CN112142543A - Dehalogenation method of covalent organic framework material photocatalytic halogenated aromatic compound - Google Patents
Dehalogenation method of covalent organic framework material photocatalytic halogenated aromatic compound Download PDFInfo
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- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
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Abstract
A dehalogenation method of halogenated aromatic compounds comprises the following steps: under the action of a photocatalyst, the halogen substituent on the aromatic ring of the halogenated aromatic compound is removed to obtain the aromatic compound. The reaction system of the invention can selectively dehalogenate the halogenated aromatic compounds to synthesize the aromatic compounds under the action of the photocatalyst, the hydrogen donor and the alkali, and the GC yield of the product can reach more than 92 percent and can reach 99 percent at most.
Description
Technical Field
The invention belongs to the technical field of photochemical organic synthesis, and particularly relates to a dehalogenation method of a halogenated aromatic compound.
Background
In recent years, the defunctionalization reaction has attracted the scientific community attention. Many industrially important drugs and pesticide molecules can be synthesized via dehalogenation of halogenated aromatic compounds. The meaning of synthesizing aromatic molecules through the dehalogenation reaction of halogenated aromatic compounds is that highly functionalized aromatic compounds existing in nature, such as phenols, aromatic alcohols and aromatic carboxylic acid compounds, can be utilized to generate the halogenated aromatic compounds through the functional group conversion reaction, and then the halogen is removed to synthesize the aromatic compounds.
Aromatic compounds and derivatives thereof are a common and important structural fragment in organic synthesis, and are widely present in natural and artificial synthetic drugs. The classic synthesis methods for synthesizing the aromatic compounds by dehalogenating the halogenated aromatic compounds mainly comprise three methods, namely a zero-valent iron powder reduction method, a noble metal catalytic hydrogenation reduction method and a metal cathode electro-reduction method, but the methods are stoichiometric synthesis methods or require noble metals and dangerous hydrogen.
The prior reaction for synthesizing the aromatic compound by removing the functional group and dehalogenating the halogenated aromatic compound has the problems of non-mild conditions, environmental pollution, high cost, difficult separation of the catalyst and the product, difficult regeneration and utilization of the catalyst and the like. Because of the global energy and environmental problems, the development of society and science and technology makes the chemical production which is the primary purpose of environmental protection indispensable, and the urgent needs for some chemical products all make us to find a simpler, green, cheap, high-yield, high-efficiency and high-selectivity synthetic method.
In recent years, research on heterogeneous photocatalysis has been advanced. As a novel heterogeneous organic photocatalytic material, a Covalent Organic Framework (COF) has the advantages of high crystallinity, large specific surface area, regular pore structure, high structure controllability, high stability of water, acid and alkali, easiness in separation, good reusability and the like. Under the irradiation of visible light, COF photocatalyst can generate charge separation, generate holes andthe electron pair initiates respective surface oxidation and reduction reactions in a conduction band and a valence band, and simultaneously generated secondary free radical oxidation species such as superoxide anion free radical, singlet oxygen and the like can generate organic mineralization reaction to generate CO2And H2And O. However, because the excited-state carrier lifetime is short in COF materials, the reduction reaction often requires a reaction time of the order of milliseconds, which makes it difficult to realize a reduced organic counter-strain having synthetic value using conduction band electrons. Therefore, COF photocatalysis is less applied to reduction type organic synthesis reaction with high synthesis value, such as dehalogenation reaction of halogenated aromatic compounds.
Disclosure of Invention
In order to improve the problems, the invention provides a dehalogenation method of halogenated aromatic compounds, which comprises the following steps:
under the action of a photocatalyst, the halogen substituent on the aromatic ring of the halogenated aromatic compound is removed to obtain the aromatic compound.
According to an embodiment of the invention, the photocatalyst is selected from COF catalysts, such as at least one of TpTta, TAPA-TFP COF, TpPa-1.
