CN113443965B - Method for generating aryl phenol compound by hydrolyzing diaryl ether compound - Google Patents

Method for generating aryl phenol compound by hydrolyzing diaryl ether compound Download PDF

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CN113443965B
CN113443965B CN202110549508.7A CN202110549508A CN113443965B CN 113443965 B CN113443965 B CN 113443965B CN 202110549508 A CN202110549508 A CN 202110549508A CN 113443965 B CN113443965 B CN 113443965B
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diaryl ether
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CN113443965A (en
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姜雪峰
周怡琳
胡德庆
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East China Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
    • C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
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    • 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
    • C07C45/61—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
    • C07C45/64—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 introduction of functional groups containing oxygen only in singly bound form
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Abstract

The invention discloses a method for hydrolyzing a diaryl ether compound to generate an aryl phenol compound, which utilizes visible light to excite a photosensitizer for catalysis. In a reaction solvent, the C (sp) of the raw material of the formula (1) is cleaved with the aid of an acid 2 ) -O bond, hydrolysis to obtain two molecules of arylphenolic compounds of formula (3) and (4). The invention can catalyze the reaction at room temperature, is green and environment-friendly, and is simple to operate; wide universality, higher reaction yield and strong functional group tolerance; the synthesis method can realize hydrolysis conversion of various small-scale diaryl ether compounds, hydrolysis of the aclonifen, the triclosan and the lignin template substrate, even hydrolysis of the triclosan and the lignin template substrate in a large scale, realize gram-level degradation, and provide a new strategy for recovering phenol derivatives, degrading pesticides and purifying wastewater containing a bactericide or herbicide through lignin hydrolysis. The invention has wide application prospect and use value.

Description

Method for generating aryl phenol compound by hydrolyzing diaryl ether compound
Technical Field
The invention belongs to the technical field of organic synthesis, and relates to a method for hydrolyzing a diaryl ether compound to generate an aryl phenol compound, in particular to a method for efficiently and conveniently synthesizing the aryl phenol compound by hydrolyzing the compound.
Background
Diaryl ether compounds are a very important class of compounds and widely exist in herbicides, bactericides, dyes and lignin. Such as the weedicide, is a contact herbicide used before or after the emergence, can kill most annual weeds, such as barnyard grass, cattle hair grass, monochoria vaginalis, sparganium stoloniferum and the like in paddy fields, and can also kill crab grass, green bristlegrass, Echinochloa stolonifera and the like in dry fields; triclosan is an efficient and safe externally-applied antibacterial disinfectant which is popular internationally, can kill staphylococcus aureus and escherichia coli, and has the disinfection effect on pyogenic coccus and pathogenic fungi in intestinal tracts. The existence of the substances in farmland wastewater and dye production wastewater threatens the safety of food and drinking water of people. And lignin is the only and most abundant resource of the benzene ring-containing plants, and the annual yield exceeds 1500 hundred million tons. However, in industries using plant fiber as raw material, such as paper making, textile, wood hydrolysis, etc., a large amount of lignin is wasted, resulting in resource waste and environmental pollution. Therefore, the effective exploitation and utilization of lignin, especially the recovery of aromatic compounds, not only can efficiently utilize renewable resources, but also can solve the problems of environmental pollution and energy crisis. Lignin is linked by C-C bonds (5-5, beta-beta, beta-1) or C-O bonds (4-O-5, alpha-O-4, beta-O-4), so that the breaking of these C-C bonds and C-O bonds is the key to the recovery of aromatic compounds, and among the C-O bonds, the breaking of the 4-O-5 structure is most challenging because its Bond Dissociation Energy (BDE) is 77.74kcal/mol, which is higher than that of alpha-O-4 (BDE <57.28kcal/mol) and beta-O-4 (BDE <69.35kcal/mol), so that the breaking study of the 4-O-5 structure is widely carried out.
Figure BDA0003074832460000011
Diaryl ether-containing compound
Currently, the recovery of aromatics by cleavage of the 4-O-5 bond, hydrogenolysis and hydrolysis, are two major routes. In order to avoid the generation of further hydrogenation products such as cyclopentane and derivatives thereof, transition metals such as nickel, iron and cobalt are sequentially applied to the highly selective hydrogenolysis fracture of a 4-O-5 structure, and hydrogen sources are developed from the initial hydrogen requiring 1-6 atmospheres to the safer and more convenient LiAlH 4 Alternatively, another 2.5 equivalents and more of a strong base, e.g. t BuONa、 t BuOK is also necessary, and plays a role in promoting the circulation of the catalyst in the system, andthe temperature is above 120 ℃, and the template substrate diphenyl ether DPE can obtain the corresponding hydrogenolysis products of benzene and phenol with better yield. In addition, metal-free catalyzed hydrogenolysis was developed, the source of hydrogen in the reaction being from Et 3 SiH or NaH, but the equivalent of the compound is still required to be added into the reaction system t BuOK, and the reaction temperature needs to be raised appropriately. The process of producing two molecules of phenol by hydrolysis of DPE is more difficult than hydrogenolysis. The calculations show that the DPE hydrolysis process has a Gibbs free energy of-7.1 kcal/mol, which is lower than-14.2 kcal/mol of the hydrogenolysis process, two reported hydrolysis works use supercritical water, and DPE can be carried out in a 15% phosphoric acid aqueous solution or 0.63g/cm at a temperature above 315 ℃ and a pressure of 10-33MPa 3 The conversion rate of the phenol in the potassium carbonate solution of (2) is 69% or more.
In consideration of practical application practicability, it is particularly important to find a method for preparing aryl phenol compounds by cleaving diaryl ethers under mild conditions, which is environmentally friendly and easy and convenient to operate.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a method for hydrolyzing a diaryl ether compound and generating an aryl phenol compound. The diaryl ether compound can be a symmetrical diaryl ether compound which comprises a charge-donating group or a charge-absorbing group at a para position or a meta position, or an asymmetrical diaryl ether compound which comprises a substituent group-free group at one side, a charge-donating group or a charge-absorbing group at a para position, a meta position or an ortho position at the other side, a herbicide with multiple substituent groups, a degerming agent and a lignin 4-O-5 structure template substrate, wherein the two sides of the substituent group are respectively at the same or different substitution sites and have different substitution groups.
The method has the advantages of mild reaction conditions, high reaction yield and good substrate functional group compatibility. The fluid reaction of the invention can realize the conversion of the simple diphenyl ether substrate, and can also realize the conversion of the degerming agent and the lignin 4-O-5 structure template substrate. The method has wide application prospect and use value, provides a synthetic method with simple operation, high efficiency and environmental protection for recovering phenol from the lignin 4-O-5 structure, and also provides a feasible strategy for purifying wastewater containing a bactericide and a herbicide.
The invention provides a method for hydrolyzing a diaryl ether compound to generate an aryl phenol compound, which takes the diaryl ether compound shown in a formula (1) and water shown in a formula (2) as reaction raw materials, and the aryl phenol compound shown in the formula (3) and the formula (4) is obtained by reaction in a solvent under the action of a catalyst and the assistance of acid in an illumination environment. The reaction process equation is shown in the reaction formula (a):
Figure BDA0003074832460000021
or, the method takes a diaryl ether compound shown in formula (1) as a reaction raw material, and the diaryl ether compound reacts with water in a solvent or water in air in a light environment under the action of a catalyst and the assistance of an acid to obtain aryl phenol compounds shown in formulas (3) and (4), wherein the reaction process is shown in a reaction formula (b);
Figure BDA0003074832460000031
wherein Ar is 1 And Ar 2 Each independently selected from benzene ring, substituted benzene ring, naphthalene ring, etc.; the substituent is C1-10 alkyl, C1-10 alkoxy, halogen, acyl, cyano, nitro, trifluoromethyl and hydroxyl.
