CN109012747B - Application of copper (I) coordination polymer - Google Patents

Application of copper (I) coordination polymer Download PDF

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CN109012747B
CN109012747B CN201810776616.6A CN201810776616A CN109012747B CN 109012747 B CN109012747 B CN 109012747B CN 201810776616 A CN201810776616 A CN 201810776616A CN 109012747 B CN109012747 B CN 109012747B
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CN109012747A (en
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李红喜
张梦娟
郎建平
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Suzhou University
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Abstract

The invention discloses an application of a copper (I) coordination polymer. Specifically, the copper (I) coordination polymer of the present invention has the chemical formula [ Cu6I2(μ4‑I)2(μ4‑5‑phpymt)2]nWherein 5-phpymt is an anion formed by losing proton of a sulfhydryl group in 5-phenyl-2-mercaptopyrimidine, and n is any positive integer. The coordination polymer can catalyze the conversion from arylboronic acid compounds to phenolic compounds under the irradiation of visible light, and has the characteristics of high conversion efficiency, wide application range, mild reaction conditions and the like. After the conversion reaction is finished, centrifugally separating the copper (I) coordination polymer from the reaction system, and performing the next round of reaction by simple water washing, wherein the copper (I) coordination polymer can still keep stable after circulating for at least 5 times, and the catalytic activity of the copper (I) coordination polymer is not obviously reduced.

Description

Application of copper (I) coordination polymer
The invention relates to a copper (I) coordination polymer, a preparation method and application thereof, a divisional application of the invention with the application date of 2016, 5, 16 and the application number of 2016103227336, belonging to the technical part of products.
Technical Field
The invention belongs to the technical field of catalytic chemistry, and relates to a copper (I) coordination polymer, in particular to a copper (I) coordination polymer containing a 5-phenyl-2-mercaptopyrimidine anion bridging ligand, a preparation method thereof, and application thereof in preparing phenolic compounds by photocatalysis of aryl boronic acid compounds.
Background
Phenol is an organic chemical raw material widely used for manufacturing medicines, chemical agricultural products, natural product artificial substitutes, dyes, spices and explosives. The traditional processes for industrially producing phenol mainly comprise an cumene method, a toluene-benzoic acid method, a sulfonation method, a benzene one-step oxidation method and the like, but the methods have defects, such as low atom utilization rate, complex reaction, more byproducts, easy environmental pollution and the like.
In order to overcome the above disadvantages, more and more researches are focused on the use of transition metal catalysts to achieve efficient synthesis of phenol, such as hydroxylation of halogenated aromatic hydrocarbons using metal catalysts, oxidative hydroxylation of aryl boronic acids using oxidizing agents, hydroxylation of phenyl boronic acids using transition metal catalysts, etc., but most of these reactions require oxidizing agents or inorganic bases and the conversion efficiency is relatively low.
In recent years, many groups of subjects use ruthenium bipyridine complexes, Methylene Blue (MB), Rose Bengal (RB) and the like as visible light photocatalysts to realize efficient conversion of phenylboronic acid into phenol, and the method has the characteristics of very mild reaction conditions and environmental friendliness. However, the catalysts used are not easily separable and recycling of the catalysts is not possible (see zuo, y. q., Chen, j. r., Xiao, w. j.,et al., Highly Efficient Aerobic Oxidative Hydroxylation of Arylboronic Acids: Photoredox Catalysis Using Visible Light[J], Angew. Chem. Int. Ed., 2012, 51(3):784-788). Currently, there are only a few reports in the literature of the use of heterogeneous catalysts to catalyze the oxidative hydroxylation of phenylboronic acid under visible light irradiation (see Toyao, t., Ueno, n., Matsuoka, m.,et al., Visible-light, photoredox catalyzed, oxidative hydroxylation of arylboronic acids using a metal-organic framework containing tetrakis(carboxyphenyl)porphyrin groups[J], Chem. Commun., 2015, 51, 16103-16106）。
disclosure of Invention
In view of the above circumstances, an object of the present invention is to provide a copper (I) coordination polymer, a method for producing the same, and use thereof. The coordination polymer is used as a photocatalyst, and can catalyze the oxidative hydroxylation (oxidative hydroxylation) reaction of aryl boric acid compounds in a mixed solvent of water and acetonitrile under the irradiation of visible light, so that the phenolic compounds are finally prepared. In addition, in the reaction system, the copper (I) coordination polymer used as the photocatalyst can be recycled for more than 5 times, is still stable after 5 times of recycling, has no obvious reduction of the catalytic activity, and is an effective and efficient photocatalyst.
