CN111116362B - Preparation method of 2-fluoro methyl acrylate - Google Patents
Preparation method of 2-fluoro methyl acrylate Download PDFInfo
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- CN111116362B CN111116362B CN201911368079.2A CN201911368079A CN111116362B CN 111116362 B CN111116362 B CN 111116362B CN 201911368079 A CN201911368079 A CN 201911368079A CN 111116362 B CN111116362 B CN 111116362B
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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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- 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
- C07C67/317—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
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Abstract
A preparation method of 2-fluoro methyl acrylate comprises the steps of adding a solvent into a reaction kettle, dissolving methyl acrylate in the solvent, controlling the reaction temperature in the reaction kettle after emptying, introducing fluorine gas, raising the temperature in the reaction kettle, removing HF under an alkaline condition to obtain 2-fluoro methyl acrylate mother liquor and standing; raising the temperature of the 2-methyl fluoroacrylate mother liquor, and then carrying out thermal filtration on the 2-methyl fluoroacrylate mother liquor to obtain 2-methyl fluoroacrylate filtrate; recrystallizing the 2-methyl fluoroacrylate filtrate to obtain a crude product of 2-methyl fluoroacrylate; rectifying the crude product of the 2-fluoro methyl acrylate, and collecting fractions to obtain a pure product of the 2-fluoro methyl acrylate; the invention has low requirement on equipment, but can effectively inhibit F 2 The activity of the method reduces the generation of byproducts, not only can improve the yield and the purity of the product, but also can effectively remove reaction raw materials and solvents to obtain high-purity 2-fluoro methyl acrylate.
Description
Technical Field
The invention belongs to the field of pharmaceutical chemicals, and particularly relates to a preparation method of 2-fluoro methyl acrylate.
Background
The plastic optical fiber has the characteristics of large core diameter, soft texture, easy connection, light weight, low price and the like, and is more and more widely applied. Fluoro methyl acrylate is the first choice for the research of fluorine-containing plastic optical fiber, and because the production cost of perfluoro monomer is too high, 2-fluoro acrylate is often selected in the research, wherein the most common is 2-fluoro methyl acrylate.
Currently, the synthesis of methyl 2-fluoroacrylate has the following methods:
1) 2-methyl chloropropionate is used as a raw material, and the 2-methyl fluoroacrylate is prepared through fluoro (KF), bromination and elimination reactions. However, the raw materials are corrosive, flammable and highly toxic, and have high requirements on equipment and high production cost.
2) Methyl fluoropropionate is taken as a raw material, and in the presence of BPO, 2-fluoropropionate and a nitrogen-bromine brominating agent react to generate 2-bromine-2-fluoropropionate through bromination reaction, 2-bromine-2-fluoropropionate reacts with alkali (dimethylformamide), and HBr is removed to generate 2-fluoroacrylate; however, the raw materials are not easy to obtain, the production cost is high, and the method is not suitable for industrial production.
3) In a patent of the publication No. CN105001120B entitled "fluorination of acrylic ester and derivative", methyl acrylate was used as a raw material, and fluorine gas was dissolved in a hydrofluorocarbon solvent to carry out a reaction, but the fluorine gas was too active and, even if dissolved in the hydrofluorocarbon solvent, a large amount of by-products were produced during the reaction, resulting in a low yield and troublesome post-treatment.
4) The alpha-fluoroacetate is taken as a raw material, the alpha-fluoroacetate is added into a mixed solution of oxalic acid diester and sodium alkoxide for reaction, sodium salt is obtained and condensed with paraformaldehyde, and then the sodium salt is prepared by reduced pressure distillation. The reaction process is complicated and is not suitable for industrial production.
The above synthesis methods have high requirements on equipment, and have the disadvantages of complicated process, low yield, low purity, high cost and the like, so that the synthesis methods are not suitable for industrial production.
5) The 2-fluoro methyl acrylate is prepared by an electrochemical method, and the chemical formula is as follows:
CH 2 ＝CH-COOCH 3 +F 2 ＝CH 2 F-CHF-COOCH 3
the electrochemical method has high production cost, easily-occurred organic fracture and cyclization in the reaction process, more byproducts and low conversion rate, and is not suitable for industrial production
Disclosure of Invention
In view of the drawbacks and disadvantages of the prior art, it is an object of the present invention to provide a process for preparing methyl 2-fluoroacrylate using inhibition of F 2 The method for activity and reducing raw material concentration is characterized by that methyl acrylate is dissolved in solvent according to a certain proportion, then it is undergone the process of addition reaction with fluorine gas, then HF is removed by means of elimination reaction so as to finally prepare methyl 2-fluoroacrylate. The method can reduce the activity of fluorine gas, reduce the generation of byproducts, and improve the yield and the purity of the 2-fluoro methyl acrylate.