Preferably, the first and second electrodes are formed of a metal,
Ar 1 and Ar 2 Can be selected from, but is not limited to, phenyl, p-isopropylphenyl, p-tert-butylphenyl, p-fluorophenyl, p-bromophenyl, p-acetylphenyl, p-methoxycarbonylphenyl, p-cyanophenyl, m-methylphenyl, m-tert-butylphenyl, m-trifluoromethylphenyl, m-cyanophenyl, p-nitrophenyl, m-methoxyphenyl, o-cyanophenyl, o-trifluoromethylphenyl, o-methoxycarbonylphenyl, m-fluorophenyl, 3, 5-dimethylphenyl, p-trifluorophenylMethylphenyl, o-methoxyphenyl, 2, 4-dichlorophenyl, 2-hydroxy-4-chlorophenyl, 2-methoxy-4 ethylphenyl, 2-hydroxy-3-methoxy-5-ethylphenyl, and the like.
In the invention, the reaction also comprises the steps of adding silica gel, spin-drying and separating by column chromatography after the reaction is finished.
In the invention, a diaryl ether compound (1) is used as a reaction raw material, and C (sp) is cleaved under the excitation condition of visible light and the assistance of a catalyst and an acid in a nitrogen atmosphere 2 ) -O bond, hydrolysis reaction to obtain arylphenolic compounds (3) and (4), the specific reaction mechanism being: the oxidation potential of the photo-excited catalyst (uranium species) is 2.60V vs SCE and is larger than that of the diaryl compound of the formula (1) by 1.88V vs SCE, so that a single electron transfer process can be generated, the diaryl compound of the formula (1) forms radical cation A, the carbon-oxygen bond of A is broken under the action of hydrogen ions and uranium dimers to form radical cation B and negative ion C, C is subjected to single protonation to generate phenol (3) and (4), and B is larger than that of uranium species UO because the oxidation potential of B is 1.56V vs SCE 2 2+ 0.32V vs SCE, so that the single electron transfer process occurs again, thereby producing the products (3) and (4).
Wherein, in the reaction route, the water of reaction refers to water additionally added during the reaction or water in a solvent or water in air.
Figure BDA0003074832460000041
In the present invention, the reaction is preferably carried out in nitrogen.
In the invention, the solvent is an organic solvent and is selected from any one of acetonitrile, acetone and the like; preferably, the solvent is acetone.
In the invention, the dosage of the solvent is 1-50 ml; preferably, 2 ml.
In the invention, the concentration of the diaryl ether compound in the solvent is 0.05-0.2 mol/L; preferably, it is 0.2 mol/l.
In the invention, the catalyst is a photocatalyst and is selected from any one of uranyl acetate, uranyl nitrate, zinc uranyl acetate, uranyl sulfate and the like; preferably, the catalyst is uranyl nitrate; the molar dosage of the catalyst is 4-6 mol% of the diaryl ether compound (1); preferably, the amount of catalyst is 6 mol%.
In the invention, the acid is one of trichloroacetic acid, acetic acid and the like; preferably, the acid is trichloroacetic acid; the molar amount of the acid is 1-4 equivalent of the diaryl ether compound (1); preferably, the molar amount of acid used is 2 equivalents.
In the invention, the light source used in the illumination environment is a blue light source with the wavelength of 420-460nm and the power of 1-100W.
In a specific embodiment, in a small scale reaction (0.4mmol), the light source is mild visible light, and the light source can be 1-20W blue LED lamp (wavelength 460nm) or 1-100W blue LED lamp (wavelength 430 nm); preferably, the light source is a 9W blue LED lamp (wavelength 460 nm).
In another embodiment, in the fluid reaction (10mmol), the light source is a mild visible light, and the light source can be a 1-100W blue LED lamp (wavelength 430 nm); preferably, the light source is a 12-54W blue LED lamp (wavelength 430 nm); further preferably, the light source is a 54W blue LED lamp (wavelength 430 nm).
In the invention, the molar ratio of the diaryl ether compound to water is 1:0.1-1:20, wherein the water refers to water which needs to be additionally added in the reaction process, or the water refers to water which only comes from a solvent or water in air and does not need to be additionally added in the reaction process.
In the invention, the reaction temperature is 0-40 ℃; preferably, it is carried out at room temperature of 25 ℃.
In the invention, the reaction time is 2-3 days; preferably, the time of reaction is 2 days.
In the present invention, the light irradiation is continued until the reaction is completed.
The invention also provides an application of the method in synthesis of aryl phenol compounds.
The invention also provides an aryl phenol compound obtained by the synthesis method.
In one embodiment of a small scale (0.4mmol) conversion of diaryl ether compound (1), the synthesis reaction of the present invention is to add diaryl ether compound (0.4mmol), uranyl nitrate photocatalyst (0.016mmol), trichloroacetic acid (0.8mmol), acetone (2mL) in a reaction flask A, and stir at 25 deg.C for 48 hours under visible light (blue LED lamp, 9W) irradiation; after the reaction is finished, adding silica gel for spin drying, and separating by column chromatography to obtain aryl phenol compounds (3) and (4).
The beneficial effects of the invention include: a) the visible light catalyzes the reaction at room temperature, so the method is green and environment-friendly and is simple to operate; b) wide universality, higher reaction yield and strong functional group tolerance; c) the synthetic method can realize hydrolysis conversion of various diaryl ether compounds on a small scale, hydrolysis of the aclonifen, the triclosan and the lignin template substrate, even hydrolysis of the triclosan and the lignin template substrate on a large scale, and provides a new strategy for recovering phenol derivatives, degrading pesticides and purifying wastewater containing a bactericide or herbicide by lignin hydrolysis.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples. The procedures, conditions, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited.
The synthesis reaction of the aryl phenol compound comprises the following steps: adding a diaryl ether compound (1), water, a photocatalyst uranyl nitrate, trichloroacetic acid and acetone into a reaction bottle A, and stirring at room temperature under the irradiation of visible light; after the reaction is finished, adding silica gel for spin drying, and separating by column chromatography to obtain aryl phenol compounds (3) and (4). Wherein the water of reaction in this route is additionally added water.
Or adding the diaryl ether compound (1), the photocatalyst uranyl nitrate, trichloroacetic acid and acetone into the reaction bottle A, and stirring at room temperature under the irradiation of visible light; after the reaction is finished, adding silica gel for spin drying, and separating by column chromatography to obtain aryl phenol compounds (3) and (4). Wherein the water of reaction in the route is derived from water in a solvent or water in air.
