CN108911979B - Preparation method of 3-fluoropropionate - Google Patents
Preparation method of 3-fluoropropionate Download PDFInfo
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- CN108911979B CN108911979B CN201810891949.3A CN201810891949A CN108911979B CN 108911979 B CN108911979 B CN 108911979B CN 201810891949 A CN201810891949 A CN 201810891949A CN 108911979 B CN108911979 B CN 108911979B
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- fluoropropionate
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- 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
- C07C67/307—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 halogen; by substitution of halogen atoms by other halogen atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
Abstract
The invention relates to a preparation method of 3-fluoropropionate, under the action of a fluorination catalyst prepared from titanium oxide, chromium oxide, an organic auxiliary agent and graphite, acrylic ester and hydrofluoric acid are subjected to hydrofluorination reaction to prepare the 3-fluoropropionate, the conversion rate of the acrylic ester is more than 88 percent, the selectivity of the 3-fluoroacrylic acid is up to 100 percent, and a reaction system is not sensitive to water and is used for industrial production.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a preparation method of 3-fluoropropionate.
Background
The 3-fluoropropionate includes 3-fluoropropionate methyl ester, 3-fluoropropionate ethyl ester and the like, is a fluorine-containing intermediate with relatively high application, and can be used as an intermediate for medicines and pesticides, and can also be used as a solvent of a battery electrolyte and the like.
The prior art mainly comprises the following preparation methods of 3-fluoropropionate:
mitsubishi chemical in JP2003267931 reports that ethyl 3-fluoropropionate can be obtained by fluorination reaction of ethyl propionate with fluorine gas diluted with an inert gas, but the selectivity and conversion are poor.
Hamman et al (tetrahedron letters (1983), 24(1), 57-60) reported that ethyl 2-aminopropionate reacted with HF-pyridine reagent in the presence of sodium nitrite to obtain ethyl 3-fluoropropionate and further to produce ethyl 2-fluoropropionate, and the molar ratio of HF to pyridine determined the selectivity of ethyl 3-fluoropropionate to ethyl 2-fluoropropionate.
Chuvalkin et al reported (Zhurnal organic heskoiKhimi (1993), 29(9), 1746-53) a chlorofluorination reaction in the HF-hexachloromelamine system, 2, 3, 3-tetrafluoropropyl 3-bromopropionate (CH2BrCH2CO2CH2(CF2)2H) an oxidative fluorination reaction in the HF-hexachloromelamine system to give 2, 2, 3, 3-tetrafluoropropyl 3-fluoropropionate (CH2FCH2CO2CH2(CF2)2H) in about 40% yield.
Chinese patent CN103159626A discloses a preparation method of 3-fluoropropionate, which is a preparation method of 3-fluoropropionate, in an anhydrous environment, under the existence of a solvent, acrylic acid alkyl ester reacts with anhydrous hydrofluoric acid to prepare the corresponding 3-fluoropropionate, but the moisture content in the hydrofluoric acid is required to be less than 200ppm, and the anhydrous condition is extremely strict, so that the industrial production is not facilitated.
Therefore, the preparation of 3-fluoropropionate is more challenging, and the industrial application of the addition reaction of using acrylic acid as the raw material to prepare 3-fluoropropionate is still to be improved.
Disclosure of Invention
The invention aims to provide a preparation method of 3-fluoropropionate, which takes acrylic ester as a raw material to react with anhydrous hydrofluoric acid to generate the corresponding 3-fluoropropionate.
The technical scheme adopted by the invention is as follows: under the action of a fluorination catalyst, carrying out hydrofluorination reaction on acrylate and hydrofluoric acid to prepare 3-fluoropropionate, wherein the catalyst is prepared from titanium oxide, chromium oxide, an organic auxiliary agent and graphite; the molar ratio of the hydrofluoric acid to the alkyl acrylate is 1-60: 1, and the preferable ratio is 5-50: 1; the reaction temperature is preferably 20-100 ℃, and more preferably 30-85 ℃; the reaction time is preferably 1 to 12 hours, and more preferably 3 to 10 hours.
The mass ratio of the catalyst to the alkyl acrylate is preferably 0.05-0.5: 1.
The raw material used by the invention is alkyl acrylate, the molecular formula is CH2 ═ CHCOOR, and R ═ C1-C8 alkyl. From the viewpoint of availability, the alkyl acrylate is preferably methyl acrylate, ethyl acrylate or butyl acrylate.
