CN117342907A - Method for preparing phenol by hydroxylation reaction of boric acid derivative in air under no-alkali condition without light catalyst - Google Patents

Method for preparing phenol by hydroxylation reaction of boric acid derivative in air under no-alkali condition without light catalyst Download PDF

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CN117342907A
CN117342907A CN202311164662.8A CN202311164662A CN117342907A CN 117342907 A CN117342907 A CN 117342907A CN 202311164662 A CN202311164662 A CN 202311164662A CN 117342907 A CN117342907 A CN 117342907A
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acid
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boric acid
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何海峰
申亮
袁好梦
黄钰贞
王明聪
冯朝轩
茅德睿
胡一帆
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Jiangxi Science and Technology Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C07B41/02—Formation or introduction of functional groups containing oxygen of hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form

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Abstract

The invention relates to the technical field of organic synthesis, in particular to a method for preparing phenol by hydroxylation reaction of boric acid derivatives in air under the condition of no light catalyst and no alkali. The method comprises the following steps: under the condition of room temperature, oxygen in air is used as an oxidant, arylboronic acid and an ether solvent are subjected to oxidative hydroxylation reaction under the irradiation of light, and the reaction is completed and post-treatment is carried out to obtain the phenolic compound. In the preparation process, the phenolic compound is prepared in high yield under the conditions of no need of adding transition metal as a catalyst, no need of adding a photocatalyst, no need of adding an oxidant, no need of adding alkali, no need of heating and photocatalysis.

Description

Method for preparing phenol by hydroxylation reaction of boric acid derivative in air under no-alkali condition without light catalyst
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method for preparing phenol by hydroxylation reaction of boric acid derivatives in air under the condition of no light catalyst and no alkali.
Background
Phenolic compounds are important organic chemical raw materials and have wide application in the fields of medicine, organic synthesis, industry and the like. In recent years, with the rapid development of industries such as industry and electronics industry, the demand of phenolic compounds has increased greatly, so that researchers are continually exploring more superior methods for synthesizing phenolic compounds. Hydroxylation of arylboronic acids is one of the most efficient methods for synthesizing phenolic compounds, however, there is currently a certain disadvantage to this approach. For example, the initial research on aryl boronic acid hydroxylation has focused on the use of metal photocatalysts (ACS sustaiable chem.eng.2020,8, 2682-2687), while in some cases strong bases are required (Green chem.,2019,21,4614-4618), or in the absence of metal catalysts, stoichiometric strong oxidants are used (org.lett., 2012,14,3494-3497;Tetrahedron Lett, 2015,56,1524-1527), or with the aid of microwave reaction equipment (Green chem.,2019,21,4614-4618).
In recent years, the research on the formation of phenols by photocatalytic oxidation and hydroxylation of arylboronic acids has received a great deal of attention. However, in these photocatalytic reactions, a photocatalyst is required, and most of the photocatalysts have problems of complicated synthesis, high cost and the like, and although patent CN 110668921A reports a method for preparing phenol by aerobic hydroxylation of a boric acid derivative under the condition of no catalyst, the method still requires addition of an organic base, has a long reaction time (24 hours), and is a uv light source.
Therefore, the development of a green, efficient, mild, simple oxidation process for the synthesis of phenolic compounds is of great importance.
Disclosure of Invention
Aiming at the problems, the invention provides a method for preparing phenol by hydroxylation reaction of boric acid derivatives in air under the condition of no light catalyst and no alkali, wherein in the preparation process, transition metal is not required to be added as a catalyst, oxidant is not required to be added, acid and alkali are not required to be added, and the phenol compound is prepared by efficiently oxidizing aryl boric acid in the air under the conditions of heating and photocatalysis.
The invention aims to provide a method for preparing phenol by hydroxylation reaction of boric acid derivatives in air under the condition of no light catalyst and no alkali, which comprises the following steps:
under the condition of room temperature, oxygen in air is used as an oxidant, arylboronic acid and an ether solvent are subjected to oxidative hydroxylation reaction under the irradiation of light, and the reaction is completed and post-treatment is carried out to obtain the phenolic compound.
Preferably, the reaction time is from 5 to 60 minutes.
Preferably, the reaction time is 5min.
