CN115417751A - Method for hydroxylation of benzene ring C-H phenol - Google Patents
Method for hydroxylation of benzene ring C-H phenol Download PDFInfo
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- CN115417751A CN115417751A CN202210666993.0A CN202210666993A CN115417751A CN 115417751 A CN115417751 A CN 115417751A CN 202210666993 A CN202210666993 A CN 202210666993A CN 115417751 A CN115417751 A CN 115417751A
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Abstract
The invention relates to the technical field of organic chemistry, in particular to a method for hydroxylation of benzene ring C-H phenol, which comprises the following steps: mixing raw materials, a solvent, a boron compound, a halogenating agent, a nitrogen-containing heterocyclic compound, an oxidant and an amide compound, and stirring and reacting for 12-72 hours at the temperature of 20-50 ℃ under the illumination of 380-456 nm under the sealed condition; the raw material is a compound containing a benzene ring, and the benzene ring structure of the compound containing the benzene ring is at least one hydrogen atom. The invention uses near ultraviolet visible light as reaction energy, is green and environment-friendly, has high energy utilization rate, and can efficiently realize the conversion from light energy to chemical energy; the reaction attacks free radical cation species generated under visible light catalysis by using cheap and easily available oxygen, and a wide range of target products are efficiently and greenly prepared. The method can be widely applied to fully-synthesized synthetic building blocks and new drug derivatization.
Description
Technical Field
The invention relates to the technical field of organic chemistry, in particular to a method for hydroxylation of benzene ring C-H phenol.
Technical Field
Phenols are very important intermediates in the chemical, pharmaceutical and materials industries. The classical process for the preparation of phenols is based on the decomposition of cumene hydroperoxide (Hock process) or the pyrolysis of sodium benzenesulfonate (Dow process) with sulfuric acid. However, both protocols suffer from low yield and inefficient use of energy. Several alternative methods of synthesizing functionalized phenols have been developed, such as nucleophilic aryl substitution of active aryl halides, phenylalkyne transformations, and copper-mediated transformation of aryl diazonium salts and aryl borates. However, the practical application of these methods is limited due to the harsh reaction conditions, narrow substrate ranges and difficulties in substrate access. Recently, several groups have reported iridium or palladium based catalytic systems for the production of phenol from aryl halides, providing a milder, more useful access to phenol. However, the high price and scarcity of sources of precious metals has limited the widespread use of these catalysts.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a method for hydroxylating benzene ring C-H phenol.
The purpose of the invention is realized by the following technical scheme:
a method for hydroxylation of a benzene ring C-H phenol, comprising the steps of: mixing raw materials, a solvent, a boron compound, a halogenating agent, a nitrogen-containing heterocyclic compound, an oxidant and an amide compound, and stirring and reacting for 12-72 hours at the temperature of 20-50 ℃ under the action of 380-456 nm light under a sealed condition; the raw material is a compound containing a benzene ring, and the benzene ring structure of the compound containing the benzene ring is at least one hydrogen atom.
Preferably, the starting material is a compound of formula (I):
wherein R is 1 、R 2 、R 3 、R 4 、R 5 The same or different from each other and each is independently selected from the group consisting of hydrogen, alkyl, alkoxy, heteroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, heteroalkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl, heteroalkynyl, cycloalkynyl, heterocycloalkynyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, heteroaryloxy, halogen, hydroxyl, mercapto, aldehyde, sulfonic acid, carboxyl, acid halide, ester, amide, amino, imino, nitro, cyano, nitroso.
Preferably, the solvent is one of N, N-dimethylformamide, ethyl acetate and acetonitrile.
Preferably, the boron compound is one of pinacol diborate, neopentyl glycol diborate, bis (2-methyl-2, 4-pentanediol) borate, bis (2, 4-dimethyl-2, 4-pentanediol) borate and tetrahydroxy diboron.
