catalytic activity was not significantly reduced (Rogin. carbon nanotubes and nitrogen-doped carbon nanotubes liquid phase catalytic oxidation of benzyl alcohol and ethylbenzene [ D ] was ].Guangdong university of south China's science,2013)。
Benzophenone is an important fine chemical intermediate and additive, and benzophenone series products are widely used in the fields of medicines, pesticides, dyes, plastics and the like. The method for synthesizing benzophenone comprises four methods, the first method is a carbon tetrachloride method, namely benzene and carbon tetrachloride are reacted in AlCl3Under the action ofCarrying out Friedel-Crafts alkylation reaction on a diphenyl dichloromethane intermediate, and then carrying out hydrolysis reaction to obtain benzophenone; the second method is the benzoyl chloride method, i.e. the method is carried out by reacting benzene with benzoyl chloride in AlCl3Carrying out Friedel-Crafts acylation reaction under the action to prepare benzophenone; the third method is benzyl chloride method, i.e. benzyl chloride and benzene are mixed in AlCl3Under the action of Friedel-Crafts alkylation reaction to synthesize diphenyl methane, and then concentrated nitric acid is used for oxidizing the diphenyl methane into benzophenone. The fourth method is the phosgene method, i.e. benzene with phosgene in anhydrous AlCl3Reacting under the catalysis to generate benzophenone.
All the above four methods use AlCl3As the catalyst, HCl was produced as a by-product. Among them, the carbon tetrachloride method uses CCl although the reaction conditions are relatively mild4It has carcinogenicity, and is difficult to separate and purify. Benzoyl chloride used in the benzoyl chloride process has a strong pungent odor, requires distillation for purification before use, and the reactant benzene has carcinogenicity. The benzyl chloride method is similar to the carbon tetrachloride method in reaction process, the reaction route of the method is long, in addition, the nitric acid oxidation process is difficult to control, and the requirements on a reaction system are quite strict. Although the phosgene method has short process route, relatively low raw material cost, high reaction conversion rate and easy product purification, the method uses the highly toxic substance phosgene, thereby causing great threat to the safety of production and personnel.
PdCl for Hao subject group2Catalyzing the aromatic acyl chloride to perform cross-coupling reaction with the organic bismuth compound (Tetrahedron Letters2006, 47(39): 6975-6978), it was found that the yield of benzophenone was 95% with triethylamine as the basic reagent, the reaction temperature was 80 ℃, the reaction time was 4 h.
Genet problem group use [ Rh (CH)2CH2)2Cl]2And P: (t-Bu)3The composite catalyst of the composition catalyzes the coupling reaction between aromatic aldehyde and aryl trifluoroborate (Journal of the American Chemical society, 2004, 126(47): 15356-15357), and the benzophenone compound is obtained with excellent yield at a reaction temperature of 80 ℃.
9-fluorenone is an important organic intermediate with wide application, and in the field of medicine, the anti-spasm drug 2-hydroxyaminoacetylfluorenone is synthesized by 9-fluorenone; in the field of pesticides, it can be used for synthesizing insecticides and plant growth regulators; in the field of dyes, can be used for synthesizing aromatic diamine dyes. The production process for synthesizing 9-fluorenone by using fluorene as a raw material has the characteristics of simple operation and the like, and more importantly, the economic value of the 9-fluorenone is far higher than that of the fluorene. Conventional synthesis methods for synthesizing 9-fluorenone from fluorene include gas phase oxidation and liquid phase oxidation. The process for preparing 9-fluorenone by gas phase oxidation is to vaporize fluorene at high temperature, namely the reaction temperature is usually higher than 300 ℃, in the reaction process, the fluorene is easy to generate deep oxidation reaction, and in addition, the preparation process of the catalyst is complex.
The liquid phase oxidation method is one of the main methods for industrially preparing 9-fluorenone, but the method generates a large amount of waste liquid containing metal ions, and the purification, separation and purification of the product are difficult. In order to improve the selectivity of fluorene oxidation to synthesize 9-fluorenone, many researchers have been working on the development of novel catalysts, including metal compounds, peroxo metal complex catalysts, metalloporphyrin catalysts, and the like.