Preferably, the ratio of arylboronic acid to ethereal solvent is 1mmol:1-10mL.
Preferably, the ratio of arylboronic acid to ethereal solvent is 1mmol:3mL.
Preferably, the light source used for illumination is an ultraviolet lamp, a xenon lamp, an LED lamp or an incandescent lamp.
Preferably, the light source used for illumination is a xenon lamp.
Preferably, the ether solvent is one or two of tetrahydrofuran and 2-methyl-tetrahydrofuran.
Preferably, the arylboronic acid is one of phenylboronic acid, o-methylphenylboronic acid, m-methylphenylboronic acid, p-methylphenylboronic acid, 4-methoxyphenylboronic acid, 2-fluorophenylboronic acid, 4-chlorophenylboronic acid, 2, 4-dichlorobenzeneboronic acid, 2-chloro-5-methylphenylboronic acid, 2, 6-di-tert-butyl-4-methylphenylboronic acid, α -naphthylboronic acid, β -naphthylboronic acid, 4-aldyl phenylboronic acid, 2-carboxamidophenylboronic acid, 4- (benzyloxycarbonyl) phenylboronic acid, m-trifluoromethylphenylboronic acid, p-nitrophenylboronic acid, 4-methyl-3-nitrophenylboronic acid.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a novel method for preparing phenolic compounds for the first time, which uses O in the air at room temperature and under the illumination 2 As an oxidant, tetrahydrofuran and/or 2-methyltetrahydrofuran are used as solvents, and arylboronic acid is subjected to oxidative hydroxylation reaction to generate phenolic compounds. The method can rapidly complete the reaction at room temperature for 5 minutes under a xenon lamp without adding a photocatalyst or alkali, and has the advantages of mild reaction conditions, simplicity in operation, high safety, fewer side reactions, short reaction time and the like.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
As shown in Table 1, the method adopts the arylboronic acid as the raw material, takes air as the oxidant in tetrahydrofuran or 2-methyltetrahydrofuran solvent, and converts the boric acid group in the arylboronic acid into hydroxyl under the irradiation of a light source. The reaction conditions of the present invention are shown in Table 1.
TABLE 1 optimization of reaction conditions a
Examples Solvent(s) Alkali addition Light source Yield (%)
1 Tetrahydrofuran (THF) Without any means for Ultraviolet lamp 90
2 Tetrahydrofuran (THF) Without any means for Blue/green LED lamp 85/88
3 Tetrahydrofuran (THF) Without any means for Filament lamp 92
4 Tetrahydrofuran (THF) Without any means for Xenon lamp 98
5 b Tetrahydrofuran (THF) Without any means for Xenon lamp 0
6 Tetrahydrofuran (THF) Without any means for Light-shielding 0
7c Tetrahydrofuran (THF) Triethylamine Xenon lamp 51
8 2-methyltetrahydrofuran Without any means for Xenon lamp 91
9 N, N-dimethylformamide Without any means for Xenon lamp 12
10 Ethanol Without any means for Xenon lamp 15
11 Toluene (toluene) Without any means for Xenon lamp 16
12 2-methyltetrahydrofuran Without any means for Xenon lamp 93
a Reaction conditions: phenylboronic acid (1.0 mmol), air (1 atm), light source (15W), solvent (3.0 mL), room temperature, 5min, isolated yield. b Under nitrogen. c base (1.5 mmol),
we selected phenylboronic acid as the template substrate and screened out the optimal reaction conditions (Table 1). Experimental resultsIt was shown that the expected products were obtained in high yields in the absence of a catalyst using tetrahydrofuran as solvent, an air atmosphere and room temperature using an ultraviolet lamp, a blue/green LED lamp, an incandescent lamp and a xenon lamp, respectively, as light sources (examples 1 to 4). The control experiment in which the yield of irradiation of the xenon lamp light source near the sunlight was 98% did not reach the expected effect under dark conditions, confirming the necessity of continuous irradiation of the light source (example 6). When air is replaced with nitrogen, the reaction is terminated (example 5), indicating that air plays an important role in the reaction. The present invention attempts to add the organic base Et on the basis of example 4 3 The addition of N as an additive significantly reduced the yield (example 7), indicating that the addition of base inhibited the reaction from proceeding. Studies with the solvents (example 9-example 12) showed that 2-methyltetrahydrofuran and tetrahydrofuran are the best solvents with yields of 93% and 98% (example 4, example 12), respectively. Thus, 4 is the optimal reaction condition.
Based on optimizing the reaction conditions, we extended the substrate range of boric acid (table 2). Arylboronic acids containing different functional groups on the aromatic ring have proven to be compatible under standard conditions and provide the corresponding hydroxylation products. Arylboronic acids having various substituents in the para position of the aromatic ring, including electron donating groups such as alkyl (example 15), alkoxy (example 16), electron withdrawing groups such as halogen (examples 18, 19), aldehyde (example 25), nitro (example 29), react well to provide the desired product under standard conditions. It is noted that tertiary butyl groups with large steric hindrance on the aromatic ring (example 26) can also be adapted to the reaction conditions. Thus, from these results, it can be inferred that the electronic properties of the substituents have little influence on the reaction efficiency. Furthermore, the optimum reaction conditions are equally applicable to fused rings, which can be successfully subjected to an aerobic hydroxylation reaction without a catalyst, giving corresponding products in 92% and 94% (example 23, example 24).
Table 2 implementation of the different examples and yield a of the target product
a Reaction conditions: boric acid (1.0 mmol), air (1 atm), light source (15W), solvent (3.0 mL), room temperature, 5min, isolated yield.
The following is a specific explanation of example 4 and examples 13 to 30:
example 4
Sequentially adding 1.0mmol phenylboronic acid and 3mL tetrahydrofuran into a reaction bottle, irradiating with xenon lamp, reacting at room temperature under air condition for 5min, tracking the reaction progress by thin layer chromatography, adding 5.0mL HCl (2.0M) into the reaction bottle after the reaction, extracting with ethyl acetate (3×10mL), mixing organic phases, washing the organic phase with water for 2 times, and removing Na 2 SO 4 Drying, filtering, concentrating, separating by column chromatography to obtain target phenol with yield of 98%, and making the product structure pass through 1 H NMR 13 C NMR identification. 1 H NMR(400MHz,DMSO-d 6 )δ(ppm):9.37(s,1H),7.16-7.21(m,2H),6.76-6.87(m,3H). 13 C NMR(100MHz,DMSO-d 6 )δ(ppm):157.36,129.35,118.82,115.26.
Example 13
Sequentially adding 1.0mmol o-methyl phenylboronic acid and 3mL tetrahydrofuran into a reaction bottle, irradiating with xenon lamp, reacting at room temperature under air condition for 5min, tracking the reaction progress by thin layer chromatography, adding 5.0mL HCl (2.0M) into the reaction bottle after the reaction, extracting with ethyl acetate (3×10mL), mixing organic phases, washing the organic phase with water for 2 times, and removing Na 2 SO 4 Drying, filtering, concentrating, separating by column chromatography to obtain target product o-methylphenol with yield of 95%, and making the product structure pass through 1 H NMR 13 C NMR identification. 1 H NMR(400MHz,CDCl 3 )δ(ppm):7.09-7.16(m,2H),6.88(t,J＝7.4Hz,1H),6.79(d,J＝8.0Hz,1H),4.89(s,1H),2.28(s,3H). 13 C NMR(100MHz,CDCl 3 )δ(ppm):153.75,131.07,127.15,123.80,120.80,114.94,15.74
Example 14
Sequentially adding 1.0mmol of M-tolueneboronic acid and 3mL of tetrahydrofuran into a reaction bottle, irradiating with a xenon lamp, reacting at room temperature under air condition for 5min, tracking the reaction progress by thin layer chromatography, adding 5.0mL of HCl (2.0M) into the reaction bottle after the reaction is finished, extracting with ethyl acetate (3×10mL), combining organic phases, washing the organic phases with water for 2 times, and using Na-free solution 2 SO 4 Drying, filtering, concentrating, separating by column chromatography to obtain target product of m-methylphenol with 96% yield, and making the product have the structure of 1 H NMR 13 C NMR identification. 1 H NMR(400MHz,CDCl 3 )δ(ppm):7.21(t,J＝7.6Hz,1H),6.86(d,J＝7.6Hz,1H),6.77(d,J＝7.9Hz,2H),6.50(s,1H),2.38(s,3H). 13 C NMR(100MHz,CDCl 3 )δ(ppm):155.28,140.01,129.59,121.86,116.31,112.56,21.39.