Preferably, the halogenating machine has the general formula:
wherein R is 6 、R 7 The same or different, and each is independently selected from the group consisting of hydrogen, alkyl, alkoxy, heteroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, heteroalkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl, heteroalkynyl, cycloalkynyl, heterocycloalkynyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, heteroaryloxy, halogen, hydroxy, mercapto, aldehyde, sulfonic acid, carboxy, acid halide, ester, amide, amino, imino, nitro, cyano, nitroso.
Preferably, the nitrogen-containing heterocycle is of the general formula:
wherein R is 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 The same or different from each other and each is independently selected from the group consisting of hydrogen, alkyl, alkoxy, heteroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, heteroalkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl, heteroalkynyl, cycloalkynyl, heterocycloalkynyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, heteroaryloxy, halogen, hydroxyl, mercapto, aldehyde, sulfonic acid, carboxyl, acid halide, ester, amide, amino, imino, nitro, cyano, nitroso.
Preferably, the amine compound is one of triethylamine, diisopropylethylamine, N' -tetramethylethylenediamine, and diisopropylamine.
Preferably, the oxidant is one of oxygen, ozone, sodium bromate, potassium bromate and potassium persulfate.
Preferably, the light source used for illumination is a Kessil lamp.
Compared with the prior art, the invention has the following technical effects:
the method for hydroxylation of benzene ring C-H phenol disclosed by the invention has the advantages that the reaction system is simple, the strict non-metallization of the whole reaction system can be realized, the C-H bond on the aromatic ring is converted into the C-O bond in one step, the reaction process is safe and controllable, and the operation in the preparation production process is simplified; the reaction has high site selectivity and few byproducts, and solves the problem of high difficulty in separating the structural isomers. The near ultraviolet visible light is used as reaction energy, the reaction condition is mild, the environment is protected, the energy utilization rate is high, and the conversion from light energy to chemical energy can be efficiently realized; the reactants are simple and commercially available raw materials, are low in price and very easy to obtain, do not need to be subjected to additional modification protection before reaction, can be directly used for preparation and production, simplify the operation steps and shorten the reaction route; the aryl C-O functional group has the advantages of progressive property and environmental friendliness, can be widely applied to the fields of medicines, pesticides, synthetic industry and the like, and can effectively reduce the economic cost.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below with reference to specific examples and comparative examples. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Unless otherwise specified, the devices used in this example are all conventional experimental devices, the materials and reagents used are commercially available, and the experimental methods without specific reference are also conventional experimental methods.
Example 1
This example provides a p-hydroxyanisole of the formula (a):
the preparation method comprises the following steps:
anisole (0.2mmol, 1.0eq), pinacol diboron ester (0.8 mmol, 4.0eq), diisopropylethylamine (1.0mmol, 5.0eq), N-bromosuccinimide (0.22 mmol, 1.1 eq), isoquinoline (0.04mmol, 0.2eq) and acetonitrile (0.5 mL) are added into a dried 2mL sample bottle, the sample bottle is sealed, an oxygen balloon is introduced, the mixture is stirred uniformly at room temperature, and then the mixture is irradiated by a 390nm LED under stirring, and the reaction time is 12 to 72 hours. After the reaction is finished, the filtrate is dried by spinning, and the target product, white solid and 89.70% of yield are obtained by column chromatography separation.
The result of the correlation characterization analysis is as follows: 1 H NMR(CDCl 3 ，600MHz)δ6.77–6.72(m,4H), 3.72(s,J＝2.0Hz,3H)； 13 C NMR(CDCl 3 100 MHz) delta 153.7,149.6,116.1,114.9, 55.9 the results further confirm the molecular structure of the product as in molecular structure a above.
Example 2
This example provides a process for the preparation of 2-methyl-4-methoxyphenol. The structural formula of the 2-methyl-4-methoxyphenol is shown as the following molecular structural formula b:
the preparation method refers to the preparation method of p-hydroxyanisole in example 1, and is characterized in that m-methylanisole (0.2 mmol) is adopted to replace anisole, filtrate is dried in a spinning mode, column chromatography separation is carried out, and a target product is obtained, wherein the yield is 66.86%.