Li et al synthesize ferriporphyrin molecule Fe (TPP) Cl, under the combined action of chloramine and oxygen, fluorene liquid phase is oxidized to synthesize 9-fluorenone, the reaction obtains better effect, the product yield is 86%, but the catalyst has the defects of high price, difficult recovery and the like (the catalyst is expensive)Tetrahedron Letter. 2005, 46(46): 8013-8015)。
Matsushita et al studied the effect of composite catalyst on the catalytic oxidation of fluorene to 9-fluorenone ((Chemical Communications.1999, 265-266). These catalysts include RuCl3、CoCl2、AlCl3And the like. The reaction is carried out for 3 hours at the reaction temperature of 70 ℃, and the yield of 9-fluorenone can reach 93 percent. The composite catalyst synthesized by combining the transition metal salt has the problems of difficult recycling and the like due to high price.
Wang et al used 3-methylpyridine-N-hydroxyphthalimide (Py-NHPI) and Co (PF)6)2As a composite catalyst system, using ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (b) [bmim][PF6]) Reacting with oxygen at 65 deg.C under normal pressure for 24 hr to obtain 9-fluorenone (F) with yield of 96%Tetrahedron Letters. 2005, 46(27): 4647-4651.)。
The oxidation of aromatic hydrocarbons to obtain aromatic ketones has been one of the hot research, and because the alpha-H bond energy of aromatic hydrocarbons is large and activation is difficult, methods such as heavy metal catalysis or Friedel-Crafts reaction are mostly adopted in the prior art. However, these methods usually have harsh reaction conditions, high cost and serious environmental pollution caused by more three wastes. In addition, the preparation process of the catalyst is complicated and complicated, which causes great inconvenience to the purification process of the product. In recent years, attention has been paid to a catalyst-free oxidation reaction system. Therefore, the development process of the aromatic ketone synthesis technology which is simple, has no catalytic system and is environment-friendly has great practical significance and potential application value.
Disclosure of Invention
The invention provides a method for preparing aromatic ketone by oxidizing aromatic hydrocarbon with ozone, which does not need a catalyst and has the advantages of mild process conditions, high atom economy, environmental friendliness, high efficiency and the like.
The invention adopts the following technical scheme: a method for preparing aromatic ketone by oxidizing aromatic hydrocarbon with ozone comprises the steps of taking ozone as an oxidant, taking the aromatic hydrocarbon as a reactant, taking any one of a bubbling stirring kettle or a super-gravity rotating packed bed as a reactor, adding the reactant and a reaction solvent into the reactor, controlling the gas phase concentration of the ozone in the reactor to be 10-200 mg/L, controlling the temperature of the reaction solution to be-20-50 ℃, and reacting for 10-60min to obtain the aromatic ketone compound.
The method comprises the following specific steps:
(1) sequentially adding a reactant aromatic hydrocarbon and a reaction solvent into a liquid storage tank of the reactor;
(2) adjusting a pressure reducing valve of an oxygen steel cylinder, setting the partial pressure to be 0.1MPa, generating ozone mixed gas after oxygen enters an ozone generator, setting the gas flow to be 100L/h, enabling the ozone mixed gas to enter a reactor to react with reactants, and controlling the gas phase concentration of ozone to be 10-200 mg/L;
(3) introducing the ozone mixed gas into a reaction device, and setting the temperature of the reaction liquid to react for 10-60 min;
(4) after the reaction is finished, adding a saturated sodium thiosulfate solution into the reaction solution, extracting and separating to obtain an organic phase, or introducing nitrogen into the reaction solution to blow out residual ozone, removing the reaction solvent by a rotary evaporator, and obtaining the high-purity aromatic ketone compound by distillation or silica gel column chromatography.
The reaction solvent is any one of acetonitrile, dichloromethane, ethyl acetate or acetone; the reactant is any one of ethylbenzene, diphenylmethane or fluorene; the adding proportion of the reactant aromatic hydrocarbon to the reaction solvent is 10-50 g: 500 ml.
And an eluent in the silica gel column chromatography is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 5: 1-10: 1.
The supergravity rotating packed bed of the present invention is a disclosed device, and includes various forms of supergravity reactors (refer to application numbers 200510032296.6, 201510093434.5, 201510093447.2) such as packed beds, and the packing includes any one of wire mesh, perforated plates, foam materials and structured packing.