In order to achieve the purpose, the invention adopts the following technical scheme:
a copper (I) coordination polymer with a chemical formula of [ Cu6I2(μ4-I)2(μ4-5-phpymt)2]nWherein 5-phpymt is an anion formed by losing proton of a sulfhydryl group in 5-phenyl-2-mercaptopyrimidine, and n is any positive integer.
Figure DEST_PATH_IMAGE001
The coordination polymer is basically distributed in a two-dimensional layered manner, and a repeating structural unit when n =1 is taken as an example: the 5-phenyl-2-mercaptopyrimidine structure is approximately positioned on two sides of a two-dimensional plane respectively, each 1S atom is coordinated with 2 Cu atoms, each 1N atom is coordinated with 1 Cu atom to form mu4-5-phpymt bridged coordination; 2 of 4I atoms are each coordinated to 4 Cu atomsForm mu4-I is in bridged coordination, the remaining 2 each being coordinated to only 1 Cu atom; 4 of the 6 Cu atoms are each coordinated to 1S atom, 1N atom and 1I atom, and the remaining 2 are each coordinated to 3I atoms; 6 Cu atoms and 4I atoms [ Cu ]6I2(μ4-I)2]Units of [ Cu ] each6I2(μ4-I)2]Cell passing mu4The-5-phpymt ligand is linked to other units to form a two-dimensional structure.
The crystals of the coordination polymer belong to a monoclinic system and have a space group ofC2/mCell parameter ofa = 12.5100(9) Å，b = 9.4515(6) Å，c = 12.0472(9) Å，α = 90.00 °，β= 107.004(8) °，γ = 90.00 °，V= 1362.16(17) nm3，Z = 1。
A method for producing the above copper (I) complex polymer comprises the steps of:
adding cuprous iodide, 5-phenyl-2-mercaptopyrimidine and a solvent into a reaction container according to the molar ratio of cuprous iodide to 5-phenyl-2-mercaptopyrimidine = 2-5: 1, introducing inert gas for 0.5-1 hour, sealing the reaction container, heating to 100-140 ℃, and reacting for 24-72 hours; and after the reaction is finished, cooling the temperature of the reaction system to room temperature, filtering, washing and drying to obtain the copper (I) coordination polymer.
Preferably, in the above preparation method, the molar ratio between the cuprous iodide and the 5-phenyl-2-mercaptopyrimidine is 4: 1.
Preferably, in the above preparation method, the inert gas is selected from any one of nitrogen, neon and argon, and is preferably nitrogen.
Preferably, in the above preparation method, the solvent is a mixed solvent of acetonitrile and N, N-dimethylformamide, and preferably, the volume ratio between the acetonitrile and the N, N-dimethylformamide is 20: 1.
Preferably, in the above preparation method, the heating is performed by an oven.
Preferably, in the above preparation method, the reaction temperature is 120 ℃ and the reaction time is 48 hours.
The application of the copper (I) coordination polymer in preparing phenolic compounds by photocatalysis of aryl boric acid compounds, wherein the aryl boric acid compounds are selected from any one of phenyl boric acid, alkyl substituted phenyl boric acid (preferably methyl substituted phenyl boric acid), alkoxy substituted phenyl boric acid (preferably methoxy substituted phenyl boric acid), acyl substituted phenyl boric acid (preferably acetyl substituted phenyl boric acid), nitro substituted phenyl boric acid, naphthalene boric acid and phenyl diboronic acid.
