CN111100101A - Catalytic synthesis method of 3-benzofuranone compounds - Google Patents
Catalytic synthesis method of 3-benzofuranone compounds Download PDFInfo
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- CN111100101A CN111100101A CN201911336308.2A CN201911336308A CN111100101A CN 111100101 A CN111100101 A CN 111100101A CN 201911336308 A CN201911336308 A CN 201911336308A CN 111100101 A CN111100101 A CN 111100101A
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- ethynylphenol
- derivative
- benzofuranone
- dichloromethane
- synthesis method
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
- C07D307/86—Benzo [b] furans; Hydrogenated benzo [b] furans with an oxygen atom directly attached in position 7
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
- C07D307/82—Benzo [b] furans; Hydrogenated benzo [b] furans with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
- C07D307/83—Oxygen atoms
Abstract
The invention discloses a catalytic synthesis method of 3-benzofuranone compounds, which comprises the following steps: dissolving a 2-ethynylphenol derivative in a solvent dichloromethane at normal temperature and normal pressure, wherein the molar volume ratio of the 2-ethynylphenol derivative to the dichloromethane is 1:5mmol/mL, so as to obtain a dichloromethane solution of the 2-ethynylphenol derivative; adding mercury trifluoromethanesulfonate and pyridine-N-oxide into a dichloromethane solution of the 2-ethynylphenol derivative, wherein the molar use amounts of the mercury trifluoromethanesulfonate and the pyridine-N-oxide are 5% and 120% of the molar use amount of the 2-ethynylphenol derivative respectively; then, the mixture was stirred at room temperature for 1 hour to react and produce a 3-benzofuranone compound. The catalyst used in the catalytic synthesis method has the advantages of market price of the mercury trifluoromethanesulfonate lower than 30 yuan/gram, low cost, simple operation, short reaction time, mild reaction conditions, high reaction yield and high yield of 91.0-96.0%.
Description
Technical Field
The invention relates to a synthesis method of a compound, in particular to a catalytic synthesis method of a 3-benzofuranone compound.
Background
The 3-benzofuranone compound has good physiological activity, and the derivatives thereof have antibacterial, antiviral, and antioxidant effects. The 3-benzofuranone compound is also an important medical and chemical intermediate, and can be widely used for synthesizing medicines, pesticides, novel antioxidants, food additives and the like. Therefore, the development of a practical and efficient method for synthesizing the 3-benzofuranone compound has important practical significance and application value.
At present, a method for synthesizing a 3-benzofuranone compound by using o-chlorophenyl diketone and phenylboronic acid as raw materials, a rhodium complex and palladium acetate as catalysts, potassium phosphate as alkali and toluene as a solvent is reported in documents. The invention patent CN108752299A discloses a method for synthesizing 3-benzofuranone compounds by taking a phenol derivative and phenylpropanoic acid as raw materials and methanol as a solvent in the presence of a rhodium catalyst, a cobalt acetate hydrate and a sodium pivalate hydrate. The existing technology for synthesizing the 3-benzofuranone compounds has the following defects: 1) the cost of the catalyst is too high, and the price of the catalyst is very high whether the catalyst is a rhodium catalyst or a palladium catalyst; 2) the reaction conditions are complex; 3) the reaction time is too long.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a catalytic synthesis method of 3-benzofuranone compounds, which has the advantages of low cost, simple operation, short reaction time and high yield, aiming at the defects of the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows: a catalytic synthesis method of 3-benzofuranone compounds comprises the following steps: dissolving a 2-ethynylphenol derivative in a solvent dichloromethane at normal temperature and normal pressure, wherein the molar volume ratio of the 2-ethynylphenol derivative to the dichloromethane is 1:5mmol/mL, so as to obtain a dichloromethane solution of the 2-ethynylphenol derivative; adding mercury trifluoromethanesulfonate and pyridine-N-oxide into a dichloromethane solution of the 2-ethynylphenol derivative, wherein the molar use amounts of the mercury trifluoromethanesulfonate and the pyridine-N-oxide are 5% and 120% of the molar use amount of the 2-ethynylphenol derivative respectively; then, stirring for 1 hour at room temperature, and reacting to generate the 3-benzofuranone compound, wherein the reaction equation is as follows:
wherein, the 2-ethynylphenol derivative has a structure shown in a formula I, the 3-benzofuranone compound has a structure shown in a formula II, and in the formula I and the formula II, R1Are all selected from hydrogen atoms, methyl groups, methoxy groups, fluorine atoms, chlorine atoms or nitro groups.
The invention achieves the purposes of reducing the cost and shortening the reaction time by designing a brand new reaction process. Firstly, the selected raw material 2-ethynylphenol derivative can generate addition reaction with oxidant pyridine-N-oxide under the catalysis of cheap mercury triflate to generate enolpyrylium salt, and the generated enolpyrylium salt can generate S in moleculesNThe 2' nucleophilic substitution reaction generates the 3-benzofuranone compound, the reaction process is rapid, can be completed within 1 hour, and has mild reaction conditions and high reaction yield, and the yield can reach 91.0-96.0%.