According to an embodiment of the invention, the TAPA-TFP COF has the structure:
according to an embodiment of the invention, the TpPa-1 has the structure:
according to an embodiment of the present invention, the preparation method of the photocatalyst TpTta is described in Chem Commun.2017,53, 11469-11471.
According to an embodiment of the invention, the preparation method of TAPA-TFP COF is described in chem.Commun.,2019,55, 2680-2683.
According to an embodiment of the present invention, the TpPa-1 is prepared according to the method reference j.am.chem.soc.2012, 134, 19524-.
According to an embodiment of the present invention, the light source of the light is LED, sunlight or simulated sunlight; the wavelength of the LED light source is 345-470nm, preferably 395-420nm, such as 395nm and 420 nm; the power of the LED light source is 50-150 watts, such as 100 watts; the power of the simulated sunlight is 200-400 watts, such as 300 watts.
According to an embodiment of the invention, the halogenated aromatic compound contains at least one halogen substituent and optionally also comprises one, two or more RaA group;
the R isaSelected from hydroxy, cyano, amino, haloalkyl, ═ O, unsubstituted or substituted by one, two or more RbSubstituted of the following groups: alkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, arylalkyl, heteroarylalkyl, cycloalkylalkyl, heterocyclylalkyl, alkyloxy, cycloalkyloxy, heterocyclyloxy, aryloxy, heteroaryloxy, -C (O) -alkyl;
the R isbSelected from ═ O, alkyl, cyano, hydroxy, amino, halogen;
for example, the RaIs selected from-C (O) CH3Cyano, CF3；
Preferably, the halogenated aromatic compounds comprise halogenated aromatic compounds and halogenated heteroaromatic compounds;
the halogenated aromatic compound is selected from at least one of p-bromoacetophenone, p-bromobenzonitrile, o-chlorotrifluoromethylbenzene, bromobenzene and p-trifluoromethyl bromobenzene.
Depending on the target compound, it will be understood by those skilled in the art that other groups on the aromatic ring of the halogenated aromatic compound, other than the halogen substituent, may be inert or reactive, preferably inert, under the reaction conditions described above.
According to an embodiment of the invention, the reaction is preferably carried out in the presence of a hydrogen donor; the hydrogen donor is selected from an alcohol compound and/or an organic amine, and the alcohol compound is selected from at least one of methanol, ethanol and isopropanol; the organic amine is selected from at least one of primary amine, secondary amine and tertiary amine, such as at least one of ethylamine, propylamine, butylamine, isopropylamine, diethylmethylamine, dimethylethylamine, diisopropylethylamine, triethylamine and tributylamine.
According to an embodiment of the present invention, the reaction is preferably carried out in the presence of a base; the base is selected from organic bases or inorganic bases, preferably inorganic bases, for example at least one selected from potassium carbonate, cesium carbonate, sodium carbonate, potassium phosphate, sodium phosphate, cesium phosphate, potassium hydroxide, potassium tert-butoxide, sodium hydroxide.
According to an embodiment of the invention, the reaction is optionally with or without the addition of a solvent; when no solvent is added, the hydrogen donor serves as a reaction solvent, for example, the alcohol compound serves as a reaction solvent; when a solvent is used, the solvent is an inert organic solvent, which may be selected from any organic solvent that is inert under the above-mentioned reaction conditions, particularly does not chemically react with the raw materials and products, and is selected from one, two or more of ester solvents, hydrocarbon solvents, halogenated hydrocarbon solvents, alcohol solvents, amide solvents, sulfone solvents, pyrrolidone solvents, nitrile solvents, and other solvents; the ester solvent is at least one selected from ethyl acetate and butyl acetate; the hydrocarbon solvent is selected from at least one of benzene, toluene, xylene, hexane and cyclohexane; the halogenated hydrocarbon solvent is at least one selected from dichloromethane, trichloromethane, 1, 2-dichloroethane and chlorobenzene; the alcohol solvent is at least one selected from methanol, ethanol, isopropanol, n-propanol and n-butanol; the amide solvent is selected from N, N-Dimethylformamide (DMF); the sulfone solvent is selected from dimethyl sulfoxide (DMSO); the pyrrolidone solvent is selected from N-methyl pyrrolidone (NMP); the nitrile solvent is selected from acetonitrile; the other solvent is selected from pyridine.