Example 15
Sequentially adding 1.0mmol of p-tolueneboronic acid and 3mL of tetrahydrofuran into a reaction bottle, irradiating with a xenon lamp, reacting at room temperature under air condition for 5min, tracking the reaction progress by thin layer chromatography, adding 5.0mL of HCl (2.0M) into the reaction bottle after the reaction is finished, extracting with ethyl acetate (3×10mL), combining organic phases, washing the organic phases with water for 2 times, and using Na-free solution 2 SO 4 Drying, filtering, concentrating, separating by column chromatography to obtain target product p-methylphenol with yield of 98%, and making the product structure pass through 1 H NMR 13 C NMR identification. 1 H NMR(400MHz,CDCl 3 )δ(ppm):7.07(d,J＝8.3Hz,2H),6.78(d,J＝8.4Hz,2H),5.70(s,1H),2.31(s,3H). 13 C NMR(100MHz,CDCl 3 )δ(ppm):153.09,130.16,130.11,115.24,20.50
Example 16
Sequentially adding 1.0mmol of 4-methoxyphenylboronic acid and 3mL of tetrahydrofuran into a reaction bottle, irradiating with xenon lamp, reacting at room temperature under air condition for 5min, tracking the reaction progress by thin layer chromatography, and adding 5.0mL of HCl (20M), extraction with ethyl acetate (3X 10 mL), combining the organic phases, then washing the organic phase 2 times with water, with Na-free solution 2 SO 4 Drying, filtering, concentrating, separating by column chromatography to obtain target product 4-methoxyphenol with 99% yield, and making the product have the structure of 1 H NMR 13 C NMR identification. 1 H NMR(400MHz,CDCl 3 )δ(ppm):6.77-6.81(m,4H),5.08(s,1H),3.77(s,3H). 13 C NMR(100MHz,CDCl 3 )δ(ppm):153.59,149.58,116.17,115.01,55.94
Example 17
Sequentially adding 1.0mmol of 2-fluorobenzeneboronic acid and 3mL of tetrahydrofuran into a reaction bottle, irradiating with a xenon lamp, reacting at room temperature under air condition for 5min, tracking the reaction progress by thin layer chromatography, adding 5.0mL of HCl (2.0M) into the reaction bottle after the reaction is finished, extracting with ethyl acetate (3X 10 mL), combining organic phases, washing the organic phases with water for 2 times, and using Na-free solution 2 SO 4 Drying, filtering, concentrating, separating by column chromatography to obtain target product 2-fluorophenol with 93% yield, and making the product have the structure of 1 H NMR 13 C NMR identification. 1 H NMR(400MHz,CDCl 3 )δ(ppm):7.02-7.11(m,3H),6.85-6.89(m,1H),5.88(s,1H). 13 C NMR(100MHz,CDCl 3 )δ(ppm):152.19,150.30,143.55,143.44,124.89,124.86,120.94,120.88,117.47,117.45,115.70,115.55.