Specifically, the above use may be embodied as a method for producing a phenolic compound from an arylboronic acid compound using the above copper (I) coordination polymer, which comprises the steps of:
according to the molar ratio of boric acid group to copper (I) coordination polymer to alkali =1: 0.01-0.03: 1, adding aryl boric acid compound, copper (I) coordination polymer, alkali and solvent into a reaction vessel equipped with a stirring device, and carrying out open reaction for 24-72 hours at room temperature under the irradiation of visible light; after the reaction is finished, ethyl acetate is adopted for extraction, organic phases are combined, and the phenolic compound is obtained after drying, filtering, decompression concentration and silica gel column chromatography purification.
Preferably, in the above method, the molar ratio between the boric acid group, the copper (I) complex polymer and the base is 1:0.02: 1.
Preferably, in the above method, the arylboronic acid compound is selected from any one of phenylboronic acid, alkyl-substituted phenylboronic acid (preferably methyl-substituted phenylboronic acid), alkoxy-substituted phenylboronic acid (preferably methoxy-substituted phenylboronic acid), acyl-substituted phenylboronic acid (preferably acetyl-substituted phenylboronic acid), nitro-substituted phenylboronic acid, naphthalene boronic acid, and benzene diboronic acid.
Preferably, in the above method, the base is selected from any one of triethylamine, N-diisopropylethylamine, and N, N-diisopropylisobutylamine, preferably triethylamine.
Preferably, in the above method, the solvent is a mixed solvent of acetonitrile and water in equal volume.
Preferably, in the above method, the stirring device is a magnetic stirring device.
Preferably, in the above method, the light source of visible light is a fluorescent lamp, preferably a 45W fluorescent lamp.
Preferably, in the above method, the reaction time is 48 hours.
Compared with the prior art, the invention adopting the technical scheme has the following advantages:
(1) the invention discloses a copper (I) coordination polymer as a photocatalyst, which can catalyze the conversion of arylboronic acid compounds to phenolic compounds under the irradiation of visible light;
(2) the conversion of the arylboronic acid compound to the phenolic compound disclosed by the invention has the characteristics of high conversion efficiency (the aryl boronic acid with a simple structure can reach 80 percent, even more than 95 percent of conversion rate, and the aryl boronic acid with higher steric hindrance can also reach about 75 percent of conversion rate), wide application range (not only suitable for the conversion of the phenylboronic acid, but also suitable for the conversion of other condensed ring arylboronic acids, and capable of realizing the conversion of the phenylboronic acids substituted by various substituents), mild reaction conditions (the reaction can be carried out under an open reaction at room temperature, and a water removal and oxygen removal process is not needed), and the like;
(3) after the conversion reaction is finished, centrifugally separating a copper (I) coordination polymer from a reaction system, adding the copper (I) coordination polymer into a reaction container containing an aryl boric acid compound, alkali and a mixed solvent through simple water washing, and carrying out the next round of reaction, wherein the copper (I) coordination polymer can be circulated for at least 5 times, can still keep stable after being circulated for 5 times, and has no obvious reduction in catalytic activity; in the case of phenylboronic acid, the yields obtained after 5 cycles are 95%, 91%, 89%, 84% and 79% in this order, and the powder diffraction experiments after the cycle catalysis show that the structure of the catalyst remains unchanged.
Drawings
FIG. 1 is a schematic view of the crystal structure of the copper (I) coordination polymer of the present invention.
FIG. 2 is a graph comparing the yields of copper (I) coordination polymer of the present invention cyclically catalyzing the oxidative hydroxylation of phenylboronic acid.
FIG. 3 is a simulated powder diffraction diagram of the copper (I) coordination polymer of the present invention and a real powder diffraction diagram of the copper (I) coordination polymer after the oxidative hydroxylation of phenylboronic acid by cyclic catalysis.
Detailed Description
The invention will be further described with reference to the accompanying drawings and specific embodiments. Unless otherwise indicated, reagents, materials, instruments and the like used in the following examples are commercially available.
Example 1: [ Cu ]6I2(μ4-I)2(μ4-5-phpymt)2]nAnd (4) preparing.
Adding cuprous iodide (19.0 mg, 0.10 mmol), 5-phenyl-2-mercaptopyrimidine (4.7 mg, 0.025 mmol), acetonitrile (2 mL) and N, N-dimethylformamide (0.1 mL) into a 10 mL heat-resistant glass tube, blowing nitrogen for 0.5 h, sealing the tube, putting into an oven, and reacting at 120 ℃ for 48 h; after the reaction is finished, slowly cooling at the speed of 5 ℃/h, cooling to room temperature, filtering the reaction solution, washing a filter cake by acetonitrile and diethyl ether, and drying to obtain orange blocky crystals [ Cu6I2(μ4-I)2(μ4-5-phpymt)2]n(yield: 12.2 mg; yield: 58%, calculated as Cu).
Elemental analysis (%): c40H28Cu12I8N8S4(case of n = 2), theoretical value: c19.01, H1.12, N4.43; experimental values: c18.88, H1.32, N4.36.
IR (KBr pellet, cm)-1）：3031 (w), 1601 (m), 1551 (w), 1525 (w), 1489 (w), 1367 (s), 1348 (m) 1164 (s), 1151 (m), 762 (m), 693 (m)。
The obtained product was subjected to single crystal X-ray diffraction test, and its crystallographic parameters are shown in Table 1, and its crystal structure is shown in FIG. 1.
Figure DEST_PATH_IMAGE002
The above data show that the target product [ Cu ] is successfully obtained in this example6I2(μ4-I)2(μ4-5-phpymt)2]n。
Example 2: oxidative hydroxylation of phenylboronic acid under visible light irradiation.
Figure DEST_PATH_IMAGE003
Phenyl boric acid (1 mmol) and [ Cu ]6I2(μ4-I)2(μ4-5-phpymt)2]n（0.02 mmol）、Et3N (1 mmol) was added to a quartz tube equipped with a magnetic stirrer, and then a mixed solvent (3 mL) of water and acetonitrile (v/v =1: 1) was added, and the mixture was subjected to an open reaction at room temperature for 48 hours under irradiation of a 45W fluorescent lamp; after completion of the reaction, extraction was performed with ethyl acetate (3X 5 mL), and the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by a rotary evaporator and then subjected to separation and purification by a silica gel column chromatography to obtain phenol as an aimed product (yield 95%).
The nuclear magnetic data of the product obtained are as follows:
1H-NMR (400 MHz, DMSO-d6) δ 9.32 (s, 1H), 7.36-7.02 (m, 2H), 6.75 (d, J = 7.5 Hz, 3H)；
13C-NMR (100 MHz, DMSO-d6) δ 157.20, 129.10, 118.68, 114.77。
separating [ Cu ] from the reaction system by centrifugation6I2(μ4-I)2(μ4-5-phpymt)2]nAfter simple water washing, adding into the mixture containing phenylboronic acid and Et3N and a mixed solvent of water and acetonitrile (v/v =1: 1) in a quartz tube equipped with a magnetic stirrer, for the next round of the conversion reaction; the photocatalyst was recycled according to the above procedure, the yields obtained after 5 cycles were 95%, 91%, 89%, 84% and 79% in this order (the results are shown in fig. 2), and the powder diffraction experiments after the cyclic catalysis showed that the structure of the catalyst remained unchanged (the results are shown in fig. 3).
Example 3: oxidative hydroxylation of 4-methoxyphenylboronic acid under irradiation of visible light.
Figure DEST_PATH_IMAGE004
4-methoxyphenylboronic acid (1 mmol) and [ Cu ]6I2(μ4-I)2(μ4-5-phpymt)2]n（0.02 mmol）、Et3N (1 mmol) was added to a quartz tube equipped with a magnetic stirrer, and then a mixed solvent (3 mL) of water and acetonitrile (v/v =1: 1) was added, and the mixture was subjected to an open reaction at room temperature for 48 hours under irradiation of a 45W fluorescent lamp; after completion of the reaction, extraction was performed with ethyl acetate (3 × 5 mL), and the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by a rotary evaporator and then subjected to separation and purification by a silica gel column chromatography to obtain the objective 4-methoxyphenol (yield 97%).