According to an embodiment of the present invention, the solvent is preferably a nitrile solvent, an amide solvent, a sulfone solvent, such as acetonitrile, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO).
According to an embodiment of the invention, the molar ratio of the halogenated aromatic compound, the hydrogen donor and the base is 1 (1-25) to (1-10), preferably 1 (1-20) to (1-5), such as 1:8:2, 1:20:1 and 1:10: 1.
According to an embodiment of the present invention, the concentration of the photocatalyst in the reaction system is 0.1 to 50g/L, preferably 1 to 8g/L, e.g., 1g/L, 2g/L, 5 g/L.
According to an embodiment of the invention, the reaction is preferably carried out in a transparent reactor, for example a closed transparent reactor.
According to an embodiment of the invention, the reaction is preferably carried out in an inert atmosphere; the inert atmosphere is nitrogen, helium, argon and the like.
According to an embodiment of the invention, the pressure of the inert atmosphere is between 0.01 and 2MPa, such as 0.01 MPa.
According to an embodiment of the invention, the time of the reaction is 10 minutes to 24 hours, preferably 8 minutes to 24 hours, e.g. 8 to 20 hours, such as 8 hours, 10 hours, 12 hours, 18 hours, 20 hours.
According to an embodiment of the invention, the temperature of the reaction is 10-50 ℃, e.g. 25 ℃.
According to an embodiment of the present invention, the reaction may be performed by adding the photocatalyst, the halogenated aromatic compound, the hydrogen donor, the base, and optionally the solvent, stirring, and then irradiating with light, or irradiating with light at the beginning of stirring, and continuing stirring to obtain the aromatic compound.
According to an embodiment of the invention, if stirring is followed by illumination, the stirring time before illumination is from 10 minutes to 1 hour, preferably from 20 to 50 minutes, for example 30 minutes.
Term interpretation and definition
The term "more" means more than three.
The term "halogen" refers to F, Cl, Br and I. In other words, F, Cl, Br, and I may be described as "halogen" in the present specification.
The term "alkyl" is understood to mean preferably a straight-chain or branched, saturated monovalent hydrocarbon radical having from 1 to 40 carbon atoms, preferably C1-10An alkyl group. "C1-10Alkyl "is understood to preferably mean a straight-chain or branched, saturated monovalent hydrocarbon radical having 1,2, 3,4, 5,6, 7, 8, 9 or 10 carbon atoms. The alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a 2-methylbutyl group, a 1-ethylpropyl group, a 1, 2-dimethylpropyl group, a neopentyl group, a 1, 1-dimethylpropyl group, a 4-methylpentyl group, a 3-methylpentyl group, a 2-ethylbutyl group, a 1-ethylbutyl group, a 3, 3-dimethylbutyl group, a 2, 2-dimethylbutyl group, a 1, 1-dimethylbutyl group, a 2, 3-dimethylbutyl group, a 1, 3-dimethylbutyl group or a 1, 2-dimethylbutyl group. In particular, the radicals have 1,2, 3,4, 5,6 carbon atoms ("C)1-6Alkyl groups) such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, more particularly groups having 1,2 or 3 carbon atoms ("C)1-3Alkyl groups) such as methyl, ethyl, n-propyl or isopropyl.
The term "cycloalkyl" is understood to mean an unsaturated monovalent monocyclic or bicyclic hydrocarbon ring, preferably having 3 to 20 carbon atoms, preferably "C3-10Cycloalkyl groups ". The term "C3-10Cycloalkyl "is understood to mean a saturated monovalent monocyclic or bicyclic hydrocarbon ring having 3,4, 5,6, 7, 8, 9 or 10 carbon atoms. Said C is3-10Cycloalkyl groups may be monocyclic hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl, or bicyclic hydrocarbon groups such as decalin rings.