Example 18
Sequentially adding 1.0mmol of 4-fluorobenzeneboronic acid and 3mL of tetrahydrofuran into a reaction bottle, irradiating with a xenon lamp, reacting at room temperature under air condition for 5min, tracking the reaction progress by thin layer chromatography, adding 5.0mL of HCl (2.0M) into the reaction bottle after the reaction is finished, extracting with ethyl acetate (3X 10 mL), combining organic phases, washing the organic phases with water for 2 times, and using Na-free solution 2 SO 4 Drying, filtering, concentrating, separating by column chromatography to obtain target product 4-fluorophenol with yield of 95%, and making the product structure pass through 1 H NMR 13 C NMR identification. 1 H NMR(400MHz,CDCl 3 )δ(ppm):6.91-6.95(m,2H),6.78-6.81(m,2H). 13 C NMR(100MHz,CDCl 3 )δ(ppm):158.39,156.50,151.13,151.12,116.44,116.38,116.21,116.03
Example 19
Sequentially adding 1.0mmol of 4-chlorobenzoic acid and 3mL of tetrahydrofuran into a reaction bottle, irradiating with xenon lamp, reacting at room temperature under air condition for 5min, tracking the reaction progress by thin layer chromatography, adding 5.0mL of HCl (2.0M) into the reaction bottle after the reaction is finished, extracting with ethyl acetate (3×10mL), combining organic phases, washing the organic phases with water for 2 times, and using Na-free solution 2 SO 4 Drying, filtering, concentrating, separating by column chromatography to obtain target product 4-chlorophenol with 92% yield, and making the product structure pass through 1 H NMR 13 C NMR identification. 1 H NMR(400MHz,CDCl 3 )δ(ppm):7.16-7.13(m,2H),6.72-6.75(m,2H),5.08(s,1H). 13 C NMR(100MHz,CDCl 3 )δ(ppm):153.94,129.62,125.75,116.80
Example 20
Sequentially adding 1.0mmol of 2, 4-dichlorobenzoic acid and 3mL of tetrahydrofuran into a reaction bottle, irradiating with xenon lamp, reacting at room temperature under air condition for 5min, tracking the reaction progress by thin layer chromatography, adding 5.0mL of HCl (2.0M) into the reaction bottle after the reaction is finished, extracting with ethyl acetate (3X 10 mL), mixing organic phases, washing the organic phases with water for 2 times, and removing Na 2 SO 4 Drying, filtering, concentrating, separating by column chromatography to obtain target product 2, 4-dichlorophenol with 91% yield, and making the product structure pass through 1 H NMR 13 C NMR identification. 1 H NMR(400MHz,DMSO-d6)δ(ppm):10.42(s,1H),7.38(d,J＝1.9Hz,1H),7.15-7.17(m,1H),6.96(d,J＝8.7Hz,1H). 13 C NMR(100MHz,DMSO-d6)δ(ppm):152.27,129.03,127.80,122.62,120.60,117.64.
Example 21
Sequentially adding 1.0mmol of 2-chloro-5-methylphenylboronic acid and 3mL of tetrahydrofuran into a reaction bottle, irradiating with xenon lamp, reacting at room temperature under air condition for 5min, tracking the reaction progress by thin layer chromatography, adding 5.0mL of HCl (2.0M) into the reaction bottle after the reaction, extracting with ethyl acetate (3×10mL), and mixing the organic materialsThe phases were then washed with water 2 times, with Na-free organic phase 2 SO 4 Drying, filtering, concentrating, separating by column chromatography to obtain target product 2-chloro-5-methylphenol with 93% yield, and making the product have the following structure 1 H NMR 13 C NMR identification. 1 H NMR(400MHz,DMSO-d 6 )δ(ppm):9.94(s,1H),7.13-7.16(m,1H),6.80(s,1H),6.57(d,J＝8.0Hz,1H),2.34(s,3H). 13 C NMR(100MHz,DMSO-d 6 )δ(ppm):152.71,137.49,129.33,120.65,117.18,116.68,20.49
Example 22
Sequentially adding 1.0mmol of 2, 6-di-tert-butyl-4-methylphenylboronic acid and 3mL of tetrahydrofuran into a reaction bottle, irradiating with a xenon lamp, reacting at room temperature under air conditions for 5min, tracking the reaction progress by thin layer chromatography, adding 5.0mLHCl (2.0M) into the reaction bottle after the reaction is finished, extracting with ethyl acetate (3X 10 mL), mixing the organic phases, washing the organic phases with water for 2 times, and removing Na 2 SO 4 Drying, filtering, concentrating, separating by column chromatography to obtain target product 2, 6-di-tert-butyl-4-methylphenol with 94% yield, and the product structure is obtained by 1 H NMR 13 C NMR identification. 1 H NMR(400MHz,DMSO-d 6 )δ(ppm):6.88(s,2H),6.62(s,1H),2.35(s,3H),1.38(s,18H). 13 C NMR(100MHz,DMSO-d 6 )δ(ppm):151.48,139.10,127.94,124.84,21.01
Example 23
Sequentially adding 1.0mmol alpha-naphthalene boric acid and 3mL tetrahydrofuran into a reaction bottle, irradiating with xenon lamp, reacting at room temperature under air condition for 5min, tracking reaction progress by thin layer chromatography, adding 5.0mL HCl (2.0M) into the reaction bottle after reaction, extracting with ethyl acetate (3×10mL), mixing organic phases, washing the organic phase with water for 2 times, and removing Na 2 SO 4 Drying, filtering, concentrating, separating by column chromatography to obtain target product alpha-naphthol with 92% yield, and making the product structure pass through 1 H NMR 13 C NMR identification. 1 H NMR(400MHz,CDCl 3 )δ(ppm):8.19-822(m,1H),7.82-7.85(m,1H),7.46-7.52(m,3H),7.31-7.34(m,1H),6.82(dd,J＝7.4,0.5Hz,1H),4.58(s,1H). 13 C NMR(100MHz,CDCl 3 )δ(ppm):151.38,134.80,127.71,126.47,125.86,125.29,124.39,121.55,120.73,108.68.