The nuclear magnetic data of the product obtained are as follows:
1H-NMR (400 MHz, DMSO-d6) δ 8.88 (s, 1H), 6.74 (d, J = 8.7 Hz, 2H), 6.67 (d, J = 8.6 Hz, 2H), 3.65 (s, 3H)；
13C-NMR (100 MHz, DMSO-d6) δ 151.98, 151.09, 115.69, 114.39, 55.31。
example 4: oxidative hydroxylation of 2-methylphenylboronic acid under irradiation of visible light.
Figure DEST_PATH_IMAGE005
2-Methylphenylboronic acid (1 mmol) and [ Cu ]6I2(μ4-I)2(μ4-5-phpymt)2]n（0.02 mmol）、Et3N (1 mmol) was added to a quartz tube equipped with a magnetic stirrer, and then a mixed solvent (3 mL) of water and acetonitrile (v/v =1: 1) was added, and the mixture was subjected to an open reaction at room temperature for 48 hours under irradiation of a 45W fluorescent lamp; after the reaction was completed, extraction was performed with ethyl acetate (3X 5 mL), and the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by a rotary evaporatorAnd then separated and purified by a silica gel chromatography column method to obtain the target product 2-methylphenol (yield 81%).
The nuclear magnetic data of the product obtained are as follows:
1H-NMR (400 MHz, DMSO-d6) δ 9.24 (s, 1H), 7.11-6.96 (m, 2H), 6.85 (m, 1H), 6.70 (d, J = 6.0 Hz, 1H), 2.18 (s, 3H)；
13C-NMR (100 MHz, DMSO-d6) δ 155.51, 130.63, 126.68, 123.89, 118.86, 114.70, 16.06。
example 5: oxidative hydroxylation of 3-methylphenylboronic acid under irradiation of visible light.
Figure DEST_PATH_IMAGE006
3-Methylphenylboronic acid (1 mmol) and [ Cu ]6I2(μ4-I)2(μ4-5-phpymt)2]n（0.02 mmol）、Et3N (1 mmol) was added to a quartz tube equipped with a magnetic stirrer, and then a mixed solvent (3 mL) of water and acetonitrile (v/v =1: 1) was added, and the mixture was subjected to an open reaction at room temperature for 48 hours under irradiation of a 45W fluorescent lamp; after completion of the reaction, extraction was performed with ethyl acetate (3 × 5 mL), and the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by a rotary evaporator and then subjected to separation and purification by a silica gel column chromatography to obtain the objective 3-methylphenol (yield 91%).
The nuclear magnetic data of the product obtained are as follows:
1H-NMR (400 MHz, DMSO-d6) δ 9.98 (s, 1H), 7.51 (d, J = 6.2 Hz, 2H), 7.41 (s, 1H), 7.30-7.25 (m, 1H), 3.82 (s, 3H)；
13C-NMR (100 MHz, DMSO-d6) δ 157.45, 138.48, 129.30, 119.86, 116.26, 112.71, 21.17。
example 6: oxidative hydroxylation of 4-methylphenylboronic acid under irradiation of visible light.
Figure DEST_PATH_IMAGE007
4-Methylphenylboronic acid (1 mmol) and [ Cu ]6I2(μ4-I)2(μ4-5-phpymt)2]n（0.02 mmol）、Et3N (1 mmol) was added to a quartz tube equipped with a magnetic stirrer, and then a mixed solvent (3 mL) of water and acetonitrile (v/v =1: 1) was added, and the mixture was subjected to an open reaction at room temperature for 48 hours under irradiation of a 45W fluorescent lamp; after completion of the reaction, extraction was performed with ethyl acetate (3 × 5 mL), and the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by a rotary evaporator and then subjected to separation and purification by a silica gel column chromatography to obtain the objective 4-methylphenol (yield 96%).