And (3) performing characterization data analysis on the prepared product b, wherein the result is as follows: 1 H NMR(CDCl 3 ,400MHz)δ 6.76-6.66(m,2H),6.62(dd,J＝8.7,2.9Hz,1H),4.86(s,1H),3.75(s,3H),2.23(s,3H)； 13 C NMR(CDCl 3 100 MHz) delta 153.5,147.9,125.1,116.7,115.6,111.9,55.8,16.1 the results further confirm the molecular structure of the product as in molecular structure b above.
Example 3
This example provides a process for the preparation of 4-phenoxyphenol. The structural formula of the 4-phenoxyphenol is shown as the following molecular structural formula c:
the preparation method refers to the preparation method of p-hydroxyanisole in example 1, and is characterized in that diphenyl ether (0.2 mmol) is adopted to replace anisole, filtrate is dried in a spinning mode, column chromatography separation is carried out, and the target product is obtained, wherein the yield is 75.34%.
The prepared product c is subjected to characterization data analysis, and the result is as follows: 1 H NMR(400MHz, Chloroform-d)δ7.31(dd,J＝8.5,7.5Hz,2H),7.06(t,J＝7.4Hz,1H),6.96(t,J＝8.9 Hz,4H),6.83(d,J＝8.9Hz,2H),4.80(s,1H)； 13 c NMR (101MHz, chloroform-d) delta 158.5,151.6,150.2,129.5,122.3,121.1,117.6,117.1 this further confirms the molecular structure of the product as described above for molecular structure C.
Example 4
This example provides a method for preparing methyl 5-methoxysalicylate. The structural formula of the methyl 5-methoxysalicylate is shown as the following molecular structural formula d:
the preparation method refers to the preparation method of p-hydroxyanisole in example 1, and is characterized in that methyl 2-methoxybenzoate (0.2 mmol) is used for replacing anisole, filtrate is dried in a spinning mode, column chromatography separation is conducted, and a target product is obtained, and the yield is 70.92%.
The prepared product d is subjected to characterization data analysis, and the result is as follows: 1 H NMR(400MHz,CDCl 3 )δ 7.30(d,J＝3.2Hz,1H),6.97(dd,J＝8.9,3.2Hz,1H),6.85(d,J＝8.9Hz,1H),5.19(brs, 1H,OH),3.87(s,3H),3.82(s,3H).； 13 C NMR(100MHz,CDCl 3 ) Delta 166.8,153.7,149.3, 120.8,120.6,118.4,114.2,57.0,52.5, which further confirms the molecular structure of the product as described above for molecular structure d.
Example 5
This example provides a method for preparing 2, 5-dimethoxyphenol. The structural formula of the 2, 5-dimethoxyphenol is shown as the following molecular structural formula e:
the preparation method refers to the preparation method of p-hydroxyanisole in example 1, and is different in that p-xylylene ether (0.2 mmol) is adopted to replace anisole, filtrate is dried in a spinning mode, column chromatography separation is carried out, and a target product is obtained, and the yield is 59.13%.
And (3) performing characterization data analysis on the prepared product e, wherein the result is as follows: 1 H NMR(400MHz,CDCl 3 ) δ6.74(d,J＝8.8Hz,1H),6.54(d,J＝2.9Hz,1H),6.35(dd,J＝8.8,2.9Hz,1H),5.74(s, 1H),3.80(s,3H),3.71(s,3H).； 13 C NMR(100MHz,CDCl 3 ) Delta 154.5,146.4,140.9,111.5, 104.2,101.7,56.5,55.5 the results further confirm that the product molecular structure is just like structure e above.
Example 6
This example provides a method for preparing 3-fluoro-4-methoxyphenol. The structural formula of the 3-fluoro-4-methoxyphenol is shown as the following molecular structural formula f:
the preparation method refers to the preparation method of p-hydroxyanisole in example 1, and is characterized in that 2-fluoroanisole (0.2 mmol) is adopted to replace anisole, filtrate is dried in a spinning mode, column chromatography separation is carried out, and a target product, a white solid and the yield are 46.73%.