Example 24
Sequentially adding 1.0mmol beta-naphthalene boric acid and 3mL tetrahydrofuran into a reaction bottle, irradiating with xenon lamp, reacting at room temperature under air condition for 5min, tracking reaction progress by thin layer chromatography, adding 5.0mL HCl (2.0M) into the reaction bottle after the reaction, extracting with ethyl acetate (3×10mL), mixing organic phases, washing the organic phase with water for 2 times, and removing Na 2 SO 4 Drying, filtering, concentrating, separating by column chromatography to obtain target product beta-naphthol with yield of 94%, and making the product structure pass through 1 H NMR 13 C NMR identification. 1 H NMR(400MHz,CDCl 3 )δ(ppm):7.75-7.79(m,2H),7.68(d,J＝8.2Hz,1H),7.42-7.46(m,1H),7.34-7.36(m,1H),7.16(d,J＝2.4Hz,1H),7.12(dd,J＝8.8,2.5Hz,1H). 13 C NMR(100MHz,CDCl 3 )δ(ppm):153.35,134.61,129.87,128.96,127.78,126.54,126.39,123.64,117.77,109.54
Example 25
Sequentially adding 1.0mmol of 4-aldehyde phenylboronic acid and 3mL of tetrahydrofuran into a reaction bottle, irradiating with a xenon lamp, reacting at room temperature under air condition for 5min, tracking the reaction progress by thin layer chromatography, adding 5.0mL of HCl (2.0M) into the reaction bottle after the reaction is finished, extracting with ethyl acetate (3X 10 mL), combining organic phases, washing the organic phases with water for 2 times, and using Na-free solution 2 SO 4 Drying, filtering, concentrating, separating by column chromatography to obtain target product 4-aldehyde phenol with yield of 90%, and making the product structure pass through 1 H NMR 13 C NMR identification. 1 H NMR(400MHz,DMSO-d 6 )δ(ppm):10.57(s,1H),9.77(s,1H),7.74(d,J＝8.1Hz,2H),6.93(d,J＝8.2Hz,2H). 13 C NMR(100MHz,DMSO-d 6 )δ(ppm):190.75,163.29,132.02,128.40,115.80
Example 26
1.0mmol of 2-formamidophenylboronic acid and 3mL of tetrahydrofuran are sequentially added into a reaction flask, and the mixture is irradiated by a xenon lamp in a roomThe reaction was carried out under air at room temperature for 5min, followed by thin layer chromatography, after the completion of the reaction, 5.0mL of HCl (2.0M) was added to the flask, extraction was carried out with ethyl acetate (3X 10 mL), the organic phases were combined, then the organic phase was washed with water 2 times, and the mixture was washed with Na-free solution 2 SO 4 Drying, filtering, concentrating, separating by column chromatography to obtain target product 2-formamidophenol with 89% yield, and making the product structure pass through 1 H NMR 13 C NMR identification. 1 H NMR(400MHz,DMSO-d 6 )δ(ppm):13.03(s,1H),8.40(s,1H),7.86(d,J＝8.0Hz,2H),7.38(t,J＝7.7Hz,1H),6.82-6.89(m,2H). 13 C NMR(100MHz,DMSO-d 6 )δ(ppm):172.14,161.10,134.02,128.08,118.31,117.39,114.36
Example 27
Sequentially adding 1.0mmol of 4- (benzyloxycarbonyl) phenylboronic acid and 3mL of tetrahydrofuran into a reaction bottle, irradiating with a xenon lamp, reacting at room temperature under air condition for 5min, tracking the reaction progress by thin layer chromatography, adding 5.0mL of HCl (2.0M) into the reaction bottle after the reaction is finished, extracting with ethyl acetate (3X 10 mL), combining organic phases, washing the organic phases with water for 2 times, and using Na-free solution 2 SO 4 Drying, filtering, concentrating, separating by column chromatography to obtain target product 4- (benzyloxycarbonyl) phenol with yield of 87%, and making the product structure pass through 1 H NMR 13 C NMR identification. 1 H NMR(400MHz,DMSO-d 6 )δ(ppm):10.49(s,1H),7.87(d,J＝7.2Hz,2H),7.33-7.45(m,5H),6.88(d,J＝7.2Hz,2H),5.29(s,2H). 13 C NMR(100MHz,DMSO-d 6 )δ(ppm):165.39,162.17,136.47,131.51,128.44,127.93,127.81,120.15,115.39,65.55