The nuclear magnetic data of the product obtained are as follows:
1H-NMR (400 MHz, DMSO-d6) δ 9.06 (s, 1H), 6.95 (d, J = 7.9 Hz, 2H), 6.64 (d, J = 8.1 Hz, 2H), 2.17 (s, 3H)；
13C-NMR (100 MHz, DMSO-d6) δ 154.55, 129.75, 127.17, 114.76, 19.96。
example 7: oxidative hydroxylation of 2, 6-dimethylphenylboronic acid under irradiation with visible light.
Figure DEST_PATH_IMAGE008
2, 6-dimethylphenylboronic acid (1 mmol) and [ Cu ]6I2(μ4-I)2(μ4-5-phpymt)2]n（0.02 mmol）、Et3N (1 mmol) was added to a quartz tube equipped with a magnetic stirrer, and then a mixed solvent (3 mL) of water and acetonitrile (v/v =1: 1) was added, and the mixture was subjected to an open reaction at room temperature for 48 hours under irradiation of a 45W fluorescent lamp; after completion of the reaction, extraction was performed with ethyl acetate (3 × 5 mL), and the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by a rotary evaporator and then subjected to separation and purification by a silica gel column chromatography to obtain the objective 2, 6-dimethylphenol (yield 75%).
The nuclear magnetic data of the product obtained are as follows:
1H-NMR (400 MHz, DMSO-d6) δ 8.17 (s, 1H), 6.90 (d, J = 7.4 Hz, 2H), 6.64 (t, J = 7.4 Hz, 1H), 2.10 (s, 6H)；
13C-NMR (100 MHz, DMSO-d6) δ 152.97, 127.89, 124.27, 119.14, 16.48。
example 8: oxidative hydroxylation of 2,4, 6-trimethylphenylboronic acid under visible light irradiation.
Figure DEST_PATH_IMAGE009
2,4, 6-trimethylphenylboronic acid (1 mmol) and [ Cu ]6I2(μ4-I)2(μ4-5-phpymt)2]n（0.02 mmol）、Et3N (1 mmol) was added to a quartz tube equipped with a magnetic stirrer, and then a mixed solvent (3 mL) of water and acetonitrile (v/v =1: 1) was added, and the mixture was subjected to an open reaction at room temperature for 48 hours under irradiation of a 45W fluorescent lamp; after completion of the reaction, extraction was performed with ethyl acetate (3X 5 mL), and the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by a rotary evaporator and then subjected to separation and purification by a silica gel column chromatography to obtain the objective 2,4, 6-trimethylphenol (yield 74%).
The nuclear magnetic data of the product obtained are as follows:
1H-NMR (400 MHz, DMSO-d6) δ 7.89 (s, 1H), 6.69 (s, 2H), 2.11 (s, 9H)；
13C-NMR (100 MHz, DMSO-d6) δ 150.75, 128.79, 127.47, 123.97, 19.66, 16.06。
example 9: oxidative hydroxylation of 4-acetylphenylboronic acid under visible light irradiation.
Figure DEST_PATH_IMAGE010
Reacting 1 mmol of 4-acetylphenylboronic acid,[Cu6I2(μ4-I)2(μ4-5-phpymt)2]n（0.02 mmol）、Et3N (1 mmol) was added to a quartz tube equipped with a magnetic stirrer, and then a mixed solvent (3 mL) of water and acetonitrile (v/v =1: 1) was added, and the mixture was subjected to an open reaction at room temperature for 48 hours under irradiation of a 45W fluorescent lamp; after completion of the reaction, extraction was performed with ethyl acetate (3X 5 mL), and the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by a rotary evaporator and then subjected to separation and purification by a silica gel column chromatography to obtain p-4-acetylphenol as an objective product (yield 86%).
The nuclear magnetic data of the product obtained are as follows:
1H-NMR (400 MHz, DMSO-d6) δ 10.34 (s, 1H), 7.84 (d, J = 8.2 Hz, 2H), 6.85 (d, J = 8.2 Hz, 2H), 2.47 (s, 3H)；
13C-NMR (100 MHz, DMSO-d6) δ 195.75, 161.79, 130.69, 128.49, 115.13, 25.86。
example 10: oxidative hydroxylation of 4-nitrophenylboronic acid under irradiation of visible light.