The invention takes ozone as an oxidant, and selectively oxidizes and synthesizes aromatic hydrocarbon into aromatic ketone compounds under mild reaction conditions in the process of not adding any metal catalyst. The method has the advantages of simple process, high efficiency, green, mild reaction conditions, high conversion rate and the like. And low-toxicity and low-boiling point reagents such as acetone, ethyl acetate, dichloromethane and the like are selected as solvents, so that the solvents are favorably recycled. The method has the advantages of environmental protection, high atom economy and the like, and has wide industrial application prospect. The method has the advantages of simple operation, environmental protection, high atom economy, mild reaction conditions and easy industrialization.
Drawings
FIG. 1 is a formula of synthesizing acetophenone by oxidizing ethylbenzene with ozone according to the present invention;
FIG. 2 is a diagram of the equation for synthesizing benzophenone by using diphenylmethane oxide by ozone;
FIG. 3 is a formula of the present invention for synthesizing 9-fluorenone by ozone oxidation of fluorene;
FIG. 4 shows the hydrogen spectrum of acetophenone prepared by the present invention (1H NMR)；
FIG. 5 shows the hydrogen spectrum of benzophenone prepared by the present invention1H NMR)；
FIG. 6 shows a hydrogen spectrum of 9-fluorenone prepared by the present invention (1H NMR)。
Detailed Description
The following further describes embodiments of the present invention. So that those skilled in the art can understand the invention, it should be understood that the invention is not limited in scope to the specific embodiments, but that various changes may be apparent to those skilled in the art, which changes are within the spirit and scope of the invention as defined and defined in the claims, and that all inventive concepts utilizing the inventive concepts are protected.
A method for preparing aromatic ketone by oxidizing aromatic hydrocarbon with ozone comprises the steps of taking ozone as an oxidant, taking the aromatic hydrocarbon as a reactant, taking any one of a bubbling stirring kettle or a super-gravity rotating packed bed as a reactor, adding the reactant and a reaction solvent into the reactor, controlling the gas phase concentration of the ozone in the reactor to be 10-200 mg/L, controlling the temperature of the reaction solution to be-20-50 ℃, and reacting for 10-60min to obtain the aromatic ketone compound.
The method comprises the following specific steps:
(1) and sequentially adding 10-50 g of reactant aromatic hydrocarbon and 500 mL of reaction solvent into a bubbling stirring kettle or a liquid storage tank of a supergravity reactor.
(2) Adjusting a pressure reducing valve of an oxygen steel cylinder, setting the partial pressure to be 0.1MPa, generating ozone mixed gas after oxygen enters an ozone generator, setting the gas flow to be 100L/h, introducing the ozone mixed gas into a reactor to react with reactants, and controlling the gas phase concentration of ozone to be 10-200 mg/L;
(3) and introducing the ozone mixed gas into a reaction device, setting the temperature of the reaction liquid to be-20-50 ℃, and setting the reaction time to be 10-60 min.
(4) After the reaction is finished, adding a saturated sodium thiosulfate solution into the reaction solution, extracting and separating to obtain an organic phase, or introducing nitrogen into the reaction solution to blow out residual ozone, removing the reaction solvent by using a rotary evaporator, and then carrying out distillation or silica gel column chromatography to obtain the high-purity arone compound.
The present invention will be further described with reference to the following examples.
Example 1: weighing 10g of ethylbenzene, dissolving in 500 mL of ethyl acetate, placing in a bubbling reactor, adjusting the gas phase concentration of ozone to 80 mg/L, reacting at 20 ℃ for 45min, adding saturated sodium thiosulfate solution into the reaction solution, extracting and separating to obtain an organic phase, removing the organic solvent by using a rotary evaporator, and performing silica gel column chromatography (eluent is V) Petroleum ether/VEthyl acetate=5: 1) to obtain 6.79 g of acetophenone, yield 60%.