Example 1
Figure BDA0003074832460000051
Adding 1a (0.4mmol,68.0mg), uranyl nitrate hydrate (4 mol%/0.016 mmol,8mg) into a 25mL reaction tube, wherein the water of formula (2) is derived from acetone dimerization and dehydration in the reaction formula (c), the ratio of 1a to water effectively participating in the reaction is 1:0.8, trichloroacetic acid (0.8mmol,130.7mg) and acetone (2mL), evacuating and exchanging nitrogen for 3 times at-78 deg.C, stirring at 25 deg.C under the irradiation of a 9W blue LED lamp (wavelength 460nm) for 48 hours, concentrating after the reaction is finished, and performing column chromatography (V) PE /V EA 10/1) to give a white solid 2a (60.2mg, 80%);
1 H NMR(400MHz,CDCl 3 )δ7.28-7.24(m,2H),6.95(t,J＝8.0Hz,1H),6.85(d,J＝8.0Hz,2H),5.02(brs,1H). 13 C NMR(100MHz,CDCl 3 )δ155.3,129.7,120.8,115.3.IR(neat)3237,1594,1498,1472,1221,1071,810cm -1 .MS(EI)m/z 94.
fluid chemistry: in a 250mL three-neck flask, 1a (10.0mmol,1.70g), uranyl nitrate hydrate (4 mol%/0.4 mmol,201mg), water of formula (2) was derived from acetone in reaction formula (c) through dimerization and dehydration, the ratio of 1a to water effectively participating in the reaction was 1:0.78, trichloroacetic acid (20mmol,3.26g), acetone (50mL), after evacuation and nitrogen exchange, the reaction solution was circulated in a polytetrafluoroethylene tube (o.d.: 2mm, i.d.: 1mm, length h ═ 5.68m, volume ═ 4.45mL) under the action of a pump (flow rate 0.5mL/min), while a polytetrafluoroethylene tube was irradiated with a 54 watt blue LED lamp (wavelength 430nm), reacted at 25 ℃ for 48 hours, after completion of the reaction, extracted, concentrated, and subjected to column chromatography (V column chromatography) (V ═ 0.0.0 mmol,1.70g), and concentrated PE /V EA 10/1) gave a brown solution 2a (78%, 2.34 g).
Figure BDA0003074832460000061
Example 2
Figure BDA0003074832460000062
Adding 1b (0.2mmol,50.8mg), uranyl nitrate hydrate (4 mol%/0.008 mmol,4mg) into a 25mL reaction tube at a ratio of water to water effective for the reaction of 1:0.64 as in example 1, 1b, trichloroacetic acid (0.4mmol,65.4mg), acetone (2mL), evacuating at-78 deg.C for 3 times, stirring at 25 deg.C under irradiation of 9W blue LED lamp (wavelength 460nm) for 48 hr, concentrating, and performing column chromatography (V) PE /V EA 10/1) to give 2b (34.8mg, 64%) as a brown solid;
1 H NMR(400MHz,CDCl 3 )δ7.11(d,J＝8.0Hz,2H),6.78(d,J＝8.0Hz,2H),4.43(brs,1H),2.89-2.83(m,1H),1.23(d,J＝8.0Hz,6H). 13 C NMR(100MHz,CDCl 3 )δ153.3,127.4,115.1,33.3,24.2.IR(neat)3317,2959,1612,1512,1225,1174,827cm -1 .MS(EI)m/z 136.
example 3
Figure BDA0003074832460000071
Adding 1c (0.2mmol,56.4mg), uranyl nitrate hydrate (4 mol%/0.008 mmol,4mg) into a 25mL reaction tube at a ratio of water to water effective for the reaction of 1, 1c as in example 1:0.68, trichloroacetic acid (0.4mmol,65.4mg), acetone (2mL), evacuating at-78 deg.C for 3 times, stirring at 25 deg.C under irradiation of 9W blue LED lamp (wavelength 460nm) for 48 hr, concentrating, and performing column chromatography (V) PE /V EA 10/1) to yield 2c (40.8mg, 68%) as a white solid;
1 H NMR(400MHz,CDCl 3 )δ7.32-7.28(m,2H),6.84-6.80(m,2H),4.95(brs,1H),1.34(s,9H). 13 C NMR(100MHz,CDCl 3 )δ153.1,143.6,126.4,114.7,34.0,31.5.IR(neat)3235,2961,1703,1515,1361,1232,1181cm -1 .MS(EI)m/z 150.
example 4
Figure BDA0003074832460000072
Adding 1d (0.2mmol,41.2mg), uranyl nitrate hydrate (4 mol%/0.008 mmol,4mg) into a 25mL reaction tube, wherein the ratio of water to water effectively participating in the reaction is 1:0.49 as in example 1, 1d, trichloroacetic acid (0.4mmol,65.4mg), acetone (2mL), evacuating at-78 deg.C for 3 times, stirring at 25 deg.C under the irradiation of 9W blue LED lamp (wavelength 460nm) for 48 hr, concentrating after the reaction is finished, and performing column chromatography (V) PE /V EA 10/1) to yield brown liquid 2d (21.9mg, 49%);
1 H NMR(400MHz,CDCl 3 )δ6.95-6.91(m,2H),6.79-6.75(m,2H),4.71(brs,1H). 13 C NMR(100MHz,CDCl 3 )δ157.3(d,J＝237Hz),151.4(d,J＝2.0Hz),116.2(d,J＝8.0Hz),116.0(d,J＝23.0Hz). 19 F NMR(376MHz,CDCl 3 )δ-124.16.IR(neat)3346,1507,1223,1195,1091,829,746cm -1 .MS(EI)m/z 112.
example 5
Figure BDA0003074832460000073
Adding 1e (0.2mmol,65.2mg), uranyl nitrate hydrate (4 mol%/0.008 mmol,4mg) to a 25mL reaction tube at a ratio of 1:0.49 of water to that of example 1, 1e and water effective for the reaction, trichloroacetic acid (0.4mmol,65.4mg), acetone (2mL), evacuating at-78 deg.C for 3 times, stirring at 25 deg.C under irradiation of 9W blue LED lamp (wavelength 460nm) for 72 hr, concentrating, and performing column chromatography (V) PE /V EA 10/1) to give brown liquid 2e (21.9mg, 49%);
1 H NMR(400MHz,CDCl 3 )δ7.35-7.32(m,2H),6.74-6.70(m,2H),4.96(brs,1H). 13 C NMR(100MHz,CDCl 3 )δ154.5,132.5,117.2,112.9.IR(neat)3322,1559,1491,1432,1165,1091,1009cm -1 .MS(EI)m/z 172.
example 6
Figure BDA0003074832460000081
1f (0.2mmol,50.8mg), uranyl nitrate hydrate (4 mol%/0.008 mmol,4mg) was added to a 25mL reaction tube in the same manner as in example 1, the ratio of 1f to water effective for the reaction was 1:0.72, trichloroacetic acid (0.4mmol,65.4mg), acetone (2mL) was evacuated at-78 ℃ and nitrogen was exchanged 3 times, the mixture was stirred at 25 ℃ for 48 hours under the irradiation of a 9W blue LED lamp (wavelength 460nm), after completion of the reaction, the mixture was concentrated and column-chromatographed (V column chromatography) PE /V EA 5/1) to give 2f (39.2mg, 72%) as a brown solid;
1 H NMR(400MHz,CDCl 3 )δ7.91(d,J＝8.0Hz,2H),6.90(d,J＝8.0Hz,2H),6.24(brs,1H),2.56(s,3H). 13 C NMR(100MHz,CDCl 3 )δ198.0,160.9,131.1,129.8,115.5,26.3.IR(neat)3384,1587,1525,1488,1350,1069,1006cm -1 .MS(EI)m/z 136.
example 7
Figure BDA0003074832460000082
1g (0.2mmol,57.2mg), uranyl nitrate hydrate (4 mol%/0.008 mmol,4mg) was added to a 25mL reaction tube in the same manner as in example 1, the ratio of 1g to water effective for the reaction was 1:0.88, trichloroacetic acid (0.4mmol,65.4mg), acetone (2mL) was evacuated at-78 ℃ for 3 nitrogen changes, stirred at 25 ℃ for 48 hours under irradiation of a 9W blue LED lamp (wavelength 460nm), concentrated after completion of the reaction, and subjected to column chromatography (V) PE /V EA 5/1) to yield 2g (53.5mg, 88%) of a white solid;
1 H NMR(400MHz,CDCl 3 )δ7.95(d,J＝8.0Hz,2H),6.88(d,J＝8.0Hz,2H),3.90(s,3H). 13 C NMR(100MHz,CDCl 3 )δ167.4,160.1,131.9,122.3,115.2,52.0.IR(neat)3276,1688,1438,1235,1172,859,770cm -1 .MS(EI)m/z 152.