Figure DEST_PATH_IMAGE011
4-Nitromethylphenylboronic acid (1 mmol) and [ Cu ]6I2(μ4-I)2(μ4-5-phpymt)2]n（0.02 mmol）、Et3N (1 mmol) was added to a quartz tube equipped with a magnetic stirrer, and then a mixed solvent (3 mL) of water and acetonitrile (v/v =1: 1) was added, and the mixture was subjected to an open reaction at room temperature for 48 hours under irradiation of a 45W fluorescent lamp; after the reaction, the reaction mixture was extracted with ethyl acetate (3X 5 mL), and the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by a rotary evaporator and then subjected to separation and purification by a silica gel column chromatography to obtain the objective 4-nitrophenol (yield: 81%).
The nuclear magnetic data of the product obtained are as follows:
1H-NMR (400 MHz, DMSO-d6) δ 11.03 (s, 1H), 8.11 (d, J = 7.8 Hz, 2H), 6.92 (d, J = 8.5 Hz, 2H)；
13C-NMR (100 MHz, DMSO-d6) δ 163.89, 139.61, 126.16, 115.77。
example 11: oxidative hydroxylation of 2-naphthalene boronic acid under irradiation of visible light.
Figure DEST_PATH_IMAGE012
2-naphthalene boronic acid (1 mmol) and [ Cu [ ]6I2(μ4-I)2(μ4-5-phpymt)2]n（0.02 mmol）、Et3N (1 mmol) was added to a quartz tube equipped with a magnetic stirrer, and then a mixed solvent (3 mL) of water and acetonitrile (v/v =1: 1) was added, and the mixture was subjected to an open reaction at room temperature for 48 hours under irradiation of a 45W fluorescent lamp; after the reaction, the mixture was extracted with ethyl acetate (3X 5 mL), and the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by a rotary evaporator and then subjected to separation and purification by a silica gel column chromatography to obtain the objective 2-naphthol (yield 86%).
The nuclear magnetic data of the product obtained are as follows:
1H-NMR (400 MHz, DMSO-d6) δ 9.71 (s, 1H), 7.78-7.72 (m, 2H), 7.67 (d, J = 8.2 Hz, 1H), 7.38 (t, J = 7.4 Hz, 1H), 7.25 (t, J = 7.4 Hz, 1H), 7.12-7.05 (m, 2H)；
13C-NMR (100 MHz, DMSO-d6) δ 155.25, 134.57, 129.26, 127.70, 127.51, 126.07, 125.95, 122.60, 118.58, 108.61。
example 12: oxidative hydroxylation of 1, 4-benzenediboronic acid under visible light irradiation.
Figure DEST_PATH_IMAGE013
1, 4-phenyl diboronic acid (0.5 mmol) and [ Cu [ ]6I2(μ4-I)2(μ4-5-phpymt)2]n（0.02 mmol）、Et3N (1 mmol) was added to a quartz tube equipped with a magnetic stirrer, and then a mixed solvent (3 mL) of water and acetonitrile (v/v =1: 1) was added, and the mixture was subjected to an open reaction at room temperature for 48 hours under irradiation of a 45W fluorescent lamp; after the reaction, the reaction mixture was extracted with ethyl acetate (3X 5 mL), and the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by a rotary evaporator and then subjected to separation and purification by a silica gel chromatography to obtain the objective 1, 4-benzenediol (yield: 75%).
The nuclear magnetic data of the product obtained are as follows:
1H-NMR (400 MHz, DMSO-d6) δ 8.61 (s, 2H), 6.55 (s, 4H)；
13C-NMR (100 MHz, DMSO-d6) δ 149.73, 115.46。

Claims (10)

1. use of a copper (I) coordination polymer in the photocatalytic preparation of phenolic compounds from arylboronic acid compounds; the chemical formula of the copper (I) coordination polymer is [ Cu ]6I2(μ4-I)2(μ4-5-phpymt)2]nWherein 5-phpymt is an anion formed by losing proton of a sulfhydryl group in 5-phenyl-2-mercaptopyrimidine, and n is any positive integer.