The reaction of the invention needs to be carried out in the presence of a solvent, and the solvent is preferably one or a combination of more than two of dichloromethane, 1, 2-dichloroethane, chloroform, acetone, pyridine, triethylamine, tetrahydrofuran or DMF.
Further, the hydrofluoric acid is not particularly limited as long as it is used as a reaction solvent as well as a fluorination reagent, and is commercially available, and the moisture is not particularly limited.
Further, the preparation method of the catalyst comprises the specific steps of uniformly mixing titanium oxide, chromium oxide, an organic auxiliary agent and graphite, tabletting and forming to obtain a catalyst precursor, and fluorinating the catalyst precursor to obtain the fluorination catalyst; the fluorination is carried out under the mixed gas of inert gas and HF, and the fluorination temperature is 300-400 ℃. Preferably, the fluorination temperature is 300-350 ℃.
The mass ratio of the chromium oxide to the titanium oxide to the organic matter II to the graphite is 81-90: 8-12: 0.5-2: 1.5-5.
Further, the organic substance II is one or more selected from amphoteric cellulose, polyoxyethylene diamine, quaternary ammonium type ammonium iodide, polyethylene glycol, and polyvinylpyrrolidone (PVP). Preferably, the amphoteric cellulose is quaternary ammonium carboxymethyl cellulose, and the quaternary ammonium carboxymethyl cellulose is one or more selected from the group consisting of glycidyl trioctyl ammonium chloride-carboxymethyl cellulose (EPTO-CMC), glycidyl dimethyltetradecyl ammonium chloride-carboxymethyl cellulose (MEQ-CMC), and trimethyl lignin ammonium chloride-carboxymethyl cellulose (TLQAS-CMC).
Further, the quaternary ammonium carboxymethyl cellulose is EPTO-CMC. But not limited to, the quaternary ammonium type carboxymethyl cellulose listed above, and other amphoteric celluloses commonly used in the art to achieve the same effect may also be used in the present invention.
Further, the quaternary ammonium type ammonium iodide is N- [3- (p-perfluorononenoxybenzoyl) propyl ] -N, N, N-trimethyl ammonium iodide. But are not limited to the N- [3- (p-perfluorononenoxybenzoyl) propyl ] -N, N, N-trimethyl ammonium iodide listed above, other quaternary ammonium type ammonium iodides commonly used in the art to achieve the same effect may also be used in the present invention.
The invention has the beneficial effects that: under the action of a fluorination catalyst prepared from titanium oxide, chromium oxide, an organic assistant and graphite, acrylic ester and hydrofluoric acid are subjected to hydrofluorination reaction to prepare 3-fluoropropionate, the conversion rate of the acrylic ester is over 88 percent, the selectivity of the 3-fluoroacrylic acid is up to 100 percent, and a reaction system is not sensitive to water and is used for industrial production.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
[ example 1 ]
I. Preparation of the catalyst
Mixing, tabletting and molding 92% of amorphous chromium oxide powder, 5% of nano titanium oxide, 1% of EPTO-CMC and 2% of graphite to obtain a fluorination catalyst precursor; then the fluorination catalyst precursor is put into a reactor, and the mixed gas of nitrogen and HF is introduced for fluorination at 350 ℃ to prepare the fluorination catalyst.
II. And (2) vacuumizing the pressure reaction container, adding 9.5g of methyl acrylate, 65g of commercially available hydrofluoric acid and 30mL of dichloromethane, adding 0.95g of the catalyst prepared in the step I, heating to about 80 ℃, keeping the temperature for reacting for about 5 hours, wherein the reaction pressure is the pressure naturally generated by the reaction, cooling to room temperature after the reaction is finished, slowly blowing out excessive hydrofluoric acid by using nitrogen, and removing residual hydrofluoric acid in the reaction liquid by adopting a method of reacting with silica gel. The reaction product is qualitatively and quantitatively detected by GC-MS and 19F-NMR, the selectivity of the reaction product 3-fluoropropionate methyl ester is 100 percent, and the conversion rate of methyl acrylate is 88 percent.
[ example 2 ]
I. Preparation of the catalyst
Mixing 85% of amorphous chromium oxide powder, 10% of nano titanium oxide, 2% of polyoxyethylene diamine and 3% of graphite, tabletting and molding to obtain a fluorination catalyst precursor; then the fluorination catalyst precursor is put into a reactor, and the mixed gas of nitrogen and HF is introduced for fluorination at 350 ℃ to prepare the fluorination catalyst.