Hydrogen spectrum of acetophenone prepared (1H NMR) as shown in figure 4,1H NMR(600 MHz, CDCl3) 7.94-7.95(m, 2H), 7.54 (t,J= 6 Hz, 1H), 7.44 (t,J= 6 Hz, 1H), 2.58 (s, 3H). By data analysis, the product was confirmed to be acetophenone and had a purity of 99%. The method has the advantages of no use of any catalyst, relatively mild reaction conditions and simple process flow.
Example 2: 10g of diphenylmethane is weighed, dissolved in 500 mL of acetonitrile and placed in a liquid storage tank, the concentration of gas-phase ozone is 200 mg/L, and the rotating speed of the hypergravity reactor is 1000 rpm. Reacting at 30 deg.C for 50 min, adding saturated sodium thiosulfate solution into the reaction solution, extracting and separating to obtain organic phase, removing organic solvent with rotary evaporator, and performing silica gel column chromatography (eluent is V)Petroleum ether/VEthyl acetate=10: 1) yield benzophenone 9.75 g, 90%.
Hydrogen spectrum of prepared benzophenone (1H NMR) as shown in figure 5,1H NMR(600 MHz, CDCl3) 7.79-7.80 (m, 4H), 7.57 (t,J= 6 Hz, 2H), 7.47 (t,J= 6 Hz, 4H). By data analysis, the product was confirmed to be benzophenone and to be 99% pure.The method has the advantages of no use of any catalyst, relatively mild reaction conditions and simple process flow.
Example 3: 10g of fluorene is weighed, dissolved in 500 mL of dichloromethane and placed in a liquid storage tank, a liquid flow meter is set to be 100L/h, a gas flow meter is set to be 90L/h, the concentration of gas-phase ozone is 130 mg/L, and the rotating speed of a supergravity reactor is 1000 rpm. Reacting at 50 deg.C for 10min, adding saturated sodium thiosulfate solution into the reaction solution, extracting and separating to obtain organic phase, removing organic solvent with rotary evaporator, and performing silica gel column chromatography (eluent is V) Petroleum ether/VEthyl acetate=5: 1) to obtain 3.21 g of 9-fluorenone, and the yield is 30%.
Hydrogen spectrum of prepared 9-fluorenone ((II))1H NMR) as shown in figure 6,1H NMR(600 MHz, CDCl3) 7.65 (d,J= 12 Hz, 2H), 7..46-7.51 (m, 4H), 7.28 (t,J= 12 Hz, 2H). By data analysis, the product was confirmed to be 9-fluorenone and to be 99% pure. The method has the advantages of no use of any catalyst, relatively mild reaction conditions and simple process flow.
Example 4: 30 g of ethylbenzene is weighed, dissolved in 500 mL of acetone and placed in a liquid storage tank, a liquid flow meter is set to be 100L/h, a gas flow meter is set to be 100L/h, the concentration of gas-phase ozone is 200 mg/L, and the rotating speed of the super-gravity reactor is 1000 rpm. Reacting at-20 deg.C for 60 min, adding saturated sodium thiosulfate solution, extracting and separating to obtain organic phase, removing organic solvent with rotary evaporator, and performing silica gel column chromatography (eluent is V)Petroleum ether/VEthyl acetate=7: 1) to obtain 9.05 g of acetophenone, yield 80%.
Hydrogen spectrum of acetophenone prepared (1H NMR) as shown in figure 4,1H NMR(600 MHz, CDCl3) 7.94-7.95(m, 2H), 7.54 (t,J= 6 Hz, 1H), 7.44 (t,J= 6 Hz, 1H), 2.58 (s, 3H). By data analysis, the product was confirmed to be acetophenone and had a purity of 99%. The method has the advantages of no use of any catalyst, relatively mild reaction conditions, simple process flow and high acetophenone yield.
Example 5: weighing 50 g of fluorene, dissolving in 500 mL of dichloromethane, placing in a bubbling reactor, wherein the gas flow meter is 100L/h, the gas-phase ozone concentration is 10 mg/L, reacting at 50 ℃ for 10 min, introducing nitrogen into the reaction liquid to blow out residual ozone, removing the organic solvent by using a rotary evaporator, and distilling to obtain 5.42 g of 9-fluorenone, wherein the yield is 10%.