The term "heterocyclyl" means a saturated or unsaturated monovalent monocyclic or bicyclic hydrocarbon ring comprising 1-5 heteroatoms independently selected from N, O or S, preferably "3-10 membered heterocyclyl". The term "3-10 membered heterocyclyl" means a saturated monovalent monocyclic or bicyclic hydrocarbon ring comprising 1-5, preferably 1-3 heteroatoms selected from N, O or S. The heterocyclic group may be attached to the rest of the molecule through any of the carbon atoms or nitrogen atom (if present). In particular, the heterocyclic group may include, but is not limited to: 4-membered rings such as azetidinyl, oxetanyl; 5-membered rings such as tetrahydrofuranyl, dioxolyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, pyrrolinyl; or a 6-membered ring such as tetrahydropyranyl, piperidinyl, morpholinyl, dithianyl, thiomorpholinyl, piperazinyl, or trithianyl; or a 7-membered ring such as diazepanyl. Optionally, the heterocyclic group may be benzo-fused. The heterocyclyl group may be bicyclic, for example but not limited to a 5,5 membered ring, such as a hexahydrocyclopenta [ c ] pyrrol-2 (1H) -yl ring, or a 5,6 membered bicyclic ring, such as a hexahydropyrrolo [1,2-a ] pyrazin-2 (1H) -yl ring. The nitrogen atom containing ring may be partially unsaturated, i.e., it may contain one or more double bonds, such as, but not limited to, 2, 5-dihydro-1H-pyrrolyl, 4H- [1,3,4] thiadiazinyl, 4, 5-dihydrooxazolyl, or 4H- [1,4] thiazinyl, or it may be benzo-fused, such as, but not limited to, dihydroisoquinolinyl. According to the invention, the heterocyclic radical is non-aromatic.
The term "aryl" is understood to mean preferably a mono-, bi-or tricyclic hydrocarbon ring having a monovalent aromatic or partially aromatic character of 6 to 20 carbon atoms, preferably "C6-14Aryl ". The term "C6-14Aryl "is to be understood as preferably meaning a mono-, bi-or tricyclic hydrocarbon ring having a monovalent or partially aromatic character with 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms (" C6-14Aryl group "), in particular a ring having 6 carbon atoms (" C6Aryl "), such as phenyl; or biphenyl, or is a ring having 9 carbon atoms ("C9Aryl), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C10Aryl radicals), such as tetralinyl, dihydronaphthyl or naphthyl, or rings having 13 carbon atoms ("C13Aryl radicals), such as the fluorenyl radical, or a ring having 14 carbon atoms ("C)14Aryl), such as anthracenyl.
The term "heteroaryl" is understood to include such monovalent monocyclic, bicyclic or tricyclic aromatic ring systems: it preferably has 5 to 20 ring atoms and contains 1 to 5 heteroatoms independently selected from N, O or S, such as "5-14 membered heteroaryl". The term "5-14 membered heteroaryl" is understood to include such monovalent monocyclic, bicyclic or tricyclic aromatic ring systems: which has 5,6, 7, 8, 9, 10, 11, 12, 13 or 14 ring atoms, in particular 5 or 6 or 9 or 10 carbon atoms, and which contains 1 to 5, preferably 1 to 3 heteroatoms independently selected from N, O or S and, in addition, can be benzo-fused in each case. In particular, heteroaryl is selected from thienyl, furyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl and the like and their benzo derivatives, such as benzofuryl, benzothienyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, benzotriazolyl, indazolyl, indolyl, isoindolyl and the like; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and the like, and benzo derivatives thereof, such as quinolyl, quinazolinyl, isoquinolyl, and the like; or azocinyl, indolizinyl, purinyl and the like and benzo derivatives thereof; or cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, pteridinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, and the like.
Unless otherwise indicated, heterocyclyl, heteroaryl or heteroarylene include all possible isomeric forms thereof, e.g., positional isomers thereof. Thus, for some illustrative, non-limiting examples, pyridyl or pyridinylene includes pyridin-2-yl, pyridinylene-2-yl, pyridin-3-yl, pyridinylene-3-yl, pyridin-4-yl, and pyridinylene-4-yl; thienyl or thienylene includes thien-2-yl, thien-3-yl and thien-3-yl.