example 8
Figure BDA0003074832460000083
Adding 1h (0.2mmol,44.0mg), uranyl nitrate hydrate (4 mol%/0.008 mmol,4mg) into a 25mL reaction tube, mixing water with the same ratio of 1h and water effectively participating in the reaction as in example 1, 1:0.97, trichloroacetic acid (0.4mmol,65.4mg), acetone (2mL), evacuating at-78 deg.C for 3 times, stirring at 25 deg.C under irradiation of 9W blue LED lamp (wavelength 460nm) for 48 hr, concentrating after the reaction is finished, and performing column chromatography (V) PE /V EA 5/1) to give a white solid 2h (46.2mg, 97%);
1 H NMR(400MHz,CDCl 3 )δ7.55(d,J＝8.7Hz,2H),6.93(d,J＝8.7Hz,2H),6.49(brs,1H). 13 C NMR(100MHz,CDCl 3 )δ160.0,134.3,119.2,116.4,103.2.IR(neat)3293,2235,1610,1587,1510,1286,1167cm -1 .MS(EI)m/z 119.
example 9
Figure BDA0003074832460000091
1i (0.2mmol,39.6mg), uranyl nitrate hydrate (4 mol%/0.008 mmol,4mg) were added to a 25mL reaction tube in the same manner as in example 1, the ratio of 1i to water effective for the reaction was 1:0.83, trichloroacetic acid (0.4mmol,65.4mg), acetone (2mL) was evacuated at-78 ℃ for 3 nitrogen changes, stirred at 25 ℃ for 48 hours under irradiation of a 9W blue LED lamp (wavelength 460nm), concentrated after completion of the reaction, and subjected to column chromatography (V) PE /V EA 10/1) to give a pale red liquid 2i (35.8mg, 83%);
1 H NMR(400MHz,CDCl 3 )δ7.13(t,J＝8.0Hz,1H),6.75(d,J＝8.0Hz,1H),6.65(d,J＝12.0Hz,2H),4.87(brs,1H),2.31(s,3H). 13 C NMR(100MHz,CDCl 3 )δ155.3,139.8,129.4,121.6,116.0,112.2,21.3.IR(neat)3314,1589,1491,1278,1154,926,773cm -1 .MS(EI)m/z 108.
example 10
Figure BDA0003074832460000092
Adding 1j (0.4mmol,113.0mg), uranyl nitrate hydrate (4 mol%/0.016 mmol,8mg) into a 25mL reaction tube, wherein the ratio of water to water in example 1, 1j to water effectively participating in the reaction is 1:0.74, trichloroacetic acid (0.8mmol,130.7mg), acetone (2mL), evacuating at-78 deg.C for 3 times, stirring at 25 deg.C under the irradiation of 9W blue LED lamp (wavelength 460nm), concentrating, and performing column chromatography (V) PE /V EA 10/1) to yield 2j (84.1mg, 74%) as a white solid;
1 H NMR(400MHz,CDCl 3 )δ7.18(t,J＝8.0Hz,1H),6.99-6.97(m,1H),6.88-6.87(m,1H),6.67-6.64(m,1H),4.81(brs,1H),1.31(s,9H). 13 C NMR(100MHz,CDCl 3 )δ155.2,153.3,129.1,117.8,112.5,112.2,34.6,31.2.IR(neat)3307,2963,1451,1280,914,780,699cm - 1 .MS(EI)m/z 150.
example 11
Figure BDA0003074832460000093
Adding 1k (0.4mmol,122.4mg), uranyl nitrate hydrate (4 mol%/0.016 mmol,8mg) into a 25mL reaction tube, wherein the ratio of water to water in example 1 and 1k to water effectively participating in the reaction is 1:0.82, trichloroacetic acid (0.8mmol,130.7mg), acetone (2mL), evacuating at-78 deg.C for 3 times, stirring at 25 deg.C under the irradiation of 9W blue LED lamp (wavelength 460nm), concentrating, and performing column chromatography (V) PE /V EA 10/1) to yield 2k (106.3mg, 82%) as a brown liquid;
1 H NMR(400MHz,CDCl 3 )δ7.36(t,J＝8.0Hz,1H),7.22(d,J＝8.0Hz,1H),7.10(s,1H),7.02(dd,J＝8.0,4.0Hz,1H),5.59(brs,1H). 13 C NMR(100MHz,CDCl 3 )155.3,132.1(q,J＝32.4Hz),130.3,123.7(q,J＝272.3Hz),118.8(d,J＝1.0Hz),117.8(q,J＝3.9Hz),112.3(q,J＝3.8Hz). 19 F NMR(376MHz,CDCl 3 )δ-62.80.IR(neat)3356,1460,1332,1128,1064,894,791cm -1 .MS(EI)m/z 162.
example 12
Figure BDA0003074832460000101
1l (0.4mmol,88.0mg), uranyl nitrate hydrate (4 mol%/0.016 mmol,8mg) was added to a 25mL reaction tube at a ratio of 1:0.82 of water to water available for reaction as in example 1, 1l, trichloroacetic acid (0.8mmol,130.7mg), acetone (2mL), evacuated at-78 deg.C for 3 times to exchange nitrogen, stirred at 25 deg.C for 72 hours under irradiation of 12W blue LED lamp (wavelength 430nm), concentrated after completion of reaction, and subjected to column chromatography (V) PE /V EA 5/1) to give 2l (78.0mg, 82%) of brown solid;
1 H NMR(400MHz,CDCl 3 )δ7.34(t,J＝8.0Hz,1H),7.26-7.22(m,1H),7.14(m,1H),7.11-7.09(m,1H),5.90(brs,1H). 13 C NMR(100MHz,CDCl 3 )δ156.1,130.6,124.5,120.7,118.7,118.5,112.8.IR(neat)3410,2924,2242,1599,1584,1318,1287cm -1 .MS(EI)m/z 119.
example 13
Figure BDA0003074832460000102
Adding 1af (0.2mmol,42.4mg), uranyl nitrate hydrate (4 mol%/0.008 mmol,4mg) into a 25mL reaction tube at a ratio of water to water effective for the reaction of example 1, 1af to 1:0.79, trichloroacetic acid (0.4mmol,65.3mg), acetone (2mL), evacuating at-78 deg.C for 3 times, stirring at 25 deg.C under irradiation of 9W blue LED lamp (wavelength 460nm) for 72 hr, concentrating, and performing column chromatography (V) PE /V EA 10/1) gave brown liquid 2a (7.5mg, 40%) which was purified by column chromatography (V) PE /V EA 5/1) was isolated as a brown solid 2f (21.5mg, 79%).
Example 14
Figure BDA0003074832460000111
1ag (0.2mmol,45.6mg), uranyl nitrate hydrate (4 mol%/0.008 mmol,4mg) were added to a 25mL reaction tube in the same manner as in example 1, the ratio of 1ag to water effective for the reaction was 1:0.7, trichloroacetic acid (0.4mmol,65.3mg), acetone (2mL) was evacuated at-78 ℃ for 3 nitrogen changes, stirred at 25 ℃ for 72 hours under irradiation of a 9W blue LED lamp (wavelength 460nm), after completion of the reaction, concentrated, and subjected to column chromatography (V) PE /V EA 10/1) gave brown liquid 2a (11.7mg, 62%) which was purified by column chromatography (V) PE /V EA 5/1) was isolated as a white solid, 2g (21.3mg, 70%).