The prepared product f is subjected to characterization data analysis, and the result is as follows: 1 H NMR(600MHz,CDCl 3 ):δ 6.82(t,J＝9.0Hz,1H),6.63(dd,J＝12.6,3.0Hz,1H),6.576.49m,1H),5.67(br s,1H), 3.82(s,3H). 13 C NMR(150MHz,CDCl 3 ) Delta 152.9,145.0,141.4,115.1,110.3,104.6, 57.2 the results further confirm the molecular structure of the product as described above.
Example 7
This example provides a method for preparing 4-aminophenol. The structural formula of the 4-aminophenol is shown as the following molecular structural formula g:
the preparation method refers to the preparation method of p-hydroxyanisole in example 1, and is different in that aniline (0.2 mmol) is adopted to replace anisole, filtrate is dried in a spinning mode, column chromatography separation is carried out, and the target product, white solid and yield are 85.91%.
The prepared product g is subjected to characterization data analysis, and the result is as follows: 1 H NMR(600MHz,CDCl 3 ) Delta 8.35 (s, 1H), 6.52-6.44 (m, 4H), 4.38 (s, 2H). The results further confirm that the molecular structure of the product is as in the above molecular structure g.
Example 8
This example provides a method for preparing 4-methoxy-3- (trifluoromethyl) phenol. The structural formula of the 4-methoxy-3- (trifluoromethyl) phenol is shown as the following molecular structural formula h:
the preparation method refers to the preparation method of p-hydroxyanisole in example 1, and is characterized in that 2- (trifluoromethyl) anisole (0.2 mmol) is adopted to replace anisole, filtrate is dried in a spinning mode, column chromatography separation is carried out, and the target product, white solid and yield are 45.32%.
And (3) performing characterization data analysis on the prepared product h, wherein the result is as follows: 1 H NMR(600MHz,CDCl 3 ):δ 7.07(d,J＝3.0Hz,1H),6.97(dd,J＝9.0,3.0Hz,1H),6.90(d,J＝8.4Hz,1H),3.85(s, 3H)； 13 C NMR(150MHz,CDCl 3 ) Delta 151.7,148.8,123.3,119.7,119.6,114.4,114.0 and 56.7, the results further confirm that the molecular structure of the product is just as that of the above molecular structure h.
Example 9
This example provides a method for preparing sesamol. The structural formula of the sesamol is shown as the following molecular structural formula i:
the preparation method refers to the preparation method of p-hydroxyanisole in example 1, except that 1, 3-benzodioxole (0.2 mmol) is used to replace anisole, filtrate is dried by spinning, and column chromatography separation is carried out to obtain the target product, the yield is 64.24%
And (3) performing characterization data analysis on the prepared product i, wherein the result is as follows: 1 H NMR(400MHz,CDCl 3 )δ 6.66(d,J＝8.4Hz,1H),6.44(d,J＝2.8Hz,1H),6.27(dd,J＝8.0,2.8Hz,1H),5.91(s, 2H),5.57(br s,1H)； 13 C NMR(100MHz,CDCl 3 ) Delta 150.5,148.2,141.6,108.3,106.8, 101.2,98.4 the results further confirm the molecular structure of the product as in i above.
Example 10
This example provides a method for preparing 4- (4-fluorophenoxy) phenol. The structural formula of the 4- (4-fluorophenoxy) phenol is shown as the following molecular structural formula j:
the preparation method refers to the preparation method of p-hydroxyanisole in example 1, and is characterized in that 4-fluorodiphenyl ether (0.2 mmol) is adopted to replace anisole, filtrate is dried in a spinning mode, column chromatography separation is carried out, a target product is obtained, and the yield is 67.60%.
