CN111100101B - Catalytic synthesis method of 3-benzofuranone compounds - Google Patents
Catalytic synthesis method of 3-benzofuranone compounds Download PDFInfo
- Publication number
- CN111100101B CN111100101B CN201911336308.2A CN201911336308A CN111100101B CN 111100101 B CN111100101 B CN 111100101B CN 201911336308 A CN201911336308 A CN 201911336308A CN 111100101 B CN111100101 B CN 111100101B
- Authority
- CN
- China
- Prior art keywords
- ethynylphenol
- benzofuranone
- derivative
- dichloromethane
- synthesis method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Furan Compounds (AREA)
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; 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/g, 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 dione 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 using a phenol derivative and phenylpropanoic acid as raw materials and using 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 invention aims to solve the technical problem of providing 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; 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 the mixture for 1 hour at room temperature to react 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, R 1 Are all selected from hydrogen atoms, methyl groups, methoxy groups, fluorine atoms, chlorine atoms or nitro groups.
The invention achieves the purposes of reducing cost and shortening reaction time by designing a brand-new reaction process. Firstly, the selected raw material 2-ethynylphenol derivative can be used at low costThe mercury triflate is catalyzed by the mercury triflate to generate addition reaction with an oxidant pyridine-N-oxide to generate enolpyrylium salt, and the generated enolpyrylium salt can generate S in molecules N The 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 more than 1000 yuan/g of the commonly used rhodium catalyst in the prior art, the catalyst of the synthesis method has the market price of less than 30 yuan/g of mercury trifluoromethanesulfonate, low cost, simple operation, short reaction time, mild reaction conditions and high reaction yield, 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. 1 1 H NMR(500MHz,CDCl 3 )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 figure 13 C NMR(126MHz,CDCl 3 )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 normal 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 stirring the mixture for 1 hour at room temperature at the stirring speed of 300r/min to react to generate 5-fluoro-3-benzofuranone, and performing silica gel column chromatography to obtain 5-fluoro-3-benzofuranone 288.4mg, wherein the yield is 94.9%. In example 4, the reaction formula for synthesizing 5-fluoro-3-benzofuranone using 4-fluoro-2-ethynylphenol as a raw material is as follows:
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 stirring the mixture for 1 hour at room temperature at the stirring speed of 1000r/min to react to generate 4-chloro-3-benzofuranone, and obtaining 775.5mg of 4-chloro-3-benzofuranone through silica gel column chromatography, wherein the yield is 92.0 percent. 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, stirring the mixture for 1 hour at room temperature at the stirring speed of 700r/min to react to generate 5-nitro-3-benzofuranone, and performing silica gel column chromatography to obtain 5-nitro-3-benzofuranone 1683.5mg with the 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; 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, R 1 Are 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911336308.2A CN111100101B (en) | 2019-12-23 | 2019-12-23 | Catalytic synthesis method of 3-benzofuranone compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911336308.2A CN111100101B (en) | 2019-12-23 | 2019-12-23 | Catalytic synthesis method of 3-benzofuranone compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111100101A CN111100101A (en) | 2020-05-05 |
| CN111100101B true CN111100101B (en) | 2022-11-11 |
Family
ID=70422947
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911336308.2A Active CN111100101B (en) | 2019-12-23 | 2019-12-23 | Catalytic synthesis method of 3-benzofuranone compounds |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111100101B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115626905B (en) * | 2022-10-20 | 2023-12-29 | 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 |
-
2019
- 2019-12-23 CN CN201911336308.2A patent/CN111100101B/en active Active
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 |
|---|
| Flexible and practical synthesis of 3-oxyindoles through gold-catalyzed intermolecular oxidation of o-ethynylanilines;Chao Shu et al.;《Chemical communications》;20140611;第50卷(第63期);第8689-8692页 * |
| Practical, Modular, and General Synthesis of 3-Coumaranones through Gold-Catalyzed Intermolecular Alkyne Oxidation Strategy;Chao Shu et al.;《Chemistry An Asian Journal》;20141006;第10卷(第1期);第91-95页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111100101A (en) | 2020-05-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112979497A (en) | Method for preparing 2-iodoaryl ether based on o-haloiodobenzene without catalyst | |
| CN111100101B (en) | Catalytic synthesis method of 3-benzofuranone compounds | |
| CN109734686B (en) | Catalytic synthesis method of 2-substituted benzofuran compound | |
| CN107353176B (en) | Method for catalytically converting cyano into deuterated methyl, aromatic deuterated methyl compound prepared by method and application of aromatic deuterated methyl compound | |
| CN109651228B (en) | Catalytic synthesis method of N-p-toluenesulfonyl-2-substituted indole compound | |
| CN115920973B (en) | Preparation method of full deuterated methanol | |
| CN107915653B (en) | Method for preparing amide by catalyzing ester and amine to react | |
| CN109336753B (en) | Synthetic method of alpha-benzyl substituted 1, 3-diketone compound | |
| CN111153923B (en) | Alkynone derivative and preparation method and application thereof | |
| CN110590728B (en) | Synthesis method of polysubstituted 4-phenyl chroman compounds | |
| CN113527308B (en) | Method for catalytic synthesis of 7-deazapurine compounds by using iron complex | |
| CN111533717B (en) | Method for synthesizing 3-arylmethylbenzo [ b ] furan compound under blue light excitation | |
| CN110627626B (en) | Preparation method of propargyl acetone compound | |
| CN111732613A (en) | Ferric iron complex containing meta-carborane ligand and preparation method and application thereof | |
| CN116023324B (en) | Deuteration method of pyridine and derivative thereof | |
| LU505773B1 (en) | A base catalyzed method for preparing substituted propargyl alcohol from paraformaldehyde and alkyne | |
| CN110590679A (en) | Method for catalytic synthesis of 5-substituted barbituric acid derivative by rare earth chloride | |
| CN117050010B (en) | Synthesis method of 2,2' -biquinoline and derivatives thereof | |
| CN118619876B (en) | Preparation method of 1-ethyl-3, 3-dimethyl-2- (methylene-d 2) -5-nitroindoline | |
| CN114315542B (en) | Preparation method of dibenzoylmethane | |
| CN118047735A (en) | Preparation method of pramoxine | |
| CN113121454B (en) | Method for preparing barbituric acid alkylation derivative by using ferrous complex | |
| CN111620839B (en) | Preparation method for synthesizing phenyl pyrrolidine derivative in series under metal catalysis | |
| CN110627718B (en) | Synthesis method of (E) -beta-monofluoroalkyl-beta, gamma-unsaturated amide | |
| CN111116466B (en) | Catalytic synthesis method of polysubstituted quinoline derivative |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |