CN111848371B - Method for preparing aromatic ketone by oxidizing aromatic hydrocarbon with ozone - Google Patents
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- 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
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- 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
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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, which aims at the defects of harsh reaction conditions, complex preparation process flow of a catalyst, more byproducts, low yield and the like in a method for synthesizing aromatic ketone compounds with aromatic hydrocarbon, wherein ozone is used as an oxidant, aromatic hydrocarbon is used as a reactant, a bubbling stirring kettle or a supergravity rotating packed bed is used as a reactor, the gas phase concentration of ozone in the reactor is controlled to be 10-200 mg/L, the temperature of a reaction solution is between-20 ℃ and 50 ℃, and the aromatic ketone compounds can be obtained by reacting for 10-60 min. Aromatic hydrocarbon is selectively oxidized to synthesize aromatic ketone compounds under mild reaction conditions in the process of not adding any metal catalyst. Simple process, high efficiency, environmental protection, high reaction condition temperature, high conversion rate, high atom economy and the like. Is favorable for recycling the solvent. Has wide industrial application prospect.
Description
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 hydrocarbon side chains is a research difficulty in organic synthesis and plays an important role in the petrochemical field. Conventionally, oxidation of aromatic hydrocarbon side chains is generally carried out using heavy metal oxidants such as potassium permanganate, potassium dichromate, chromyl chloride, and the like. These oxidizing agents are costly, often in large amounts, and are extremely environmentally polluting, 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 have become research hot spots of people. The structure of aromatic ketones is present in many functional structural molecules as well as in natural products, however the simplest aromatic ketones 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 synthesizing alpha-phenylindole, phenylglycolic 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 acetophenone comprises the steps of synthesizing acetophenone by oxidizing ethylbenzene with air, performing Friedel-crafts acylation on benzene and acetic anhydride or acetyl chloride, and synthesizing acetophenone by oxidizing phenethyl alcohol. The synthesis of acetophenone by ethylbenzene catalytic oxidation has great practical significance for the development of fine chemical engineering. At present, the method for synthesizing acetophenone by oxidizing ethylbenzene industrially has some defects such as difficult recovery and reutilization, low conversion rate, multiple side reactions and the like by using a metal catalyst.
Zhang Qiaogong et al synthesized a series of tetrahalogenated NHPI and DADCAQ (1, 4-diamino-2, 3-dichloro anthraquinone) composite catalysts, under the oxygen pressure of 0.3 MPa, the reaction temperature is 100 ℃, after 5 h reaction, ethylbenzene is oxidized to acetophenone, the conversion rate of ethylbenzene is 82.3%, and the selectivity of acetophenone is 86.9%Journal of Chemical Technology and Biotechnology. 2008, 83: 1364-1369)。
Malus asiatica et al used greening heme and NHPI in synthesizing acetophenone by ethylbenzene oxidationCatalysis Communications2007, 8:27-30), a reaction temperature of 100 ℃, an oxygen pressure of 0.3 MPa, a reaction time of 9 h, an ethylbenzene conversion of 90.32% and a selectivity of 94.3%.
Wang Yifan and the like for preparing magnesium aluminum hydrotalcite (LDHs) supported MnO by calcination reduction 4 - Catalyst, which is used in the oxidation of ethylbenzene, the yield of acetophenone is 57% at 120 deg.cApplication chemistry.2012, 29(9): 1017-1022)。
Wang Ruixin et al immobilized cobalt porphyrins of different structures on high polymer modified silica gel by coordination method, and prepared catalyst CoTNPP-P (4 VP-co-St)/SiO 2 Is applied to the oxidation of ethylbenzene, and the reaction temperature is 120 ℃ and the reaction is 12 to h, and the acetophenone yield is 25.53 percentPhysical chemistry school newspaper. 2009, 25(9): 1791-1798)。
Luo Jin et al use carbon nanotubes as catalysts, exhibit high stability in the reaction, oxygen pressure of 1.5 MPa, catalyst to ethylbenzene mass ratio of 0.2, reaction temperature of 155 ℃, reaction time of 4h, ethylbenzene conversion of 38.2%, acetophenone selectivity of 60.9%, and no significant decrease in catalytic activity after 5 repeated uses of the catalyst (Luo Jin. Carbon nanotubes and nitrogen-doped carbon nanotubes liquid phase catalyze oxidation of benzyl alcohol and ethylbenzene [ D ]]. Guangdong university of Arisaema in North China, 2013)。
Benzophenone is an important intermediate and additive for fine chemical industry, and benzophenone series products have been widely used in the fields of medicine, pesticide, dye, plastics, etc. The diphenyl ketone synthesizing process includes four processes, the first is carbon tetrachloride process, that is, benzene and carbon tetrachloride in AlCl 3 The Friedel-Crafts alkylation reaction is carried out on a diphenyl methylene dichloride intermediate under the action of the Friedel-Crafts alkylation reaction, and then the diphenyl methylene dichloride intermediate is subjected to hydrolysis reaction to obtain diphenyl ketone; the second method is benzoyl chloride method, i.e. benzene and benzoyl chloride in AlCl 3 Friedel-Crafts acylation reaction under the action to prepare diphenyl ketone; the third method is benzyl chloride method, i.e. benzyl chloride and benzene in AlCl 3 Friedel-Crafts alkylation reaction is carried out to synthesize diphenylmethane, and then the diphenylmethane is oxidized into benzophenone by using concentrated nitric acid. The fourth method is the phosgene method, i.e. benzene and phosgene in anhydrous AlCl 3 And (3) reacting under the catalysis to generate the diphenyl ketone.
AlCl is used in all four methods 3 As the catalyst, there was produced HCl as a by-product. Wherein the carbon tetrachloride method, although the reaction conditions are relatively mild, uses CCl 4 Has carcinogenicity and is difficult to separate and purify. Benzoyl chloride used in benzoyl chloride method has strong pungent smell, and is required before useTo carry out distillation purification, benzene, which is another reactant, is carcinogenic. The benzyl chloride method has a reaction process similar to that of the carbon tetrachloride method, the reaction route of the method is longer, and in addition, the nitric acid oxidation process is difficult to control and has quite strict requirements on a reaction system. Although the phosgene method has the advantages of short process route, relatively low raw material cost, high reaction conversion rate and easy purification of products, the method uses the highly toxic substance phosgene, which greatly threatens the safety of production and personnel.
PdCl for Hao subject group 2 Catalyzing the cross-coupling reaction of aromatic acyl chloride and organobismuth compoundTetrahedron Letters2006, 47 (39): 6975-6978), it was found that triethylamine was used as an alkaline agent, the reaction temperature was 80 ℃, the reaction time was 4h, and the yield of benzophenone was 95%.
Genet subject group use [ Rh (CH) 2 CH 2 ) 2 Cl] 2 And P%t-Bu) 3 The compound catalyst catalyzes aryl aldehyde and aryl trifluoro-borate to generate coupling reaction (Journal of the American Chemical society 2004, 126 (47): 15356-15357), and the benzophenone compound is obtained with excellent yield at the reaction temperature of 80 ℃.
9-fluorenone is an important organic intermediate with wide application, and in the field of medicine, the 9-fluorenone is used for synthesizing an antispasmodic drug 2-hydroxyaminoacetyl fluorenone; in the field of pesticides, can be used for synthesizing pesticides and plant growth regulators; in the dye field, the method can be used for synthesizing aromatic diamine dyes. The production process for synthesizing 9-fluorenone by using fluorene as raw material has the characteristics of simple operation and the like, and more importantly, the economic value of 9-fluorenone is far higher than that of fluorene. Traditional synthetic methods for synthesizing 9-fluorenone from fluorene include a gas phase oxidation method and a liquid phase oxidation method. The process of preparing 9-fluorenone by gas phase oxidation is to vaporize fluorene at high temperature, i.e. the reaction temperature is usually higher than 300 ℃, in the reaction process, deep oxidation reaction of fluorene is very easy to occur, and in addition, the catalyst preparation process is often complicated.
The liquid phase oxidation method is one of the main industrial methods for preparing 9-fluorenone, but the method can generate 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 synthesizing 9-fluorenone by oxidation of fluorene, many scholars have been devoted to developing novel catalysts including metal compounds, peroxometallium complex catalysts, metalloporphyrin catalysts, and the like.
Li and the like synthesize ferriporphyrin molecule Fe (TPP) Cl, under the combined action of chloramine and oxygen, fluorene is subjected to liquid-phase oxidation 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 likeTetrahedron Letter. 2005, 46(46): 8013-8015)。
Matsushita et al studied the effect of the composite catalyst on the catalytic oxidation of fluorene to 9-fluorenoneChemical Communications.1999, 265-266). These catalysts include RuCl 3 、CoCl 2 、AlCl 3 Etc. The yield of the reaction for 3h, 9-fluorenone can reach 93 percent under the condition of the reaction temperature of 70 ℃. The composite catalyst combined by the transition metal salts has the problems of difficult recovery and reutilization due to high price.
Wang et al utilized 3-methylpyridine-N-hydroxyphthalimide (Py-NHPI) and Co (PF 6 ) 2 As a composite catalyst system, ionic liquid 1-butyl-3-methylimidazole hexafluorophosphate ([ bmim)][PF 6 ]) As a reaction solvent, the mixture reacts with oxygen at the reaction temperature of 65 ℃ and under normal pressure for 24 h, and 9-fluorenone is obtained with the yield of 96 percentTetrahedron Letters. 2005, 46(27): 4647-4651.)。
The oxidation of aromatic hydrocarbons to aromatic ketones has been one of the focus of research, and because of the relatively high alpha-H bond energy of aromatic hydrocarbons, the activation is relatively difficult, and heavy metal catalysis or Friedel-Crafts reactions are often used in the traditional methods. However, the methods are generally harsh in reaction conditions, high in cost and serious in environmental pollution caused by more three wastes. In addition, the catalyst is prepared by Cheng Fanrong, which causes great inconvenience to the purification process of the product. In recent years, attention has been directed to the study of catalyst-free oxidation reaction systems. Therefore, the development process is simple, no catalytic system exists, and the environment-friendly aromatic ketone synthesis technology has great practical significance and potential application value.
Disclosure of Invention
Aiming at the defects of harsh reaction conditions, tedious catalyst preparation process flow, more byproducts, low yield and the like in the method for synthesizing the aromatic ketone compound from the aromatic hydrocarbon, the invention provides the method for preparing the aromatic ketone by oxidizing the aromatic hydrocarbon by ozone, and the preparation method does not need the catalyst and has the advantages of mild process conditions, high atomic economy, environment 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 uses ozone as oxidant, aromatic hydrocarbon as reactant, any one of bubbling stirring kettle or super-gravity rotating packed bed as reactor, reactant and reaction solvent are added into the reactor, gas phase concentration of ozone in the reactor is controlled to be 10-200 mg/L, reaction liquid temperature is-20-50 ℃, and aromatic ketone compound can be obtained after reaction for 10-60 min.
The method comprises the following specific steps:
(1) Sequentially adding reactant aromatic hydrocarbon and a reaction solvent into a liquid storage tank of a reactor;
(2) Adjusting a pressure reducing valve of an oxygen steel bottle, 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 ozone mixed gas into a reaction device, and setting the temperature of a reaction liquid to react for 10-60min;
(4) After the reaction is finished, adding saturated sodium thiosulfate solution into the reaction liquid, extracting and separating to obtain an organic phase, or introducing nitrogen into the reaction liquid to blow out residual ozone, removing the reaction solvent by a rotary evaporator, and obtaining the high-purity aromatic ketone compound by adopting 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 ratio of the reactant aromatic hydrocarbon to the reaction solvent is 10-50g:500ml.
The 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 super-gravity rotating packed bed is a device which is disclosed, and comprises a plurality of super-gravity reactors (reference application numbers 200510032296.6, 201510093434.5 and 201510093447.2) of packed beds and the like, wherein the packing comprises any one of a wire mesh, a porous plate, a foam material and a structured packing.
The invention uses ozone as oxidant, and in the course of not adding any metal catalyst, and under the mild reaction condition, aromatic hydrocarbon can be selectively oxidized to synthesize aromatic ketone compound. The method has the advantages of simple process, high efficiency, greenness, high reaction condition temperature, high conversion rate and the like. The solvent is selected from low-toxicity and low-boiling point reagents such as acetone, ethyl acetate, methylene dichloride and the like, which is favorable for recycling the solvent. The method has the advantages of green 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 an equation for synthesizing acetophenone by oxidizing ethylbenzene with ozone according to the present invention;
FIG. 2 is an equation for synthesizing benzophenone by oxidizing diphenylmethane with ozone according to the present invention;
FIG. 3 is an equation for synthesizing 9-fluorenone by oxidizing fluorene with ozone according to the present invention;
FIG. 4 shows the hydrogen spectrum of acetophenone preparation according to the present invention 1 H NMR)；
FIG. 5 shows the hydrogen spectrum of benzophenone prepared in accordance with the present invention 1 H NMR)；
FIG. 6 shows the hydrogen spectrum of 9-fluorenone prepared according to the present invention 1 H NMR)。
Detailed Description
The following describes the embodiments of the present invention further. So that those skilled in the art will readily understand the present invention, it is to be understood that the present invention is not limited to the specific embodiments, and that all changes which come within the spirit and scope of the invention as defined and defined by the appended claims are to be embraced by the invention.
A method for preparing aromatic ketone by oxidizing aromatic hydrocarbon with ozone uses ozone as oxidant, aromatic hydrocarbon as reactant, any one of bubbling stirring kettle or super-gravity rotating packed bed as reactor, reactant and reaction solvent are added into the reactor, gas phase concentration of ozone in the reactor is controlled to be 10-200 mg/L, reaction liquid temperature is-20-50 ℃, and aromatic ketone compound can be obtained after reaction for 10-60 min.
The method comprises the following specific steps:
(1) And sequentially adding 10-50g of reactant aromatic hydrocarbon and 500mL reaction solvent into a bubbling stirred tank or a liquid storage tank of a hypergravity reactor.
(2) Adjusting a pressure reducing valve of an oxygen steel bottle, 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) Introducing ozone mixed gas into a reaction device, and setting the temperature of a reaction liquid to be minus 20 DEG C o C ~50 o And C, reacting for 10-60 min.
(4) After the reaction is finished, adding saturated sodium thiosulfate solution into the reaction liquid, extracting and separating to obtain an organic phase, or introducing nitrogen into the reaction liquid to blow out residual ozone, removing the reaction solvent by using a rotary evaporator, and then obtaining the high-purity aromatic ketone compound by adopting distillation or silica gel column chromatography.
The invention will be further illustrated with reference to examples.
Example 1: 10g of ethylbenzene is weighed and dissolved in 500mL ethyl acetate and placed in a bubbling reactor, the concentration of ozone gas phase is regulated to 80 mg/L, after the reaction is carried out for 45min at the reaction temperature of 20 ℃, saturated sodium thiosulfate solution is added into the reaction solution, the organic phase is obtained by extraction and separation, after the organic solvent is removed by a rotary evaporator, the organic phase is purified by a silica gel column chromatography (eluent is V) Petroleum ether /V Acetic acid ethyl ester =5:1) to give acetophenone 6.79 g in 60% yield.
Hydrogen spectrum of acetophenone prepared 1 H NMR) is shown in figure 4, 1 H NMR(600 MHz, CDCl 3 ) δ 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 identified as acetophenone and was 99% pure. The method has the advantages of no catalyst, relatively mild reaction condition and simple process flow.
Example 2: 10g of diphenylmethane was weighed out and dissolved in 500mL acetonitrile and placed in a liquid reservoir, the gas phase ozone concentration being 200 mg/L, the rotational speed of the supergravity reactor being 1000rpm. After 50 min of reaction at 30 ℃, saturated sodium thiosulfate solution is added into the reaction solution, the organic phase is obtained by extraction and separation, the organic solvent is removed by a rotary evaporator, and then the organic phase is subjected to silica gel column chromatography (eluent is V) Petroleum ether /V Acetic acid ethyl ester =10:1) to give benzophenone 9.75 g in a yield of 90%.
Hydrogen spectrum of benzophenone prepared 1 H NMR) is shown in figure 5, 1 H NMR(600 MHz, CDCl 3 ) δ 7.79-7.80 (m, 4H), 7.57 (t, J = 6 Hz, 2H), 7.47 (t, J=6 hz,4 h). By data analysis, the product was confirmed to be benzophenone and had a purity of 99%. The method has the advantages of no catalyst, relatively mild reaction condition and simple process flow.
Example 3: 10g fluorene is weighed and dissolved in 500mL dichloromethane and placed in a liquid storage tank, a liquid flowmeter is set to be 100L/h, a gas flowmeter is set to be 90L/h, the gas-phase ozone concentration is 130 mg/L, and the rotating speed of a hypergravity reactor is 1000rpm. After 10min of reaction at 50 ℃, saturated sodium thiosulfate solution is added into the reaction solution, the organic phase is obtained by extraction and separation, the organic solvent is removed by a rotary evaporator, and then the organic phase is subjected to silica gel column chromatography (eluent is V) Petroleum ether /V Acetic acid ethyl ester =5:1) to give 9-fluorenone 3.21 g in 30% yield.
Hydrogen spectrum of 9-fluorenone prepared 1 H NMR) is shown in figure 6, 1 H NMR(600 MHz, CDCl 3 ) δ 7.65 (d, J = 12 Hz, 2H), 7..46-7.51 (m, 4H), 7.28 (t, J=12 hz,2 h). By dataAnalysis confirmed that the product was 9-fluorenone and had a purity of 99%. The method has the advantages of no catalyst, relatively mild reaction condition and simple process flow.
Example 4: 30 g ethylbenzene was weighed and dissolved in 500mL acetone and placed in a liquid storage tank, a liquid flowmeter of 100L/h was set, a gas flowmeter of 100L/h, a gas phase ozone concentration of 200 mg/L and a super gravity reactor rotational speed of 1000rpm. After the reaction is carried out for 60min at the reaction temperature of minus 20 ℃, saturated sodium thiosulfate solution is added into the reaction liquid, the organic phase is obtained by extraction and separation, the organic solvent is removed by a rotary evaporator, and the organic phase is purified by a silica gel column chromatography (the eluent is V) Petroleum ether /V Acetic acid ethyl ester =7:1) to give acetophenone 9.05 g in 80% yield.
Hydrogen spectrum of acetophenone prepared 1 H NMR) is shown in figure 4, 1 H NMR(600 MHz, CDCl 3 ) δ 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 identified as acetophenone and was 99% pure. The method has the advantages of no catalyst, relatively mild reaction conditions, simple process flow and higher acetophenone yield.
Example 5: 50g fluorene is weighed and dissolved in 500mL dichloromethane and placed in a bubbling reactor, the gas flow meter is 100L/h, the gas phase ozone concentration is 10 mg/L, after the reaction is carried out for 10min at the reaction temperature of 50 ℃, nitrogen is introduced into the reaction liquid to blow out residual ozone, then a rotary evaporator is used for removing the organic solvent, and then the 9-fluorenone 5.42 g is obtained through distillation, wherein the yield is 10%.
Hydrogen spectrum of 9-fluorenone prepared 1 H NMR) is shown in figure 4, 1 H NMR(600 MHz, CDCl 3 ) δ 7.65 (d, J = 12 Hz, 2H), 7.46-7.51 (m, 4H), 7.28 (t, J=12 hz,2 h). By data analysis, it was confirmed that the product was 9-fluorenone and the purity was 99%. The method has the advantages of no catalyst, relatively mild reaction condition and simple process flow.
Claims (3)
1. A method for preparing aromatic ketone by oxidizing aromatic hydrocarbon with ozone, which is characterized in that: ozone is used as an oxidant, aromatic hydrocarbon is used as a reactant, the reactant and a reaction solvent are added into a reactor, and the temperature of a reaction solution is between-20 ℃ and 50 ℃, so that aromatic ketone compounds can be obtained; the method comprises the following specific steps:
(1) Sequentially adding reactant aromatic hydrocarbon and a reaction solvent into a liquid storage tank of a reactor;
(2) Adjusting a pressure reducing valve of an oxygen steel bottle, 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 ozone mixed gas into a reaction device, and setting the temperature of a reaction solution to react for 10-60min;
(4) After the reaction is finished, adding a certain amount of sodium thiosulfate solution into the reaction liquid, extracting and separating to obtain an organic phase, or introducing nitrogen into the reaction liquid to blow out residual ozone, removing the reaction solvent by a rotary evaporator, and obtaining the high-purity aromatic ketone compound by adopting 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 ratio of the reactant aromatic hydrocarbon to the reaction solvent is 10-50g:500ml;
the reactor is a super-gravity rotating packed bed, and the rotating speed is 1000rpm.
2. The method for preparing aromatic ketone by oxidizing aromatic hydrocarbon with ozone according to claim 1, wherein: the volume ratio of the thiosulfate to the reaction solvent is as follows: 50-100mL:500mL.
3. The method for preparing aromatic ketone by oxidizing aromatic hydrocarbon with ozone according to claim 1, wherein: the 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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