II. Preparation of 3-fluoropropionate
And (2) vacuumizing the pressure reaction container, adding 9.5g of methyl acrylate, 65g of commercially available hydrofluoric acid and 30mL of dichloromethane, adding 0.95g of the catalyst prepared in the step I, heating to about 80 ℃, keeping the temperature for reacting for about 5 hours, wherein the reaction pressure is the pressure naturally generated by the reaction, cooling to room temperature after the reaction is finished, slowly blowing out excessive hydrofluoric acid by using nitrogen, and removing residual hydrofluoric acid in the reaction liquid by adopting a method of reacting with silica gel. The reaction product is qualitatively and quantitatively detected by GC-MS and 19F-NMR, the selectivity of the reaction product 3-fluoropropionate methyl ester is 100 percent, and the conversion rate of methyl acrylate is 92 percent.
[ example 3 ]
I. Preparation of the catalyst
Mixing 81% of amorphous chromium oxide powder, 13% of nano titanium oxide, 1% of quaternary ammonium type ammonium iodide and 5% of graphite, tabletting and molding to obtain a fluorination catalyst precursor; then the fluorination catalyst precursor is put into a reactor, and the mixed gas of nitrogen and HF is introduced for fluorination at 350 ℃ to prepare the fluorination catalyst.
II. Preparation of 3-fluoropropionate
And (2) vacuumizing the pressure reaction container, adding 9.5g of methyl acrylate, 65g of commercially available hydrofluoric acid and 30mL of dichloromethane, adding 0.95g of the catalyst prepared in the step I, heating to about 80 ℃, keeping the temperature for reacting for about 5 hours, wherein the reaction pressure is the pressure naturally generated by the reaction, cooling to room temperature after the reaction is finished, slowly blowing out excessive hydrofluoric acid by using nitrogen, and removing residual hydrofluoric acid in the reaction liquid by adopting a method of reacting with silica gel. The reaction product is qualitatively and quantitatively detected by GC-MS and 19F-NMR, the selectivity of the reaction product 3-fluoropropionate methyl ester is 100 percent, and the conversion rate of methyl acrylate is 90 percent.
Comparative example 1
Vacuumizing a pressure reaction container, adding 9.75g of methyl acrylate, 50g of commercially available hydrofluoric acid, 0.95g of aluminum fluoride and 30mL of dichloromethane, heating to 80 ℃, keeping the temperature for reaction for 7h, cooling to room temperature after the reaction is finished, slowly blowing out excessive hydrofluoric acid by using nitrogen, and removing residual hydrofluoric acid in the reaction liquid by adopting a method of reacting with silica gel. The reaction product is qualitatively and quantitatively detected by GC-MS and 19F-NMR, the selectivity of the reaction product 3-fluoropropionate methyl ester is 88 percent, and the conversion rate of methyl acrylate is 24 percent.
Comparative example 2
Vacuumizing a pressure reaction container, adding 9.75g of methyl acrylate, 50g of commercially available hydrofluoric acid, 0.95g of zinc fluoride and 30mL of dichloromethane, heating to 80 ℃, keeping the temperature for reaction for 7h, cooling to room temperature after the reaction is finished, slowly blowing out excessive hydrofluoric acid by using nitrogen, and removing residual hydrofluoric acid in the reaction liquid by adopting a method of reacting with silica gel. The reaction product is qualitatively and quantitatively detected by GC-MS and 19F-NMR, the selectivity of the reaction product 3-fluoropropionate methyl ester is 76 percent, and the conversion rate of methyl acrylate is 33 percent.
The foregoing description has disclosed fully preferred embodiments of the present invention. It should be noted that those skilled in the art can make modifications to the embodiments of the present invention without departing from the scope of the appended claims. Accordingly, the scope of the appended claims is not to be limited to the specific embodiments described above.
Claims (8)
1. A preparation method of 3-fluoropropionate comprises the following steps: reacting acrylic ester with hydrogen under the action of fluorination catalyst
Hydrofluoric acid is subjected to hydrofluorination reaction to prepare 3-fluoropropionate, and the catalyst is prepared from titanium oxide, chromium oxide, an organic auxiliary agent and graphite; the molar ratio of the hydrofluoric acid to the alkyl acrylate is 1-60: 1; the reaction temperature is 20-100 ℃; the reaction time is 1-12 h; the preparation method of the catalyst comprises the specific steps of uniformly mixing titanium oxide, chromium oxide, an organic auxiliary agent and graphite, tabletting and forming to obtain a catalyst precursor, and fluorinating the catalyst precursor to obtain the fluorination catalyst; the fluorination is carried out under the mixed gas of inert gas and HF, and the fluorination temperature is 300-400 ℃; the mass ratio of the chromium oxide to the titanium oxide to the organic auxiliary agent to the graphite is 81-90: 8-12: 0.5-2: 1.5-5;
the organic auxiliary agent is selected from one or more of amphoteric cellulose, polyoxyethylene diamine, quaternary ammonium type ammonium iodide, polyethylene glycol and polyvinylpyrrolidone (PVP); the acrylate is alkyl acrylate, the molecular formula is CH2 ═ CHCOOR, R ═ C1-C8 alkyl, and the corresponding 3-fluoropropionate is prepared by the reaction of the alkyl acrylate and hydrofluoric acid.