Hydrogen spectrum of prepared 9-fluorenone ((II))1H NMR) as shown in figure 4,1H NMR(600 MHz, CDCl3) 7.65 (d,J= 12 Hz, 2H), 7.46-7.51 (m, 4H), 7.28 (t,J= 12 Hz, 2H). By data analysis, the product was confirmed to be 9-fluorenone and to be 99% pure. The method has the advantages of no use of any catalyst, relatively mild reaction conditions and simple process flow.

Claims (6)

1. A method for preparing aromatic ketone by oxidizing aromatic hydrocarbon with ozone is characterized by comprising the following steps: the aromatic ketone compound is prepared by taking ozone as an oxidant, taking aromatic hydrocarbon as a reactant, taking any one of a bubbling stirring kettle or a super-gravity rotating packed bed as a reactor, adding the reactant and a reaction solvent into the reactor, controlling the gas phase concentration of the ozone in the reactor to be 10-200 mg/L, controlling the temperature of the reaction liquid to be-20-50 ℃, and reacting for 10-60 min.
2. The method of claim 1, wherein the aromatic ketone is prepared by ozone oxidation of aromatic hydrocarbon, and the method comprises the following steps: the method comprises the following specific steps:
(1) Sequentially adding a reactant aromatic hydrocarbon and a reaction solvent into a liquid storage tank of the reactor;
(2) adjusting a pressure reducing valve of an oxygen steel cylinder, setting the partial pressure to be 0.1MPa, generating ozone mixed gas after oxygen enters an ozone generator, setting the gas flow to be 100L/h, enabling the ozone mixed gas to enter a reactor to react with reactants, and controlling the gas phase concentration of ozone to be 10-200 mg/L;
(3) introducing the ozone mixed gas into a reaction device, and setting the temperature of the reaction liquid to react for 10-60 min;
(4) after the reaction is finished, adding a certain amount of sodium thiosulfate solution into the reaction solution, extracting and separating to obtain an organic phase, or introducing nitrogen into the reaction solution to blow out residual ozone, removing the reaction solvent by a rotary evaporator, and obtaining the high-purity aromatic ketone compound by distillation or silica gel column chromatography.
3. The method of claim 2, wherein the aromatic ketone is prepared by ozone oxidation of aromatic hydrocarbon, and the method comprises the following steps: the reaction solvent is any one of acetonitrile, dichloromethane, ethyl acetate or acetone; the reactant is any one of ethylbenzene, diphenylmethane or fluorene; the adding proportion of the reactant aromatic hydrocarbon to the reaction solvent is 10-50 g: 500 ml.
4. The method of claim 2, wherein the aromatic ketone is prepared by ozone oxidation of aromatic hydrocarbon, and the method comprises the following steps: the reactor is a supergravity rotating packed bed, and the rotating speed is 1000 rpm.
5. The method of claim 2, wherein the aromatic ketone is prepared by ozone oxidation of aromatic hydrocarbon, and the method comprises the following steps: the volume ratio of the thiosulfuric acid to the reaction solvent is as follows: 50-100 mL: 500 mL.
6. The method of claim 2, wherein the aromatic ketone is prepared by ozone oxidation of aromatic hydrocarbon, and the method comprises the following steps: and an eluent in the silica gel column chromatography is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 5: 1-10: 1.
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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN115403455A (en) * 2022-09-16 2022-11-29 吕梁学院 Method for synthesizing acetophenone by oxidizing ethylbenzene
CN116535297A (en) * 2023-04-17 2023-08-04 大连理工大学 Green intermittent and continuous method and system for preparing aromatic ketone by photocatalytic molecular oxygen oxidation

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CN105732356A (en) * 2014-10-13 2016-07-06 黄国柱 Method for preparing carboxylic acid or phenyl ketone by using ozone, singlet oxygen atom free radical or hydroxyl radical

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115403455A (en) * 2022-09-16 2022-11-29 吕梁学院 Method for synthesizing acetophenone by oxidizing ethylbenzene
CN115403455B (en) * 2022-09-16 2024-01-26 吕梁学院 Method for synthesizing acetophenone by oxidizing ethylbenzene
CN116535297A (en) * 2023-04-17 2023-08-04 大连理工大学 Green intermittent and continuous method and system for preparing aromatic ketone by photocatalytic molecular oxygen oxidation

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