Example 28
Sequentially adding 1.0mmol M-trifluoromethyl phenylboronic acid and 3mL tetrahydrofuran into a reaction bottle, irradiating with xenon lamp, reacting at room temperature under air condition for 5min, tracking the reaction progress by thin layer chromatography, adding 5.0mL HCl (2.0M) into the reaction bottle after the reaction is finished, extracting with ethyl acetate (3×10 mL), mixing organic phases, washing the organic phase with water for 2 times, and removing Na 2 SO 4 Drying, filtering, concentrating, and purifying with columnSeparating by chromatography to obtain the target product m-trifluoromethyl phenol with 82% yield, and the product structure is obtained by 1 H NMR 13 C NMR identification. 1 H NMR(400MHz,CDCl 3 )δ(ppm):7.35(t,J＝8.0Hz,1H),7.22(t,J＝7.8Hz,1H),7.02-7.04(m,1H),6.14(s,1H). 13 C NMR(100MHz,CDCl 3 )δ(ppm):155.4,132.5,132.25,131.99,131.73,130.35,118.87,118.86,117.85,117.82,112.36,112.33.
Example 29
Sequentially adding 1.0mmol of p-nitrobenzoic acid and 3mL of tetrahydrofuran into a reaction bottle, irradiating with xenon lamp, reacting at room temperature under air condition for 5min, tracking the reaction progress by thin layer chromatography, adding 5.0mL of HCl (2.0M) into the reaction bottle after the reaction is finished, extracting with ethyl acetate (3×10mL), combining organic phases, washing the organic phases with water for 2 times, and using Na-free solution 2 SO 4 Drying, filtering, concentrating, separating by column chromatography to obtain target product p-nitrophenol with 77% yield, and making the product have the structure of 1 H NMR 13 C NMR identification. 1 H NMR(400MHz,DMSO-d 6 )δ(ppm):10.96(s,1H),8.03(s,2H),6.87(s,2H). 13 C NMR(100MHz,DMSO-d 6 )δ(ppm):163.82,139.55,125.93,115.57
Example 30
Sequentially adding 1.0mmol of 4-methyl-3-nitrobenzoic acid and 3mL of tetrahydrofuran into a reaction bottle, irradiating with xenon lamp, reacting at room temperature under air condition for 5min, tracking the reaction progress by thin layer chromatography, adding 5.0mL of HCl (2.0M) into the reaction bottle after the reaction is finished, extracting with ethyl acetate (3X 10 mL), mixing organic phases, washing the organic phases with water for 2 times, and using Na-free solution 2 SO 4 Drying, filtering, concentrating, separating by column chromatography to obtain target product 4-methyl-3 nitrophenol with yield of 80%, and making the product structure pass through 1 H NMR 13 C NMR identification. 1 H NMR(400MHz,DMSO-d 6 )δ(ppm):10.11(s,1H),7.33(s,1H),7.22(d,J＝8.2Hz,1H),7.01(d,J＝8.3Hz,1H),2,36(s,3H). 13 C NMR(100MHz,DMSO-d 6 )δ(ppm):156.02,148.98,133.44,122.58,120.81,110.44,18.71
Example 31
Sequentially adding 1.0mmol phenylboronic acid and 1mL tetrahydrofuran into a reaction bottle, irradiating with xenon lamp, reacting at room temperature under air condition for 60min, tracking the reaction progress by thin layer chromatography, adding 5.0mL HCl (2.0M) into the reaction bottle after the reaction, extracting with ethyl acetate (3×10 mL), mixing organic phases, washing the organic phase with water for 2 times, and removing Na 2 SO 4 Drying, filtering, concentrating, separating by column chromatography, and obtaining the target product phenol with 98% yield.
