CN108727161B - Method for preparing phenol by efficient in-situ hydroxylation of phenylboronic acid - Google Patents
Method for preparing phenol by efficient in-situ hydroxylation of phenylboronic acid Download PDFInfo
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- CN108727161B CN108727161B CN201810801327.7A CN201810801327A CN108727161B CN 108727161 B CN108727161 B CN 108727161B CN 201810801327 A CN201810801327 A CN 201810801327A CN 108727161 B CN108727161 B CN 108727161B
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- phenylboronic acid
- efficient
- phenol
- situ
- sodium perborate
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- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 title claims abstract description 90
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 16
- 230000033444 hydroxylation Effects 0.000 title claims description 11
- 238000005805 hydroxylation reaction Methods 0.000 title claims description 11
- 229960001922 sodium perborate Drugs 0.000 claims abstract description 24
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000000654 additive Substances 0.000 claims abstract description 13
- 230000000996 additive effect Effects 0.000 claims abstract description 13
- 230000000640 hydroxylating effect Effects 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical group [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- 230000002378 acidificating effect Effects 0.000 claims 2
- 125000005619 boric acid group Chemical group 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 7
- 238000003756 stirring Methods 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 5
- 239000007800 oxidant agent Substances 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 150000002989 phenols Chemical class 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RRTCFFFUTAGOSG-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1 RRTCFFFUTAGOSG-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing phenols by directly hydroxylating phenylboronic acid in situ, which comprises the steps of adding phenylboronic acid and sodium perborate into a solvent, and directly stirring under the condition of alkalinity or acidity or without an additive to obtain phenol. The synthesis method is simple and efficient, common sodium perborate is used as an oxidant, a catalyst is not needed, and phenol can be directly and efficiently synthesized under mild conditions.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for preparing phenol by efficient in-situ hydroxylation of phenylboronic acid.
Background
Phenolic compounds play an important role in the prevention and treatment of a wide variety of diseases. One of the important chemical tasks in organic synthesis of phenol with high efficiency. The synthesis of phenol from phenylboronic acid has received a great deal of attention in organic synthesis. The phenylboronic acid has low toxicity, high stability in air, direct purchase in the market and low price. Oxidizing agents generally used for preparing phenol by the in-situ hydroxylation of phenylboronic acid are oxygen and hydrogen peroxide [ appl.Catal.A Gen.,2013,466, 60-67; appl.Catal.A. Gen,2018,562,58-66 ]. Sodium perborate is an ideal oxidizing agent, has the advantages of few byproducts, high selectivity, low price and the like, and is widely applied to organic synthesis. Therefore, the method for preparing phenol by oxidizing phenylboronic acid by using sodium perborate as an oxidizing agent is an efficient and feasible method. In a reaction system of one-step in-situ hydroxylation of phenylboronic acid, a metal catalyst [ Chin.J.org.chem.,2016,36, 862-866; tetrahedron lett, 2017,58(45), 4255-; tetrahedron lett, 2017,58(12), 1211-1215; j. organomet. chem.,2017,851,52-56], the presence of metal catalysts raises costs and presents problems with metal loss, etc. Therefore, it is important to develop a new method for preparing phenol by efficiently hydroxylating phenylboronic acid in situ without a catalyst.
Disclosure of Invention
The invention aims to provide a method for preparing phenol by efficiently hydroxylating phenylboronic acid in situ, which overcomes the defects in the prior art, adopts phenylboronic acid and sodium perborate as raw materials, directly and efficiently generates phenol under mild reaction conditions.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing phenol by efficiently hydroxylating phenylboronic acid in situ comprises the steps of adding phenylboronic acid, sodium perborate and an additive into a solvent, heating, stirring, reacting, separating and purifying to obtain phenol.
Furthermore, the molar ratio of the phenylboronic acid to the sodium perborate is 3 (1-5).
Furthermore, the molar ratio of the additive to the phenylboronic acid is 1 (1-2).
Further, the heating and stirring reaction temperature is 0-60 ℃, and the reaction time is 3 min-1 h.
Further, the reaction does not require a catalyst.
Further, the solvent is any one of water, methanol, ethanol, acetone, tetrahydrofuran, acetonitrile, dichloromethane and diethyl ether.
Furthermore, after the phenylboronic acid, the sodium perborate and the additive are added into the solvent, the concentration of the phenylboronic acid in the solvent is 0.1-0.3 mol/L.