The above definitions of the term "alkyl", such as "alkyl", apply equally to other terms containing "alkyl", such as the terms "alkyloxy", "alkyloxyalkyl", and the like. Likewise, the above definitions of the terms "cycloalkyl", "heterocyclyl", "aryl" and "heteroaryl" apply correspondingly equally to other terms containing them, such as the terms "cycloalkyloxy", "heterocyclyloxy", "aryloxy", "arylalkyl" and "heteroarylalkyl" and the like.
Advantageous effects
The invention discloses a method for synthesizing an aromatic compound by selectively carrying out C-X bond dehalogenation reaction on a halogenated aromatic compound. The reaction system of the invention can selectively dehalogenate the halogenated aromatic compounds to synthesize the aromatic compounds under the action of the photocatalyst, the hydrogen donor and the alkali, and the GC yield of the product can reach more than 92 percent and can reach 99 percent at most.
Compared with the prior art, the method has the advantages that the dehalogenation reaction conditions of the hydrogenated halogenated aromatic compounds are more green and mild by adopting noble metal catalysis. The preparation process is simple, the product can be obtained through one-step reaction, and the method is economical, environment-friendly and convenient to operate. In addition, the catalyst of the invention has low biotoxicity and low cost, the catalyst and the product are easy to separate and recycle, and the catalyst still maintains high catalytic activity after being reused for many times.
Detailed Description
The technical solution of the present invention is explained in detail by the exemplary embodiments below. These examples should not be construed as limiting the scope of the invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the starting materials and reagents described are either commercially available or prepared by known methods.
Preparation example 1 preparation of TpTta
Preparation method of TpTta reference Chem Commun.2017,53,11469-11471
TpTta was synthesized using a solvothermal method. 2,4, 6-Trihydroxyl-1, 3, 5-benzenetricarboxylic acid (0.15mmol), 2,4, 6-tris (4-aminophenyl) -s-triazine (0.15mmol), 3mL of 1, 4-dioxane, and 0.25mL of 6M aqueous acetic acid were added to a Schlenk tube. After rapid freezing in 77K (liquid nitrogen bath), three freeze-evacuate-thaw operations were performed to completely remove oxygen from the system and the Schlenk tube was flame sealed. Schlenk tube was heated at 120 ℃ for 3 days. The precipitate was collected by centrifugation, and the collected precipitate was washed three times with DMF and twice with DCM. The washed powder was dried in a vacuum oven for 12 hours.
Preparation example 2 preparation of TAPA-TFP COF
Preparation of TAPA-TFP COF reference Chem Commun.55,2680-2683
1mmol of 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic acid and 1mmol of tris (4-aminophenyl) amine were added to a Schlenk tube containing 10ml of a mixed solvent of THF to mesitylene (volume ratio: 3: 1). The Schlenk tube was sonicated for 10 minutes at room temperature, then 1ml of 6M aqueous acetic acid was added. After rapid freezing in 77K (liquid nitrogen bath), three freeze-evacuate-thaw operations were performed to completely remove oxygen from the system in N2The Schlenk tube was flame sealed under atmosphere. Then heated in an oil bath at 120 ℃ for three days. After cooling the reaction solution, the insoluble product was filtered under vacuum, the reaction flask was rinsed thoroughly with acetone, the collected solid was transferred to a 125ml conical flask, stirred in hot acetone solvent, filtered while hot, and the procedure was repeated four more times in total. The combined solids were transferred to a brown tube and dried under vacuum at 120 ℃ for 12 hours.