2. A process for the preparation of 3-fluoropropionate ester according to claim 1, wherein: the alkyl acrylate is methyl acrylate, ethyl acrylate or butyl acrylate.
3. A process for the preparation of 3-fluoropropionate ester according to claim 1, wherein: the solvent is one or more selected from dichloromethane, 1, 2-dichloroethane, chloroform, acetone, pyridine, triethylamine, tetrahydrofuran and DMF.
4. A process for the preparation of 3-fluoropropionate ester according to claim 1, wherein: the fluorination temperature is 300-350 ℃.
5. A process for the preparation of 3-fluoropropionate ester according to claim 1, wherein: the organic auxiliary agent is one or more selected from amphoteric cellulose, polyoxyethylene diamine, quaternary ammonium type ammonium iodide, polyethylene glycol and polyvinylpyrrolidone (PVP).
6. A process for the preparation of 3-fluoropropionate ester according to claim 5, wherein: the amphoteric cellulose is quaternary ammonium carboxymethyl cellulose, and the quaternary ammonium carboxymethyl cellulose is selected from one or more of epoxypropyl trioctyl ammonium chloride-carboxymethyl cellulose (EPTO-CMC), epoxypropyl dimethyl tetradecyl ammonium chloride-carboxymethyl cellulose (MEQ-CMC), and trimethyl lignin ammonium chloride-carboxymethyl cellulose (TLQAS-CMC).
7. A process for the preparation of 3-fluoropropionate ester according to claim 6, wherein: the quaternary ammonium carboxymethyl cellulose is EPTO-CMC.
8. A process for the preparation of 3-fluoropropionate ester according to claim 6, wherein: the quaternary ammonium type ammonium iodide is N- [3- (p-perfluorononenoxybenzoyl) propyl ] -N, N, N-trimethyl ammonium iodide.
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| CN109020802A (en) * | 2018-08-07 | 2018-12-18 | 陈鑫宁 | A kind of preparation method of 3- fluorine propionic acid |
| CN111253255A (en) * | 2019-11-13 | 2020-06-09 | 浙江理工大学 | Preparation method of 3-bromopropionate compound |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01249728A (en) * | 1988-03-31 | 1989-10-05 | Tokuyama Soda Co Ltd | Fluorination of organic compound |
| JPH04139138A (en) * | 1990-09-27 | 1992-05-13 | Sagami Chem Res Center | Production of halofluoro compound |
| EP0509544A2 (en) * | 1991-04-18 | 1992-10-21 | Idemitsu Kosan Company Limited | Process for producing triazine compounds |
| CN1091651C (en) * | 1996-04-17 | 2002-10-02 | 奥西蒙特公司 | Catalyst for fluorination of halogenated hydrocarbon |
| CN103159626A (en) * | 2011-12-14 | 2013-06-19 | 中化蓝天集团有限公司 | Method for preparing 3- fluoropropionate |
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- 2018-08-07 CN CN201810891949.3A patent/CN108911979B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01249728A (en) * | 1988-03-31 | 1989-10-05 | Tokuyama Soda Co Ltd | Fluorination of organic compound |
| JPH04139138A (en) * | 1990-09-27 | 1992-05-13 | Sagami Chem Res Center | Production of halofluoro compound |
| EP0509544A2 (en) * | 1991-04-18 | 1992-10-21 | Idemitsu Kosan Company Limited | Process for producing triazine compounds |
| CN1091651C (en) * | 1996-04-17 | 2002-10-02 | 奥西蒙特公司 | Catalyst for fluorination of halogenated hydrocarbon |
| CN103159626A (en) * | 2011-12-14 | 2013-06-19 | 中化蓝天集团有限公司 | Method for preparing 3- fluoropropionate |
Non-Patent Citations (1)
| Title |
|---|
| 两性纤维素合成与应用的研究进展;何爱见等;《纤维素科学与技术》;20140331;第22卷(第1期);第70-78页 * |
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