Example 15
Figure BDA0003074832460000112
Adding 1ah (0.2mmol,39.0mg), uranyl nitrate hydrate (4 mol%/0.008 mmol,4mg) into a 25mL reaction tube at a ratio of water to water effective for the reaction of example 1, 1ah to 1:0.99, trichloroacetic acid (0.4mmol,65.3mg), acetone (2mL), evacuating at-78 deg.C for 3 times, stirring at 25 deg.C under irradiation of 9W blue LED lamp (wavelength 460nm) for 72 hr, concentrating after the reaction is finished, and performing column chromatography (V) PE /V EA 10/1) brown liquid 2a (13.2mg, 70%) was isolated by column chromatography (V) PE /V EA 5/1) was isolated as a white solid for 2h (23.4mg, 99%).
Example 16
Figure BDA0003074832460000113
1am (0.2mmol,43.0mg), uranyl nitrate hydrate (4 mol%/0.008 mmol,4mg) were added to a 25mL reaction tube at a ratio of 1:0.73 of water from example 1, 1am to water available for reaction, trichloroacetic acid (0.4mmol,65.3mg), acetone (2mL), evacuated at-78 ℃ for 3 nitrogen changes, stirred at 25 ℃ for 72 hours under irradiation of a 9W blue LED lamp (wavelength 460nm), concentrated after completion of the reaction, passed through a columnChromatography (V) PE /V EA 10/1) gave brown liquid 2a (13.7mg, 73%) which was purified by column chromatography (V) PE /V EA 5/1) to give 2m (19.2mg, 69%) as a yellow solid;
1 H NMR(400MHz,CDCl 3 )δ8.19-8.15(m,2H),6.94-6.90(m,2H),6.20(brs,1H). 13 C NMR(100MHz,CDCl 3 )δ161.5,141.5,126.2,115.7.IR(neat)3366,1613,1595,1335,1297,1114,844cm -1 .MS(EI)m/z 139.
example 17
Figure BDA0003074832460000114
Adding 1an (0.4mmol,80.0mg), uranyl nitrate hydrate (4 mol%/0.016 mmol,8mg) into a 25mL reaction tube, wherein the ratio of water to 1an and water effectively participating in the reaction is 1:0.59, trichloroacetic acid (0.8mmol,130.7mg), acetone (2mL) in the same example 1, evacuating at-78 deg.C and changing nitrogen for 3 times, stirring at 25 deg.C under the irradiation of 12W blue LED lamp (wavelength 430nm) for 72 hr, concentrating after the reaction is finished, and performing column chromatography (V) PE /V EA Separation under column chromatography (V) to give brown liquid 2a (32.3mg, 56%) (10/1) PE /V EA 10/1) to give 2n (29.3mg, 59%) as a brown liquid;
1 H NMR(400MHz,CDCl 3 )δ7.14(t,J＝8.1Hz,1H),6.53-6.47(m,1H),6.45-6.40(m,2H),4.96(brs,1H),3.79(s,3H). 13 C NMR(100MHz,CDCl 3 )δ160.8,156.6,130.1,107.7,106.4,101.4,55.2.IR(neat)1584,1479,1451,1292,1250,1057,747cm -1 .MS(EI)m/z 124.
example 18
Figure BDA0003074832460000121
A25 mL reaction tube was charged with 1ao (0.2mmol,37.2mg), uranyl nitrate hydrate (4 mol%/0.008 mmol,4mg), water from the same source as in example 1, 1ao in a ratio of 1:0.61 to water available for reaction, trichloroacetic acid (0.4mmol,65.3mg),acetone (2mL), evacuating at-78 deg.C for 3 times, stirring at 25 deg.C under irradiation of 9W blue LED lamp (wavelength 460nm) for 72 hr, concentrating, and performing column chromatography (V) PE /V EA 10/1) gave brown liquid 2a (10.9mg, 58%) which was isolated by column chromatography (V) PE /V EA 5/1) to yield 2o (13.4mg, 61%) as a white solid;
1 H NMR(400MHz,CDCl 3 )δ6.88-6.86(m,2H),6.84-6.81(m,2H),5.23(brs,2H). 13 C NMR(100MHz,CDCl 3 )δ143.4,121.2,115.4.IR(neat)3450,3327,1513,1470,1364,1282,1256cm -1 .MS(EI)m/z 110.
example 19
Figure BDA0003074832460000122
Adding 1ap (0.4mmol,68.0mg), uranyl nitrate hydrate (4 mol%/0.016 mmol,8mg) into a 25mL reaction tube at a ratio of 1:0.65 of water from example 1, 1ap to water available for reaction, trichloroacetic acid (0.8mmol,130.7mg), and acetone (2mL), evacuating at-78 deg.C and changing nitrogen for 3 times, stirring at 25 deg.C under irradiation of 9W blue LED lamp (wavelength 460nm) for 72 hr, concentrating after reaction, and performing column chromatography (V) PE /V EA 10/1) gave brown liquid 2a (22.6mg, 60%) which was purified by column chromatography (V) PE /V EA 10/1) to give 2p as a white solid (42.1mg, 65%);
1 H NMR(400MHz,CDCl 3 )δ7.52(d,J＝8.0Hz,1H),7.43(t,J＝7.6Hz,1H),7.01(t,J＝8.0Hz,1H),6.96(d,J＝8.0Hz,1H),5.52(brs,1H). 13 C NMR(100MHz,CDCl 3 )δ153.4(d,J＝2.0Hz),133.5,126.8(q,J＝4.8Hz),124.1(q,J＝271.0Hz),119.1(d,J＝298.7Hz),116.4(q,J＝30.3Hz). 19 F NMR(376MHz,CDCl 3 )δ-60.85.IR(neat)3459,1616,1464,1322,1263,1163,1106cm -1 .MS(EI)m/z 162.
example 20
Figure BDA0003074832460000131
Adding 1aq (0.2mmol,39.0mg), uranyl nitrate hydrate (4 mol%/0.008 mmol,4mg) into a 25mL reaction tube at a ratio of 1:0.81 of water to that of example 1, 1aq and water effective for the reaction, trichloroacetic acid (0.4mmol,65.3mg), acetone (2mL), evacuating at-78 deg.C for 3 times, stirring at 25 deg.C under irradiation of 9W blue LED lamp (wavelength 460nm) for 72 hr, concentrating after the reaction is finished, and performing column chromatography (V) PE /V EA 10/1) gave brown liquid 2a (15.0mg, 80%) which was purified by column chromatography (V) PE /V EA 10/1) to give 2q (19.2mg, 81%) as a white solid;
1 H NMR(400MHz,CDCl 3 )δ7.52-7.45(m,2H),7.02-6.97(m,2H),6.67(brs,1H). 13 C NMR(100MHz,CDCl 3 )δ158.7,134.7,132.9,120.8,116.6,116.3,99.3.IR(neat)3262,2229,1603,1503,1234,1160,1100cm -1 .MS(EI)m/z 119.