Preparation example 3 preparation of TpPa-1
Preparation method of TpPa-1 reference J.Am.chem.Soc.2012, 134, 19524-19527
To a heat-resistant glass tube (10X 8 mm)2X 18cm) was added 63mg (0.3mmol) of 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic acid, 48mg (0.45mmol) of 1, 4-phenylenediamine (Pa-1), 1.5mL of mesitylene, 1.5mL of 1, 4-dioxane, 0.5mL of 3M aqueous acetic acid. The mixture was sonicated for 10 minutes. After the heat-resistant glass tube was rapidly frozen in 77K (liquid nitrogen bath), three freezing-vacuuming-thawing operations were performed to completely remove oxygen in the system, in N2Flame sealing the tube under atmosphere, heating at 120 deg.C for three days. Centrifuging to obtain red precipitate, and washing the precipitate with anhydrous acetone. The collected powder was exchanged 5 times with anhydrous acetone solvent. The powder was then heated in a vacuum oven at 180 ℃ for 24 hours to give a dark red powder.
Example 1
P-bromoacetophenone, diisopropylethylamine and potassium tert-butoxide in a molar ratio of 1:8:2 (0.1mmol:0.8mmol:0.2mmol) were added to a temperature-controlled transparent reaction flask containing acetonitrile and the temperature was controlled at 25 ℃. The photocatalyst TpTta was added so that the concentration of TpTta in the reaction system became 2 g/L. The concentrations of the p-bromoacetophenone, the diisopropylethylamine and the potassium tert-butoxide in a reaction system are respectively 0.1mol/L, 0.8mol/L and 0.2mol/L, the reaction system is sealed, inert gas is introduced, the pressure of the inert gas in a temperature-controlled transparent reaction bottle is 0.01MPa, the temperature is controlled to be 25 ℃, and the reaction system is stirred for half an hour to ensure that the p-bromoacetophenone is adsorbed and balanced. Then irradiating the temperature-controlled transparent reaction bottle by using a 100W 395nm LED, keeping the temperature at 25 ℃, stopping the reaction after irradiating for 8 hours, and separating a reaction product by using a column chromatography, wherein the reaction product is acetophenone, and the GC yield is 99%.
The catalyst TpTta is recycled by a high-speed centrifugation method. The recovered TpTta was subjected to another catalytic reaction according to the above-mentioned method to prepare acetophenone. From the catalytic results, the yield of the product was 90% after 5 times of recycling of the catalyst. It can be seen that the yield is not substantially changed after the catalyst is repeatedly used, i.e. the catalyst still maintains high catalytic activity.
Example 2
Adding the p-bromobenzonitrile, ethanol and potassium carbonate into a temperature-controlled transparent reaction bottle containing acetonitrile according to the molar ratio of 1:20:1(0.25mmol:5mmol:0.25mmol) and controlling the temperature at 25 ℃. Adding a photocatalyst TAPA-TFP COF to ensure that the concentration of the TAPA-TFP COF photocatalyst in the reaction system is 1 g/L. The concentrations of the p-bromobenzonitrile, the ethanol and the potassium carbonate in the reaction system are respectively 0.25mol/L, 5mol/L and 0.25 mol/L. Sealing the reaction kettle, introducing inert gas, keeping the pressure of the inert gas in the temperature-controlled transparent reaction bottle at 0.01MPa, controlling the temperature at 25 ℃ and stirring for half an hour to ensure that the bromobenzonitrile is adsorbed to be balanced, irradiating the temperature-controlled transparent reaction bottle by using a 100W 420nm LED, keeping the temperature at 25 ℃, stopping the reaction after irradiating for 10 hours, and separating a product by column chromatography, wherein the reaction product is benzonitrile, and the GC yield of the product is 92%.
And recycling the catalyst TAPA-TFP COF by adopting a high-speed centrifugation method. And carrying out secondary catalysis on the recovered TAPA-TFP COF photocatalyst according to the method to prepare benzonitrile. From the catalytic results, the yield of the product was 85% after 5 times of recycling of the catalyst. It can be seen that the yield is not substantially changed after the catalyst is repeatedly used, i.e. the catalyst still maintains high catalytic activity.