Compared with the prior art, the invention has the following beneficial technical effects:
according to the invention, phenyl boric acid, sodium perborate and an additive are adopted to directly generate phenol, phenyl boric acid and sodium perborate are used as raw materials, hydroxyl is introduced through in-situ hydroxylation, reaction under harsh conditions is not required, and the product is easy to separate and has high yield. The reaction mechanism is shown as formula (1) and formula (2):
Detailed Description
Embodiments of the invention are described in further detail below:
a method for preparing benzene phenol by oxidizing phenylboronic acid with sodium perborate comprises the steps of adding phenylboronic acid, sodium perborate and an additive into a solvent, wherein the molar ratio of the phenylboronic acid to the sodium perborate is 3: 1-3: 5, the molar ratio of the phenylboronic acid to the additive is 1: 1-1: 2, and the concentration of the phenylboronic acid in the solvent is 0.1-0.3 mol/L, heating and stirring at 0-60 ℃ for reaction for 3 min-1 h, and then separating and purifying to obtain phenol. The reaction mechanism is shown as formula (3):
the present invention is described in further detail below with reference to examples:
example 1
5mmol of phenylboronic acid, 5mmol of sodium perborate and 5mmol of additive sodium bicarbonate were added to a reactor containing 10mL of water. At 25 ℃, dissolving phenylboronic acid, sodium perborate and weak base in water, stirring and reacting for 30min at a certain temperature, then acidifying the reaction liquid to the pH value of 3-4, and separating to obtain the phenol with the yield of 92.3%.
Example 2
5mmol of phenylboronic acid, 5mmol of sodium perborate and 5mmol of additive sodium bicarbonate were added to a reactor containing 10mL of methanol. At 25 ℃, dissolving phenylboronic acid and sodium perborate in methanol, stirring and reacting for 30min at a certain temperature, then acidifying the reaction liquid to pH 3-4, and separating to obtain the yield of 91.6%.
Example 3
5mmol of phenylboronic acid and 4mmol of sodium perborate were added to a reactor containing 10mL of water and reacted at 25 ℃ for 30 min. And acidifying the reaction liquid to the pH value of 3-4, and separating to obtain the yield of 74.1%.
Example 4
5mmol of phenylboronic acid and 5mmol of sodium perborate were added to a reactor containing 10mL of water and reacted at 25 ℃ for 30 min. And acidifying the reaction solution to the pH value of 3-4, and separating to obtain the yield of 93.7%.
Example 5
5mmol of phenylboronic acid and 5mmol of sodium perborate were added to a reactor containing 10mL of water and reacted at 35 ℃ for 30 min. And acidifying the reaction solution to the pH value of 3-4, and separating to obtain the yield of 92.0%.
Example 6
3mmol of phenylboronic acid, 15mmol of sodium perborate and 6mmol of additive hydrochloric acid are introduced into a reactor containing 10mL of tetrahydrofuran. At 25 ℃, dissolving phenylboronic acid, sodium perborate and hydrochloric acid in methanol, stirring and reacting at 0 ℃ for 3min, then acidifying the reaction liquid to pH 3-4, and separating to obtain the yield of 87.1%.
Claims (6)
1. A method for preparing phenol by efficiently hydroxylating phenylboronic acid in situ is characterized in that phenylboronic acid is oxidized by sodium perborate, and a boric acid group of the phenylboronic acid is oxidized into phenolic hydroxyl group in the presence of water to obtain phenol;
the method also comprises the step of adding an additive, wherein the additive is an alkaline substance or an acidic substance, and the molar ratio of the additive to the phenylboronic acid is 1 (1-2).
2. The method for preparing phenol by the efficient in-situ hydroxylation of phenylboronic acid according to claim 1, wherein the molar ratio of phenylboronic acid to sodium perborate is 3: (1-5).
3. The method for preparing phenol by the efficient in-situ hydroxylation of phenylboronic acid according to claim 1, wherein the acidic substance is one or more of acetic acid and hydrochloric acid.
4. The method for preparing phenol by the efficient in-situ hydroxylation of phenylboronic acid according to claim 1, wherein the alkaline substance is sodium bicarbonate.
5. The method for preparing phenol by the efficient in-situ hydroxylation of phenylboronic acid according to claim 1, wherein the concentration of phenylboronic acid in water is 0.1-0.3 mol/l.
6. The method for preparing phenol by the efficient in-situ hydroxylation of phenylboronic acid according to claim 1, wherein the reaction temperature is 0-60 ℃, and the reaction time is 3 min-1 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810801327.7A CN108727161B (en) | 2018-07-18 | 2018-07-18 | Method for preparing phenol by efficient in-situ hydroxylation of phenylboronic acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810801327.7A CN108727161B (en) | 2018-07-18 | 2018-07-18 | Method for preparing phenol by efficient in-situ hydroxylation of phenylboronic acid |
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| Publication Number | Publication Date |
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| CN108727161A CN108727161A (en) | 2018-11-02 |
| CN108727161B true CN108727161B (en) | 2021-09-07 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110668921A (en) * | 2019-08-27 | 2020-01-10 | 温州大学 | Method for preparing alcohol and phenol by aerobic hydroxylation reaction of boric acid derivative under condition of no photocatalyst |
| CN110591109B (en) * | 2019-09-29 | 2021-09-24 | 上海交通大学 | Carbon-carbon double bond bridged full-carbon skeleton two-dimensional conjugated organic framework material and preparation method thereof |
| CN111151296A (en) * | 2020-01-09 | 2020-05-15 | 临沂大学 | Magnetic material loaded rhodamine B catalyst, preparation method thereof and catalytic application thereof in phenol synthesis |
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