2. Use according to claim 1, characterized in that:
the crystal of the copper (I) coordination polymer belongs to a monoclinic system, and the space group isC2/mCell parameter ofa = 12.5100(9) Å，b = 9.4515(6) Å，c = 12.0472(9) Å，α = 90.00 °，β= 107.004(8) °，γ = 90.00 °，V = 1362.16(17) nm3，Z = 1。
3. Use according to claim 1, characterized in that: the preparation method of the copper (I) coordination polymer comprises the following steps:
adding cuprous iodide, 5-phenyl-2-mercaptopyrimidine and a solvent into a reaction container according to the molar ratio of cuprous iodide to 5-phenyl-2-mercaptopyrimidine = 2-5: 1, introducing inert gas for 0.5-1 hour, sealing the reaction container, heating to 100-140 ℃, and reacting for 24-72 hours; and after the reaction is finished, cooling the temperature of the reaction system to room temperature, filtering, washing and drying to obtain the copper (I) coordination polymer.
4. Use according to claim 3, characterized in that:
the molar ratio between the cuprous iodide and the 5-phenyl-2-mercaptopyrimidine is 4: 1.
5. Use according to claim 3, characterized in that:
the solvent is a mixed solvent of acetonitrile and N, N-dimethylformamide;
the heating is accomplished by an oven;
the reaction temperature was 120 ℃ and the time was 48 hours.
6. Use according to claim 1, characterized in that:
the aryl boric acid compound is any one of phenyl boric acid, alkyl substituted phenyl boric acid, alkoxy substituted phenyl boric acid, acyl substituted phenyl boric acid, nitro substituted phenyl boric acid, naphthalene boric acid and phenyl diboric acid.
7. A process for preparing phenolic compounds from arylboronic acids using a copper (I) coordination polymer comprising the steps of:
according to the molar ratio of boric acid group to copper (I) coordination polymer to alkali =1: 0.01-0.03: 1, adding aryl boric acid compound, copper (I) coordination polymer, alkali and solvent into a reaction vessel equipped with a stirring device, and carrying out open reaction for 24-72 hours at room temperature under the irradiation of visible light; after the reaction is finished, extracting by using ethyl acetate, combining organic phases, drying, filtering, concentrating under reduced pressure, and purifying by using a silica gel column chromatography to obtain a phenolic compound; the chemical formula of the copper (I) coordination polymer is [ Cu ]6I2(μ4-I)2(μ4-5-phpymt)2]nWherein 5-phpymt is an anion formed by losing proton of a sulfhydryl group in 5-phenyl-2-mercaptopyrimidine, and n is any positive integer.
8. The method of claim 7, wherein:
the molar ratio between the boronic acid group, the copper (I) coordination polymer and the base is 1:0.02: 1.
9. The method of claim 7, wherein:
the aryl boric acid compound is any one of phenylboronic acid, alkyl substituted phenylboronic acid, alkoxy substituted phenylboronic acid, acyl substituted phenylboronic acid, nitro substituted phenylboronic acid, naphthalene boric acid and phenyl diboronic acid;
the alkali is selected from any one of triethylamine, N-diisopropylethylamine and N, N-diisopropylisobutylamine;
the solvent is a mixed solvent of acetonitrile and water with equal volume;
the stirring device is a magnetic stirring device;
the light source of the visible light is a fluorescent lamp;
the reaction time was 48 hours.
10. The method of claim 7, wherein: the crystal of the copper (I) coordination polymer belongs to a monoclinic system, and the space group isC2/mCell parameter ofa = 12.5100(9) Å，b = 9.4515(6) Å，c = 12.0472(9) Å，α= 90.00 °，β= 107.004(8) °，γ = 90.00 °，V = 1362.16(17) nm3，Z = 1。
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