Example 3
Adding o-chlorotrifluoromethylene, isopropanol and potassium phosphate into a temperature-controlled transparent reaction bottle containing dimethyl sulfoxide according to the molar ratio of 1:10:1(0.5mmol:5mmol:0.5mmol) and controlling the temperature to be 25 ℃. Adding a photocatalyst TpPa-1 to ensure that the concentration of the TpPa-1 photocatalyst in the reaction system is 5 g/L. The concentrations of the o-chlorotrifluoromethylene, the isopropanol and the potassium phosphate in the reaction system are respectively 0.5mol/L, 5mol/L and 0.5 mol/L. Sealing the reaction kettle, introducing inert gas, keeping the pressure of the inert gas in the temperature-controlled transparent reaction bottle at 0.01MPa, controlling the temperature at 25 ℃ and stirring for half an hour to ensure that the o-chlorotrifluoromethane is adsorbed and balanced, irradiating the temperature-controlled transparent reaction bottle by 300W simulated sunlight and keeping the temperature at 25 ℃, stopping the reaction after irradiating for 12 hours, and separating a product by column chromatography, wherein the reaction product is the benzotrifluoride, and the GC yield is 95%.
And (3) recycling the catalyst TpPa-1 by adopting a high-speed centrifugation method. And carrying out catalytic preparation on the recovered TpPa-1 again according to the method. From the catalytic results, the yield of the product after 5 times of recycling of the catalyst was 86%. It can be seen that the yield is not substantially changed after the catalyst is repeatedly used, i.e. the catalyst still maintains high catalytic activity.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for dehalogenating a halogenated aromatic compound is characterized by comprising the following steps:
under the action of a photocatalyst, the halogen substituent on the aromatic ring of the halogenated aromatic compound is removed to obtain the aromatic compound.
2. The method according to claim 1, wherein the photocatalyst is selected from COF catalysts.
3. The method of claim 2, wherein the COF catalyst is selected from at least one of TpTta, TAPA-TFP COF, TpPa-1.
4. The method according to any one of claims 1 to 3, wherein the light source is LED, sunlight or simulated sunlight.
5. The method according to any one of claims 1 to 4, wherein the halogenated aromatic compound contains at least one halogen substituent, and optionally further comprises one, two or more RaA group;
the R isaSelected from hydroxy, cyano, amino, haloalkyl, ═ O, unsubstituted or substituted by one, two or more RbSubstituted of the following groups: alkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, arylalkyl, heteroarylalkyl, cycloalkylalkyl, heterocyclylalkyl, alkyloxy, cycloalkyloxy, heterocyclyloxy, aryloxy, heteroaryloxy, -C (O) -alkyl;
the R isbSelected from ═ O, alkyl, cyano, hydroxy, amino, halogen.
6. The method according to any one of claims 1 to 5, wherein the halogenated aromatic compounds comprise halogenated aromatic compounds, halogenated heteroaromatic compounds.
7. The method according to any one of claims 1 to 6, wherein the halogenated aromatic compound is selected from at least one of p-bromoacetophenone, p-bromobenzonitrile, o-chlorotrifluorotoluene, bromobenzene, p-trifluoromethylbromobenzene.
8. The process according to any one of claims 1 to 7, characterized in that the reaction is carried out in the presence of a hydrogen donor; the hydrogen donor is selected from an alcohol compound and/or an organic amine, and the alcohol compound is selected from at least one of methanol, ethanol and isopropanol; the organic amine is selected from at least one of primary amine, secondary amine and tertiary amine.
9. The process according to any one of claims 1 to 8, wherein the reaction is carried out in the presence of a base; the base is selected from organic or inorganic bases, for example, at least one selected from potassium carbonate, cesium carbonate, sodium carbonate, potassium phosphate, sodium phosphate, cesium phosphate, potassium hydroxide, potassium tert-butoxide, and sodium hydroxide.
10. The method of any one of claims 1-9, wherein the molar ratio of the halogenated aromatic compound to the hydrogen donor to the base is 1 (1-25) to (1-10);
preferably, the concentration of the photocatalyst in the reaction system is 0.1-50 g/L.
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