example 21
Figure BDA0003074832460000132
Adding 1ar (0.4mmol,91.2mg), uranyl nitrate hydrate (4 mol%/0.016 mmol,8mg) into a 25mL reaction tube, wherein the ratio of water to 1ar is 1:0.92 as in example 1, the ratio of 1ar to water effectively participating in the reaction, trichloroacetic acid (0.8mmol,130.7mg), and acetone (2mL), evacuating at-78 deg.C for 3 times, stirring at 25 deg.C under the irradiation of 12W blue LED lamp (wavelength 430nm) for 72 hr, concentrating after the reaction is finished, and performing column chromatography (V) PE /V EA Separation under column chromatography (V) to give brown liquid 2a (30.5mg, 81%) (10/1) PE /V EA 5/1) to yield yellow liquid 2r (55.9mg, 92%);
1 H NMR(400MHz,CDCl 3 )δ10.77(brs,1H),7.84(dd,J＝8.0,1.7Hz,1H),7.48-7.44(m,1H),6.98(d,J＝8.4Hz,1H),6.90-6.86(m,1H),3.95(s,3H). 13 C NMR(100MHz,CDCl 3 )δ170.5,161.5,135.6,129.8,119.1,117.5,112.3,52.2.IR(neat)1674,1614,1485,1438,1301,1089,848cm -1 .MS(EI)m/z 152.
fluid chemistry: in a 250mL three-necked flask, 1ar (10.0mmol,2.28g), uranyl nitrate hydrate (4 mol%/0.4 mmol,201mg) was charged, and the source of water was the same as in example 1, the ratio of 1ar to water available to participate in the reaction was 1:0.72, trichloroacetic acid (20mmol,3.26g), acetone (50mL), after evacuating at-78 ℃ for 3 times of nitrogen exchange, the reaction mixture was circulated through a polytetrafluoroethylene tube (o.d.: 2mm, i.d.: 1mm, length h ═ 5.68m, volume ═ 4.45mL) by a pump (flow rate 0.5mL/min), and the polytetrafluoroethylene tube was irradiated with a 54 watt blue LED lamp (wavelength 430nm) to react at 25 ℃ for 48 hours, after completion of the reaction, the reaction mixture was concentrated and subjected to column chromatography (V) PE /V EA 10/1) brown liquid 2a (0.67g, 71%) was isolated by column chromatography (V) PE /V EA 5/1) was isolated as a yellow liquid 2r (1.09g, 72%).
Example 22
Figure BDA0003074832460000141
Adding 1cm (0.4mmol,108.4mg), uranyl nitrate hydrate (4 mol%/0.016 mmol,8mg) into a 25mL reaction tube, wherein the ratio of water to water in the reaction tube is 1:0.65 as in example 1, 1cm, trichloroacetic acid (0.8mmol,130.7mg), acetone (2mL), evacuating at-78 deg.C for 3 times, stirring at 25 deg.C under the irradiation of 12W blue LED lamp (wavelength 430nm) for 72 hr, concentrating, and performing column chromatography (V) PE /V EA White solid 2c (39.0mg, 65%) was isolated by column chromatography (V) 10/1 PE /V EA 5/1) was isolated as a yellow solid 2m (28.3mg, 51%).
Example 23
Figure BDA0003074832460000142
Into a 25mL reaction tube was charged 1is (0.4mmol,97.6mg), uranyl nitrate hydrate (6 mol%/0.024 mmol,12mg), water from the same source as in example 1, 1is in a ratio of 1:0.82 to water available for reaction, trichloroacetic acid (0.8mmol,130.7mg), acetone (2mL),evacuating at-78 deg.C, changing nitrogen for 3 times, stirring at 25 deg.C under the irradiation of 12W blue LED lamp (wavelength of 430nm) for 72 hr, concentrating after reaction, and performing column chromatography (V) PE /V EA 10/1) gave 2i (32.8mg, 76%) as a pink liquid which was purified by column chromatography (V) PE /V EA 5/1) to yield 2s (55.8mg, 82%) as a yellow solid;
1 H NMR(400MHz,CDCl 3 )δ7.56–7.54(m,2H),7.46(d,J＝8.7Hz,2H),7.42–7.33(m,2H),7.31–7.26(m,1H),6.91(d,J＝8.7Hz,2H),4.83(br,1H). 13 C NMR(100MHz,CDCl 3 )δ155.0,140.7,134.0,128.7,128.3,126.7,126.6,115.6.IR(neat)3403,2982,1739,1711,1597,1521,1488,1460,1373,1239,1201,1045,832,756,686cm -1 .MS(EI)m/z 170.
example 24
Figure BDA0003074832460000143
Adding 1th (0.4mmol,89.2mg), uranyl nitrate hydrate (4 mol%/0.016 mmol,8mg) into a 25mL reaction tube, wherein the ratio of water to water effectively participating in the reaction is 1:0.91 as in example 1, 1th, trichloroacetic acid (0.8mmol,130.7mg), acetone (2mL), evacuating at-78 deg.C for 3 times, stirring at 25 deg.C under the irradiation of 12W blue LED lamp (wavelength 430nm) for 72 hr, concentrating, and performing column chromatography (V) PE /V EA Separation under vacuum 5/1 gave a white solid 2h (43.3mg, 91%) which was purified by column chromatography (V) PE /V EA 10/1) to give 2t (23.9mg, 49%) as a brown solid;
1 H NMR(400MHz,CDCl 3 )δ6.58(s,1H),6.46(s,2H),4.63(brs,1H),2.27(s,6H). 13 C NMR(100MHz,CDCl 3 )δ155.3,139.5,122.5,112.9,21.2.IR(neat)3269,2920,1632,1598,1312,1158,835,cm -1 .MS(EI)m/z 122.
example 25
Figure BDA0003074832460000151
Adding 1tu (0.4mmol,106.0mg), uranyl nitrate hydrate (4 mol%/0.016 mmol,8mg) into a 25mL reaction tube at a ratio of 1tu to water available for reaction of example 1 to 0.72, trichloroacetic acid (0.8mmol,130.7mg), acetone (2mL), evacuating at-78 deg.C for 3 times, stirring at 25 deg.C under irradiation of 12W blue LED lamp (430 nm wavelength), concentrating, and performing column chromatography (V) PE /V EA Separation of 2t (19.0mg, 39%) as brown solid by column chromatography (V) 20/1 PE /V EA 10/1) to give 2u (46.7mg, 72%) as a brown solid;
1 H NMR(400MHz,CDCl 3 )δ7.51(d,J＝12.0Hz,2H),6.91(d,J＝8.0Hz,2H),5.66(brs,1H). 13 C NMR(100MHz,CDCl 3 )δ158.0,127.2(q,J＝3.7Hz),124.3(q,J＝269.0Hz),123.3(q,J＝32.8Hz),115.4. 19 F NMR(376MHz,CDCl 3 )δ-61.54.IR(neat)3357,1617,1604,1522,1319,1247,1158cm -1 .MS(EI)m/z 162.
example 26
Figure BDA0003074832460000152
Adding 1jq (0.4mmol,100.4mg), uranyl nitrate hydrate (4 mol%/0.016 mmol,8mg) into a 25mL reaction tube, wherein the ratio of water source to water in example 1, 1jq and effective water for reaction is 1:0.92, trichloroacetic acid (0.8mmol,130.7mg), acetone (2mL), evacuating at-78 deg.C for 3 times, stirring at 25 deg.C under irradiation of 9W blue LED lamp (wavelength 460nm) for 72 hr, concentrating after reaction, and performing column chromatography (V) PE /V EA 10/1 to give 2j (44.4mg, 74%) as a white solid which is purified by column chromatography (V) PE /V EA 5/1) was isolated as a brown solid 2q (43.4mg, 92%).