Example 32
Sequentially adding 1.0mmol phenylboronic acid and 10mL solution (equal amounts of tetrahydrofuran and 2-methyl-tetrahydrofuran) into a reaction bottle, irradiating with xenon lamp, reacting at room temperature under air condition for 30min, tracking the reaction progress by thin layer chromatography, adding 5.0mLHCl (2.0M) into the reaction bottle after the reaction, extracting with ethyl acetate (3×10mL), mixing organic phases, washing the organic phases with water for 2 times, and removing Na 2 SO 4 Drying, filtering, concentrating, separating by column chromatography, and obtaining the target product phenol with 98% yield.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.

Claims (9)

1. The method for preparing phenol by hydroxylation reaction of boric acid derivatives in air under the condition of no light catalyst and no alkali is characterized by comprising the following steps:
under the condition of room temperature, oxygen in air is used as an oxidant, arylboronic acid and an ether solvent are subjected to oxidative hydroxylation reaction under the irradiation of light, and the reaction is completed and post-treatment is carried out to obtain the phenolic compound.
2. The method for preparing phenol by hydroxylation reaction of boric acid derivatives in air under the condition of no light catalyst and no alkali according to claim 1, wherein the reaction time is 5-60min.
3. The method for preparing phenol by hydroxylation reaction of boric acid derivatives in air under the condition of no light catalyst and no alkali according to claim 2, wherein the reaction time is 5min.
4. The method for preparing phenol by hydroxylation reaction of boric acid derivative in air under no-alkali condition without light catalyst according to claim 1, wherein the ratio of aryl boric acid to ether solvent is 1mmol:1-10mL.
5. The method for preparing phenol by hydroxylation reaction of boric acid derivative in air under no-alkali condition without light catalyst according to claim 4, wherein the ratio of aryl boric acid to ether solvent is 1mmol:3mL.
6. The method for preparing phenol by hydroxylation reaction of boric acid derivatives in air under the condition of no light catalyst and no alkali according to claim 1, wherein the light source used for illumination is an ultraviolet lamp, a xenon lamp, an LED lamp or an incandescent lamp.
7. The method for preparing phenol by hydroxylation reaction of boric acid derivatives in air under the condition of no light catalyst and no alkali according to claim 6, wherein the light source used for illumination is a xenon lamp.
8. The method for preparing phenol by hydroxylation reaction of boric acid derivatives in air under the condition of no light catalyst and no alkali according to claim 1, wherein the ether solvent is one or two of tetrahydrofuran and 2-methyl-tetrahydrofuran.
9. The method for preparing phenol by hydroxylation reaction of boric acid derivatives in air under the condition of no light catalyst and no alkali according to claim 1, wherein the aryl boric acid is one of phenylboric acid, o-methylphenylboric acid, m-methylphenylboric acid, p-methylphenylboric acid, 4-methoxyphenylboric acid, 2-fluorophenylboric acid, 4-chlorophenylboronic acid, 2, 4-dichlorobenzoboronic acid, 2-chloro-5-methylphenylboric acid, 2, 6-di-tert-butyl-4-methylphenylboric acid, alpha-naphthylboric acid, beta-naphthylboric acid, 4-aldehyde phenylboric acid, 2-formamidophenylboric acid, 4- (benzyloxycarbonyl) phenylboric acid, m-trifluoromethylphenylboric acid, p-nitrophenylboric acid and 4-methyl-3-nitrobenzeneboric acid.
CN202311164662.8A 2023-09-11 2023-09-11 Method for preparing phenol by hydroxylation reaction of boric acid derivative in air under no-alkali condition without light catalyst Pending CN117342907A (en)

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