And (3) performing characterization data analysis on the prepared product j, wherein the result is as follows: 1 H NMR(400MHz,CDCl 3 )δ 7.15(t,J＝8.4Hz,1H),7.07-6.93(m,4H),6.55(dd,J＝8.4,2.4Hz,1H),6.52(dd,J＝ 8.4,2.4Hz,1H),6.45(t,J＝2.4Hz,1H),5.18(br s,1H)； 13 C NMR(100MHz,CDCl 3 ) Delta 159.3,158.1,156.8,15234,130.3,120.8,116.2,110.2,110.0,105.3 this result further confirms the molecular structure of the product as described above for molecular structure j.
Example 11
This example provides a process for the preparation of 4- (methylthio) phenol. The structural formula of the 4- (methylthio) phenol is shown as the following molecular structural formula k:
the preparation method refers to the preparation method of p-hydroxyanisole in example 1, and is characterized in that methyl phenyl sulfide (0.2 mmol) is adopted to replace anisole, filtrate is dried in a spinning mode, column chromatography separation is carried out, and a target product, a white solid and the yield of 50.72% are obtained.
The prepared product k is subjected to characterization data analysis, and the result is as follows: 1 H NMR(400MHz,CDCl 3 )δ 7.22(d,J＝8.8Hz,2H),6.79(d,J＝8.8Hz,2H),5.43(s,1H),2.45(s,3H)； 13 C NMR(100MHz,CDCl 3 ) Delta 154.0,130.4,128.8,116.2,18.0. This result further confirms the molecular structure of the product as in molecular structure k above.
Example 12
This example provides a method for preparing 4-pyrrolidinophenol. The structural formula of the 4-pyrrolidinylphenol is shown as the following molecular structural formula I:
the preparation method refers to the preparation method of p-hydroxyanisole in example 1, and is different in that 1-phenylpyrrolidine (0.2 mmol) is adopted to replace anisole, the filtrate is dried by spinning, and column chromatography separation is carried out to obtain the target product, wherein the yield is 47.68%.
The prepared product l is subjected to characterization data analysis, and the result is as follows: 1 H NMR(400MHz,CDCl 3 )δ 7.40(s,1H),6.72(d,J＝6.6Hz,2H),6.45(d,J＝8.4Hz,2H),3.40-3.10(m,4H), 2.01-1.85(m,4H)； 13 C NMR(100MHz,CDCl 3 ) Delta 148.0,142.5,115.7,112.7,44.9,24.9 this result further confirms the molecular structure of the product as described above for molecular structure l.
Example 13
The embodiment provides a preparation method of 6-methoxy-2-naphthol. The structural formula of the 6-methoxy-2-naphthol is shown as the following molecular structural formula I:
the preparation method refers to the preparation method of p-hydroxyanisole in example 1, and is different in that 2-naphthylmethyl ether (0.2 mmol) is adopted to replace anisole, filtrate is dried in a spinning mode, column chromatography separation is carried out, the target product is obtained, and the yield is 58.85%.
The prepared product l is subjected to characterization data analysis, and the result is as follows: 1 H NMR(500MHz,CDCl 3 )δ 7.67(d,J＝8.6Hz,1H,H),7.61(d,J＝8.6Hz,1H,H),7.17-7.08(m,4H,H),4.95(s,1H, OH)3.92(s,3H,CH3)ppm.； 13 C NMR(100MHz,CDCl 3 ) Delta 155.8,151.5,129.6,129.5, 128.2,127.6,119.1,117.8,109.5,105.7,55.1 the results further confirm the molecular structure of the product as described above for molecular structure l.
Example 14
This example provides a process for the preparation of 1, 4-benzenediol. The structural formula of the 1, 4-benzenediol is shown as the following molecular structural formula m:
the preparation method refers to the preparation method of p-hydroxyanisole in example 1, and is different in that phenol (0.2 mmol) is adopted to replace anisole, filtrate is dried in a spinning mode, column chromatography separation is carried out, and the target product is obtained and is a white solid, and the yield is 73.88%.