Example 27
Figure BDA0003074832460000153
To a 25mL reaction tube, 1qv (0.4mmol,90.0mg) was added,uranyl nitrate hydrate (4 mol%/0.016 mmol,8mg), water from the same source as in example 1, 1qv and water available for reaction at a ratio of 1:0.64, trichloroacetic acid (0.8mmol,130.7mg), acetone (2mL), evacuating and exchanging nitrogen for 3 times at-78 deg.C, stirring at 25 deg.C under the irradiation of 9W blue LED lamp (wavelength 460nm) for 72 hr, concentrating after reaction, and performing column chromatography (V) PE /V EA Separation of 2q (30.2mg, 64%) as brown solid by column chromatography (V) 10/1 PE /V EA 50/1) to yield 2v (19.2mg, 39%) as a brown liquid;
1 H NMR(400MHz,CDCl 3 )δ6.95-6.91(m,1H),6.90–6.83(m,3H),5.65(brs,1H),3.89(s,3H). 13 C NMR(100MHz,CDCl 3 )δ146.5,145.5,121.3,120.0,114.4,110.6,55.7.IR(neat)3510,3449,2932,2842,1596,1499,1443cm -1 .MS(EI)m/z 124.
example 28
Figure BDA0003074832460000161
Adding 1wq (0.2mmol,42.6mg), uranyl nitrate hydrate (4 mol%/0.008 mmol,4mg) into a 25mL reaction tube, wherein the ratio of water source to water effectively participating in the reaction is 1:0.88 as in example 1, 1wq, trichloroacetic acid (0.4mmol,65.3mg), acetone (2mL), evacuating at-78 deg.C for 3 times, stirring at 25 deg.C under irradiation of 9W blue LED lamp (wavelength 460nm) for 72 hr, concentrating after the reaction is finished, and performing column chromatography (V) PE /V EA 10/1) as a brown solid 2q (27.4mg, 88%) was isolated by column chromatography (V) PE /V EA 40/1) to give 2w (15.0mg, 67%) of brown liquid;
1 H NMR(400MHz,CDCl 3 )δ7.22-7.16(m,1H),6.65-6.59(m,3H),5.95(brs,1H). 13 C NMR(100MHz,CDCl 3 )δ164.7,162.3,156.5(d,J＝11.3Hz),130.5(d,J＝10.1Hz),111.1(d,J＝2.9Hz),107.8(d,J＝21.3Hz),103.2(d,J＝24.6Hz). 19 F NMR(376MHz,CDCl 3 )δ-111.57.IR(neat)3374,1609,1490,1460,1282,1160,1129cm -1 .MS(EI)m/z 112.
example 29
Figure BDA0003074832460000162
Adding 1sq (0.4mmol,116.0mg), uranyl nitrate hydrate (4 mol%/0.016 mmol,8mg) into a 25mL reaction tube, wherein the ratio of water source to that in example 1, 1ef to water effectively participating in the reaction is 1:0.82, trichloroacetic acid (0.8mmol,130.7mg), acetone (2mL), evacuating at-78 deg.C for 3 times, stirring at 25 deg.C under the irradiation of 12W blue LED lamp (wavelength 430nm) for 72 hr, concentrating after the reaction is finished, and performing column chromatography (V) PE /V EA 10/1) gave brown liquid 2e (49.2mg, 72%) which was purified by column chromatography (V) PE /V EA 5/1) was isolated as a brown solid 2f (44.6mg, 82%).
Example 30
Figure BDA0003074832460000163
A25 mL reaction tube was charged with 1ym (0.4mmol,113.6mg), uranyl nitrate hydrate (4 mol%/0.016 mmol,8mg) from the same source as in example 1, 1xm to 1:0.54 ratio of water available for reaction, trichloroacetic acid (0.8mmol,130.7mg), acetone (2mL), evacuated at-78 deg.C for 3 times nitrogen exchange, stirred at 25 deg.C under the irradiation of 12W blue LED lamp (wavelength 430nm) for 72 hours, concentrated after completion of the reaction, and subjected to column chromatography (V) PE /V EA 10/1) gave a brown liquid 2m (35.0mg, 54%) which was purified by column chromatography (V) PE /V EA 30/1) to give 2x (28.4mg, 51%) as a white solid;
1 H NMR(400MHz,CDCl 3 )δ7.33(d,J＝4.0Hz,1H),7.17-7.14(m,1H),6.95(d,J＝8.0Hz,1H),5.53(br,1H). 13 C NMR(100MHz,CDCl 3 )δ150.1,128.5,128.5,125.5,120.3,117.1.IR(neat)3426,1477,1406,1328,1276,1184,1094cm -1 .MS(EI)m/z 162.
example 31
Figure BDA0003074832460000171
Adding 1wx (0.4mmol,115.8mg), uranyl nitrate hydrate (4 mol%/0.016 mmol,8mg) into a 25mL reaction tube, wherein the ratio of water source to water in example 1, 1xy to water effectively participating in the reaction is 1:0.59, trichloroacetic acid (0.8mmol,130.7mg), acetone (2mL), evacuating at-78 deg.C for 3 times, stirring at 25 deg.C under the irradiation of 12W blue LED lamp (wavelength 430nm) for 72 hr, concentrating after the reaction is finished, and performing column chromatography (V) PE /V EA White solid 2x (38.2mg, 59%) was isolated by column chromatography (V) 10/1 PE /V EA 5/1) to give 2y (32.3mg, 56%) as a brown solid;
1 H NMR(400MHz,CDCl 3 )δ6.89-6.84(m,2H),6.78(t,J＝8.0Hz,1H),5.56(brs,1H),5.54(brs,1H). 13 C NMR(100MHz,CDCl 3 )δ144.7,139.2,121.2,120.4,119.7,114.2.IR(neat)3409,2925,1596,1490,1464,1326,1158cm -1 .MS(EI)m/z 144.
fluid chemistry: 1xy (10.0mmol,2.87g), uranyl nitrate hydrate (4 mol%/0.4 mmol,201mg) were added to a 250mL three-necked flask in the same ratio of 1xy, 1 in example 1, to water available for the reaction, trichloroacetic acid (20mmol,3.26g), acetone (50mL), and after evacuation and nitrogen exchange at-78 ℃ for 3 times, the reaction mixture was circulated through a polytetrafluoroethylene tube (o.d.: 2mm, i.d.: 1mm, length h ═ 5.68m, volume ═ 4.45mL) by a pump (flow rate 0.5mL/min), and simultaneously irradiated with a 54 watt blue LED lamp (wavelength 430nm) for 48 hours at 25 ℃, after the reaction was completed, the mixture was concentrated and subjected to column chromatography (V) PE /V EA 20/1) gave a brown liquid 2x (0.91g, 51%) which was isolated by column chromatography (V) PE /V EA 5/1) was isolated as a brown solid 2y (0.69g, 48%).
Example 32
Figure BDA0003074832460000172
A25 mL reaction tube was charged with 1wx (0.4mmol,103.2mg), uranyl nitrate hydrate (4 mol%/0.016 mmol,8mg), and waterThe source of (A) was as in example 1, 1nz1 with the ratio of water available for reaction being 1:0.54, trichloroacetic acid (0.8mmol,130.7mg), acetone (2mL), evacuated at-78 deg.C for 3 times, stirred at 25 deg.C under the irradiation of 12W blue LED lamp (wavelength 430nm) for 72 hours, concentrated after completion of the reaction, and subjected to column chromatography (V) PE /V EA 20/1) gave 2n (23.8mg, 48%) as a brown liquid which was isolated by column chromatography (V) PE /V EA 5/1) to give 2z1(32.8mg, 54%);
1 H NMR(400MHz,CDCl 3 )δ6.85(d,J＝8.4Hz,1H),6.70(d,J＝7.2Hz,2H),5.48(brs,1H),3.89(s,3H),2.59(q,J＝7.6Hz,2H),1.23(t,J＝7.6Hz,3H). 13 C NMR(100MHz,CDCl 3 )δ146.2,143.4,136.2,120.2,114.1,110.4,55.8,28.5,15.9.IR(neat)1598,1287,1198,1149,1041,945,686cm -1 .MS(EI)m/z 152.