Preferably, the stirring speed of the room-temperature stirring is 300-1000 r/min.
Compared with the prior art, the invention has the following advantages: the catalytic synthesis method of the 3-benzofuranone compound disclosed by the invention is used for synthesizing the 3-benzofuranone compound at normal temperature and normal pressure by using cheap mercury trifluoromethanesulfonate as a catalyst, pyridine-N-oxide as an oxidant and 2-ethynylphenol derivatives as raw materials in a dichloromethane solvent. Compared with the market price of a commonly used rhodium catalyst in the prior art which is higher than 1000 yuan/g, the catalyst mercury triflate used in the synthesis method has the market price of lower than 30 yuan/g, the cost is low, the operation is simple and easy, the reaction time is short, the reaction condition is mild, the reaction yield is high, and the yield can reach 91.0-96.0%.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of 3-benzofuranone prepared in example 1;
FIG. 2 is a NMR carbon spectrum of 3-benzofuranone prepared in example 1.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
Example 1: dissolving 0.2mmol of 2-ethynylphenol in 1mL of dichloromethane at normal temperature and normal pressure to obtain a dichloromethane solution of 2-ethynylphenol; then 0.01mmol of mercury trifluoromethanesulfonate and 0.24mmol of pyridine-N-oxide are added into the dichloromethane solution of 2-ethynylphenol; then, the mixture was stirred at a stirring rate of 600r/min at room temperature for 1 hour to react and produce 3-benzofuranone, and 24.7mg of 3-benzofuranone was obtained by silica gel column chromatography, with a yield of 92.2%. In example 1, the reaction formula for synthesizing 3-benzofuranone with 2-ethynylphenol as a raw material is as follows:
the NMR spectrum of 3-benzofuranone prepared in example 1 is shown in FIG. 1, and specific data are shown in FIG. 11H NMR(500MHz,CDCl3)δ7.68(dd,J＝7.7,1.4Hz,1H),7.62(ddd,J＝8.5,7.2,1.5Hz,1H),7.15(d,J＝8.4Hz,1H),7.12–7.07(m,1H),4.63(s,2H).
The NMR spectrum of 3-benzofuranone prepared in example 1 is shown in FIG. 2, and specific data are shown in the figure13C NMR(126MHz,CDCl3)δ199.92,174.03,137.90,124.11,122.02,121.19,113.69,74.71.
Example 2: dissolving 0.6mmol of 4-methyl-2-ethynylphenol in 3mL of dichloromethane at normal temperature and normal pressure to obtain a dichloromethane solution of 4-methyl-2-ethynylphenol; then 0.03mmol of mercury trifluoromethanesulfonate and 0.72mmol of pyridine-N-oxide are added into a dichloromethane solution of 4-methyl-2-ethynylphenol; then, the mixture was stirred at a stirring rate of 400r/min at room temperature for 1 hour to react and produce 5-methyl-3-benzofuranone, and 80.8mg of 5-methyl-3-benzofuranone was obtained by silica gel column chromatography, with a yield of 91.0%. In example 2, the reaction formula for synthesizing 5-methyl-3-benzofuranone using 4-methyl-2-ethynylphenol as a raw material is as follows:
example 3: dissolving 1.0mmol of 6-methoxy-2-ethynylphenol in 5mL of dichloromethane at normal temperature and pressure to obtain a dichloromethane solution of 6-methoxy-2-ethynylphenol; then 0.05mmol of mercury trifluoromethanesulfonate and 1.2mmol of pyridine-N-oxide are added into a dichloromethane solution of 6-methoxy-2-ethynylphenol; then stirring the mixture for 1 hour at room temperature at the stirring speed of 800r/min to react to generate 7-methoxy-3-benzofuranone, and obtaining 157.4mg of 7-methoxy-3-benzofuranone through silica gel column chromatography, wherein the yield is 96.0 percent. In example 3, the reaction formula for synthesizing 7-methoxy-3-benzofuranone using 6-methoxy-2-ethynylphenol as a raw material is as follows:
example 4: dissolving 2.0mmol of 4-fluoro-2-ethynylphenol in 10mL of dichloromethane at normal temperature and normal pressure to obtain a dichloromethane solution of 4-fluoro-2-ethynylphenol; then 0.1mmol of mercury trifluoromethanesulfonate and 2.4mmol of pyridine-N-oxide are added into a dichloromethane solution of 4-fluoro-2-ethynylphenol; then, the mixture was stirred at a stirring rate of 300r/min at room temperature for 1 hour to react and produce 5-fluoro-3-benzofuranone, which was chromatographed on a silica gel column to give 288.4mg of 5-fluoro-3-benzofuranone, with a yield of 94.9%. In example 4, the reaction formula for synthesizing 5-fluoro-3-benzofuranone using 4-fluoro-2-ethynylphenol as a raw material is:
example 5: dissolving 5.0mmol of 3-chloro-2-ethynylphenol in 25mL of dichloromethane at normal temperature and normal pressure to obtain a dichloromethane solution of 3-chloro-2-ethynylphenol; then 0.25mmol of mercury trifluoromethanesulfonate and 6.0mmol of pyridine-N-oxide are added into the dichloromethane solution of the 3-chloro-2-ethynylphenol; then, the mixture was stirred at a stirring rate of 1000r/min at room temperature for 1 hour to react and produce 4-chloro-3-benzofuranone, which was chromatographed on a silica gel column to give 775.5mg of 4-chloro-3-benzofuranone, with a yield of 92.0%. In example 5, the reaction formula for synthesizing 4-chloro-3-benzofuranone using 3-chloro-2-ethynylphenol as a raw material is as follows:
example 6: dissolving 10.0mmol of 4-nitro-2-ethynylphenol in 50mL of dichloromethane at normal temperature and normal pressure to obtain a dichloromethane solution of 4-nitro-2-ethynylphenol; then 0.5mmol of mercury trifluoromethanesulfonate and 12.0mmol of pyridine-N-oxide are added into the dichloromethane solution of 4-nitro-2-ethynylphenol; then, the mixture was stirred at a stirring rate of 700r/min at room temperature for 1 hour to react and produce 5-nitro-3-benzofuranone, which was chromatographed on a silica gel column to give 1683.5mg of 5-nitro-3-benzofuranone, with a yield of 94.0%. In example 6, the reaction formula for synthesizing 5-nitro-3-benzofuranone using 4-nitro-2-ethynylphenol as a raw material is:
Claims (2)
1. a catalytic synthesis method of 3-benzofuranone compounds is characterized by comprising the following steps: dissolving a 2-ethynylphenol derivative in a solvent dichloromethane at normal temperature and normal pressure, wherein the molar volume ratio of the 2-ethynylphenol derivative to the dichloromethane is 1:5mmol/mL, so as to obtain a dichloromethane solution of the 2-ethynylphenol derivative; adding mercury trifluoromethanesulfonate and pyridine-N-oxide into a dichloromethane solution of the 2-ethynylphenol derivative, wherein the molar use amounts of the mercury trifluoromethanesulfonate and the pyridine-N-oxide are 5% and 120% of the molar use amount of the 2-ethynylphenol derivative respectively; then, stirring for 1 hour at room temperature, and reacting to generate the 3-benzofuranone compound, wherein the reaction equation is as follows:
wherein, the 2-ethynylphenol derivative has a structure shown in a formula I, the 3-benzofuranone compound has a structure shown in a formula II, and in the formula I and the formula II, R1Are all selected from hydrogen atoms, methyl groups, methoxy groups, fluorine atoms, chlorine atoms or nitro groups.
2. The catalytic synthesis method of 3-benzofuranone compounds according to claim 1, wherein the stirring rate of stirring at room temperature is 300-1000 r/min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115626905A (en) * | 2022-10-20 | 2023-01-20 | 北京理工大学 | Method for synthesizing benzofuranone from o-alkynyl phenol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108752299A (en) * | 2018-07-18 | 2018-11-06 | 青岛科技大学 | A kind of preparation method of 3- benzofuranones |
| CN109734686A (en) * | 2019-01-07 | 2019-05-10 | 浙江万里学院 | A kind of 2- replaces the process for catalytic synthesis of benzofuran compounds |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108752299A (en) * | 2018-07-18 | 2018-11-06 | 青岛科技大学 | A kind of preparation method of 3- benzofuranones |
| CN109734686A (en) * | 2019-01-07 | 2019-05-10 | 浙江万里学院 | A kind of 2- replaces the process for catalytic synthesis of benzofuran compounds |
Non-Patent Citations (2)
| Title |
|---|
| CHAO SHU ET AL.: "Flexible and practical synthesis of 3-oxyindoles through gold-catalyzed intermolecular oxidation of o-ethynylanilines", 《CHEMICAL COMMUNICATIONS》 * |
| CHAO SHU ET AL.: "Practical, Modular, and General Synthesis of 3-Coumaranones through Gold-Catalyzed Intermolecular Alkyne Oxidation Strategy", 《CHEMISTRY AN ASIAN JOURNAL》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115626905A (en) * | 2022-10-20 | 2023-01-20 | 北京理工大学 | Method for synthesizing benzofuranone from o-alkynyl phenol |
| CN115626905B (en) * | 2022-10-20 | 2023-12-29 | 北京理工大学 | Method for synthesizing benzofuranone from o-alkynyl phenol |
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