And (3) performing characterization data analysis on the prepared product m, wherein the result is as follows: 1 H NMR(300MHz,CDCl 3 )δ 8.61(s,2H),6.55(s,4H)； 13 C NMR(75MHz,CDCl 3 ) Delta 150.1,116.0. This result further confirms the molecular structure of the product as described above for molecular structure m.
Example 15
This example provides a method for preparing 3-hydroxypyridine. The structural formula of the 3-hydroxypyridine is shown as the following molecular structural formula n:
the preparation method refers to the preparation method of p-hydroxyanisole in example 1, and is different in that pyridine (0.2 mmol) is used for replacing anisole, the filtrate is dried in a spinning mode, column chromatography separation is carried out, and the target product, brown solid and yield are 65.18%.
And (3) performing characterization data analysis on the prepared product n, wherein the result is as follows: 1 H NMR(400MHz,CDCl 3 ):δ 9.90(br s,1H),8.16(s,1H),8.04(d,J＝3.5Hz,1H),7.24-7.12(m,1H)； 13 C NMR(100 MHz,CDCl 3 ) Delta 154.0,140.4,138.2,124.4,122.3 the results further confirm that the molecular structure of the product is as described above for molecular structure n.
Example 16
This example provides a method for preparing 5-hydroxyindole. The structural formula of the 5-hydroxyindole is shown as the following molecular structural formula o:
the preparation method refers to the preparation method of p-hydroxyanisole in example 1, and is characterized in that indole (0.2 mmol) is adopted to replace anisole, filtrate is dried in a spinning mode, column chromatography separation is carried out, and the target product, light brown solid and 54.08% yield are obtained.
The prepared product o was subjected to characterization data analysis, and the result was: 1 H NMR(400MHz,DMSO):δ6.15–6.26(1H,m),6.58(1H,d,J＝8.5Hz),6.80–6.85(1H,m),7.15(1H,d,J＝8.5 Hz),7.18–7.21(1H,m),8.57(1H,br s),10.73(1H,br s)； 13 c NMR (100MHz, DMSO): 100.2,103.9,111.3,111.6,125.5,128.4,130.5,150.5. This result further confirms the molecular structure of the product as described above for molecular structure o.
Example 17
The embodiment provides a method for preparing Hydroxy-pyriproxyfen. The structural formula of the Hydroxy-pyriproxyfen is shown as the following molecular structural formula p:
the preparation method refers to the preparation method of p-hydroxyanisole in example 1, and is characterized in that pyriproxyfen (0.2 mmol) is adopted to replace anisole, the filtrate is dried in a spinning mode, and column chromatography separation is carried out to obtain a target product, namely a light yellow solid, and the yield is 44.19%.
The prepared product p is subjected to characterization data analysis, and the result is as follows: 1 H NMR(400MHz,CD 3 CN):δ 8.11(ddd,J＝5.0,2.0,0.9Hz,1H),7.62(ddd,J＝8.4,7.1,2.0Hz,1H),7.02–6.57(m, 10H),5.64–5.48(m,1H),4.21–4.00(m,2H),1.37(d,J＝6.4Hz,3H)； 13 C NMRδ 163.3,154.8,152.2,151.8,151.7,146.5,139.9,120.1,119.7,117.2,116.6,116.1,112.2, 71.5,70.6,17.3.HRMS calculated for C 20 H 20 NO 2 :338.1387[M+](ii) a 338.1387 for found; devision: -0.2ppm the results further confirm the molecular structure of the product as described above for molecular structure p.
Example 18
This example provides a method for preparing Hydroxy-diclofenac amide. The structural formula of the Hydroxy-diclofenac amide is shown as the following molecular structural formula q:
the preparation method refers to the preparation method of p-hydroxyanisole in example 1, and is characterized in that diclofenac amide (0.2 mmol) is adopted to replace anisole, filtrate is dried in a spinning mode, column chromatography separation is carried out, and a target product, a black solid and a yield of 37.74% are obtained.