fluid chemistry: 1nz1(10.0mmol,2.58g), uranyl nitrate hydrate (4 mol%/0.4 mmol,201mg) were charged into a 250mL three-necked flask, and the water was derived from 1, 1nz1 in a ratio of 1:0.81 to water effective for the reaction, trichloroacetic acid (20mmol,3.26g), acetone (50mL), and after evacuating and exchanging nitrogen at-78 ℃ for 3 times, the reaction mixture was circulated through a polytetrafluoroethylene tube (O.D.: 2mm, I.D.: 1mm, length h ═ 5.68m, volume ═ 4.45mL) by a pump (flow rate 0.5mL/min), and the polytetrafluoroethylene tube was irradiated with a 54 watt blue LED lamp (wavelength 430nm) at the same time, reacted at 25 ℃ for 48 hours, and after the reaction was completed, the mixture was concentrated, and the reaction was purified by column chromatography (V column chromatography) PE /V EA 20/1) gave 2n (0.47g, 65%) as a brown liquid which was isolated by column chromatography (V) PE /V EA 5/1) to yield 2z1(0.71g, 81%) as a brown liquid.
Example 33
Figure BDA0003074832460000181
In a 25mL reaction tube, 1z (0.4mmol,120.8mg), uranyl nitrate hydrate (4 mol%/0.016 mmol,8mg) were added, the ratio of the water source to the water effective for the reaction in example 1, 1z was 1:0.36, trichloroacetic acid (0.8mmol,130.7mg), acetone (2mL) in-Evacuating at 78 deg.C, exchanging nitrogen for 3 times, stirring at 25 deg.C under the irradiation of 12W blue LED lamp (wavelength of 430nm) for 72 hr, concentrating, and performing column chromatography (V) PE /V EA 20/1 brown liquid 2z1(8.5mg, 14%) was isolated by column chromatography (V) PE /V EA 5/1) to give 2z2(14.6mg, 22%) as a brown liquid;
1 H NMR(400MHz,CDCl 3 )δ7.53(s,2H),6.95(d,J＝8.0Hz,1H),6.04(s,1H),3.96(s,3H),2.56(s,3H). 13 C NMR(100MHz,CDCl 3 )δ197.0,150.4,146.5,130.0,123.9,113.7,109.6,55.9,26.1.IR(neat)3324,1659,1577,1518,1292,1222,851cm -1 .MS(EI)m/z 166.
example 34
Figure BDA0003074832460000191
Adding 1a (0.4mmol,68.0mg), uranyl nitrate hydrate (4 mol%/0.016 mmol,8mg), water of formula (2) as external additive, diphenyl ether and the molar ratio thereof being 1:20, trichloroacetic acid (0.8mmol,130.7mg), and acetonitrile (2mL) into a 25mL reaction tube, evacuating at-78 deg.C and changing nitrogen for 3 times, stirring at 25 deg.C under irradiation of 9W blue LED lamp (wavelength 460nm) for 48 hr, concentrating after reaction, and performing column chromatography (V) PE /V EA 10/1) was isolated as a white solid 2a (37.6mg, 50%).
Example 35
Figure BDA0003074832460000192
Adding 1a (0.4mmol,68.0mg), uranyl nitrate hydrate (4 mol%/0.016 mmol,8mg), water of formula (2) as external additive, 1 a/water molar ratio of 1:20, trifluoroacetic acid (0.8mmol,91.2mg), acetone (2mL) into a 25mL reaction tube, evacuating at-78 deg.C for 3 times, stirring at 25 deg.C under irradiation of 9W blue LED lamp (wavelength 460nm) for 48 hr, concentrating, and performing column chromatography (V) PE /V EA 10/1) was isolated as a white solid 2a (30.1mg, 40%).
The invention can realize the technical effects of hydrolyzing the diaryl ether compound (1) to generate the aryl phenol compounds (3) and (4) within the temperature range of 0-40 ℃, preferably within the room temperature range.
The protection of the present invention is not limited to the above embodiments. Variations and advantages that may occur to those skilled in the art are intended to be included within the present invention without departing from the spirit and scope of the inventive concept and are intended to be protected by the following claims.

Claims (10)

1. A method for hydrolyzing a diaryl ether compound to generate an aryl phenol compound is characterized in that the diaryl ether compound shown in a formula (1) and water shown in a formula (2) are used as reaction raw materials, and the aryl phenol compound shown in the formulas (3) and (4) is obtained by reacting in a solvent under the action of a catalyst and the assistance of acid in an illumination environment, wherein the reaction process is shown in a reaction formula (a);
Figure DEST_PATH_IMAGE002
reaction formula (a);
or the like, or, alternatively,
the method comprises the steps of taking a diaryl ether compound shown as a formula (1) as a reaction raw material, reacting the diaryl ether compound with water in a solvent under the action of a catalyst and the assistance of acid in an illumination environment to obtain aryl phenol compounds shown as formulas (3) and (4), wherein the reaction process is shown as a reaction formula (b);
Figure DEST_PATH_IMAGE004
reaction formula (b);
the catalyst is a photocatalyst uranyl nitrate; the acid is any one of trichloroacetic acid, trifluoroacetic acid and acetic acid; the solvent is organic solvent acetone; the light source used in the illumination environment is a blue light source with the wavelength of 420-460nm and the power of 1-100W;
wherein Ar is 1 And Ar 2 Each independently is phenyl or phenyl containing substituent; the substituent is C1-4 alkyl, methoxy, fluorine, chlorine, bromine, acetyl, cyano, nitro, trifluoromethyl, hydroxyl, p-methoxycarbonyl and phenyl.
2. The method of claim 1, wherein Ar is Ar 1 、Ar 2 Each independently is phenyl, p-isopropylphenyl, p-tert-butylphenyl, p-fluorophenyl, p-bromophenyl, p-acetylphenyl, p-methoxycarbonylphenyl, p-cyanophenyl, m-methylphenyl, m-tert-butylphenyl, m-trifluoromethylphenyl, m-cyanophenyl, p-nitrophenyl, m-methoxyphenyl, o-cyanophenyl, o-trifluoromethylphenyl, o-methoxycarbonylphenyl, m-fluorophenyl, 3, 5-dimethylphenyl, p-trifluoromethylphenyl, o-methoxyphenyl, 2, 4-dichlorophenyl, 2-hydroxy-4-chlorophenyl, 2-methoxy-4 ethylphenyl, 2-hydroxy-3-methoxy-5-ethylphenyl, biphenyl.
3. The process of claim 1, wherein the catalyst is used in an amount of 4 mol% to 6 mol% based on the diaryl ether compound represented by formula (1).
4. The process of claim 1, wherein the acid is used in a molar amount of 1 to 4 equivalents with respect to the diaryl ether compound of formula (1).
5. The method of claim 1, wherein the solvent is used in an amount of 1 to 50 ml.
6. The process of claim 1, wherein the concentration of the diaryl ether compound in the solvent is from 0.05 to 0.2 mol/l.
7. The method of claim 1, wherein the illumination is for a period of 2 to 3 days.
8. As in claimThe method of claim 1, wherein the reaction is between 0 and 40 o And (C) performing.
9. The process of claim 1, wherein the molar ratio of diaryl ether compound to water is from 1:0.1 to 1: 20.
10. Use of a process according to any one of claims 1-9 in the hydrolysis of diaryl ether compounds and in the synthesis of aryl phenol compounds.
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