The prepared product q was subjected to characterization data analysis, and the result was: 1 H NMR(400MHz,CD 3 CN):δ 7.60(d,J＝8.1Hz,2H),7.48(dd,J＝8.7,7.6Hz,1H),6.89(d,J＝2.4Hz,1H),6.76(brs, 1H,OH),6.62(dd,J＝8.4,2.5Hz,1H),6.23(d,J＝8.4Hz,1H),3.68(s,2H).； 13 C NMR δ(100MHz,CDCl 3 ):δ174.1,154.1,137.0,136.0,132.2,131.6,130.1,126.9,114.6, 113.8,110.1,36.5.HRMS calculated for C 15 H 16 NO 2 Cl 2 :294.0083[M+](ii) a found: 294.0082visualization.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (9)
1. A method for hydroxylation of benzene ring C-H phenol is characterized by comprising the following steps: mixing raw materials, a solvent, a boron compound, a halogenating agent, a nitrogen-containing heterocyclic compound, an oxidant and an amide compound, and stirring and reacting for 12-72 hours at the temperature of 20-50 ℃ under the illumination of 380-456 nm under the sealed condition; the raw material is a compound containing a benzene ring, and the benzene ring structure of the compound containing the benzene ring is at least one hydrogen atom.
2. A process for the C-H phenolic hydroxylation of benzene rings according to claim 1, characterized in that said starting material is a compound of formula (I):
wherein R is 1 、R 2 、R 3 、R 4 、R 5 Are the same or different from each other and are each independently selected from the group consisting of hydrogen, alkyl, alkoxy, heteroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, heteroalkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl, heteroalkynyl, cycloalkynyl, heterocycloalkynyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, heteroarylOxy, halogen, hydroxyl, sulfydryl, aldehyde group, sulfonic group, carboxyl, acyl halide group, ester group, amide group, amino group, imino group, nitro group, cyano group and nitroso group.
3. The method for hydroxylation of benzene ring C-H phenols according to claim 1, characterized in that said solvent is one of N, N-dimethylformamide, ethyl acetate, acetonitrile.
4. The method of hydroxylating a phenyl ring C-H phenol according to claim 1, wherein said boron compound is one of pinacol diborate, neopentyl glycol diborate, bis (2-methyl-2, 4-pentanediol) borate, bis (2, 4-dimethyl-2, 4-pentanediol) borate, tetrahydroxydiboron.
5. The process for the hydroxylation of benzene ring C-H phenols according to claim 1, wherein said halogenating machine has the general formula:
wherein R is 6 、R 7 The same or different, and each is independently selected from the group consisting of hydrogen, alkyl, alkoxy, heteroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, heteroalkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl, heteroalkynyl, cycloalkynyl, heterocycloalkynyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, heteroaryloxy, halogen, hydroxyl, mercapto, aldehyde, sulfonic acid, carboxyl, acid halide, ester, amide, amino, imino, nitro, cyano, nitroso.
6. The method of hydroxylating a phenol having a benzene ring C-H according to claim 1, wherein said nitrogen-containing heterocycle has the general formula:
wherein R is 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 The same or different from each other and each is independently selected from the group consisting of hydrogen, alkyl, alkoxy, heteroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, heteroalkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl, heteroalkynyl, cycloalkynyl, heterocycloalkynyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, heteroaryloxy, halogen, hydroxyl, mercapto, aldehyde, sulfonic acid, carboxyl, acid halide, ester, amide, amino, imino, nitro, cyano, nitroso.
7. The method of C-H phenol hydroxylation of a benzene ring according to claim 1, wherein said amine compound is one of triethylamine, diisopropylethylamine, N' -tetramethylethylenediamine, diisopropylamine.
8. The method of hydroxylating a benzene ring C-H phenol according to claim 1, wherein said oxidizing agent is one of oxygen, ozone, sodium bromate, potassium persulfate.
9. The method for hydroxylation of benzene ring C-H phenol according to claim 1, wherein the light source used for illumination is Kessil lamp.
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