The invention aims to realize the following technical scheme, and provides a preparation method of 2-fluoro methyl acrylate, which comprises the following steps:
(1) adding a solvent into a reaction kettle, dissolving a raw material methyl acrylate in the solvent, purging a reaction device with nitrogen, evacuating, controlling the reaction temperature in the reaction kettle to be-30 to-10 ℃, introducing fluorine gas while stirring, performing an addition reaction, and then purging with nitrogen to discharge tail gas in the reaction kettle;
(2) raising the temperature in the reaction kettle to 30-40 ℃, and removing HF under an alkaline condition to obtain a 2-methyl fluoroacrylate mother liquor;
(3) standing the 2-methyl fluoroacrylate mother liquor at-10-0 ℃;
(4) heating the reaction kettle, raising the temperature of the 2-methyl fluoroacrylate mother liquor to 40-60 ℃, and then carrying out heat filtration on the 2-methyl fluoroacrylate mother liquor to obtain 2-methyl fluoroacrylate filtrate;
(5) recrystallizing the 2-methyl fluoroacrylate filtrate in a salt bath at 0 ℃ to obtain a crude product of 2-methyl fluoroacrylate;
(6) rectifying the crude product of the 2-methyl fluoroacrylate, and collecting fractions at the temperature of 90 ℃ to obtain a pure product of the 2-methyl fluoroacrylate.
Preferably, the solvent in step (1) is any one of acetonitrile, methanol, and dimethyl sulfoxide.
Preferably, the purity of the raw material methyl acrylate in the step (1) is not less than 99%.
Preferably, in the step (1), the molar ratio of the raw material methyl acrylate to the fluorine gas is 1:1 to 1: 2.
Preferably, the reaction temperature in the reaction kettle in the step (1) is-25 ℃ to-10 ℃.
Preferably, the concentration of the fluorine gas introduced in the step (1) is 10 to 20%.
Preferably, the HF elimination method in the step (2) under the alkaline condition is to add sodium hydroxide and sodium fluoride into the reaction kettle.
Preferably, the standing time in the step (3) is 12-24 h.
Preferably, in the step (4), the reaction kettle is heated, when the temperature of the 2-methyl fluoroacrylate mother liquor is raised to 50 ℃, the 2-methyl fluoroacrylate mother liquor is subjected to thermal filtration, and a 2-methyl fluoroacrylate filtrate is obtained.
The invention has the following advantages:
the invention has low requirement on equipment, but can effectively inhibit F 2 The activity of the method reduces the generation of byproducts, not only can improve the yield and the purity of the product, but also can effectively remove reaction raw materials and solvents to obtain high-purity 2-fluoro methyl acrylate.
The foregoing is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood, the present invention can be implemented according to the content of the description, and in order to make the above and other objects, features and advantages of the present invention more clearly understood, the following specific examples are given as follows:
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description will be given to the specific implementation, structure, characteristics and effects of the preparation method of methyl 2-fluoroacrylate according to the present invention with reference to the preferred examples.
The invention provides a preparation method of 2-fluoro methyl acrylate, which comprises the following steps:
(1) adding a solvent into a reaction kettle, wherein the solvent is any one of acetonitrile, methanol and dimethyl sulfoxide, dissolving raw material methyl acrylate with the purity of not less than 99 percent in the solvent, and using nitrogen gasPurging the reaction apparatus to perform substitution, controlling the reaction temperature in the reaction kettle to be-30 ℃ to-10 ℃, introducing fluorine gas with the concentration of 10-20% while stirring, controlling the molar ratio (1: 1-1: 2) of methyl acrylate and fluorine gas, performing addition reaction to prepare CH 2 F-CHFCOOCH 3 Purging the intermediate product with nitrogen to exhaust tail gas from the reactor;
(2) the temperature in the reaction kettle is increased to 30-40 ℃, and quantitative NaOH and NaF are added to lead CH 2 F-CHFCOOCH 3 Removing HF to obtain 2-methyl fluoroacrylate mother liquor, reacting the removed HF with NaF to produce NaHF 2 ；
(3) Then standing the 2-fluoro methyl acrylate mother liquor for 12 to 24 hours at the temperature of between 10 ℃ below zero and 0 ℃;
(4) heating the reaction kettle, raising the temperature of the 2-methyl fluoroacrylate mother liquor to 40-60 ℃, and then carrying out heat filtration on the 2-methyl fluoroacrylate mother liquor to obtain 2-methyl fluoroacrylate filtrate;
(5) recrystallizing the 2-methyl fluoroacrylate filtrate in a salt bath at 0 ℃ to obtain a crude 2-methyl fluoroacrylate product;
(6) rectifying the crude product of the 2-methyl fluoroacrylate, and collecting fractions at the temperature of 90 ℃ to obtain a pure product of the 2-methyl fluoroacrylate.
The chemical reaction formula is as follows:
NaF+HF＝NaHF 2
the alkali metal salt is sodium fluoride (analytically pure);
methyl acrylate may be abbreviated as MA, and for convenience of description hereinafter, MA is used in place of methyl acrylate in some places.
The experimental steps are as follows:
(1) adding 1mol of MA and 500ml to 1000ml of acetonitrile solvent into a reaction kettle. Purging the reaction device with nitrogen for replacement and evacuation, controlling the reaction temperature to be-30 to-10 ℃, and introducing fluorine gas with the concentration of 10 to 20 percent at the flow rate of 3 to 10g/h while stirring. After the reaction is finished, blowing and discharging tail gas in the reaction kettle by using nitrogen;
(2) raising the temperature in the reaction kettle to 30-40 ℃, adding NaF into the reaction kettle, and reacting for about 2-3 h at the temperature to obtain 2-methyl fluoroacrylate mother liquor;
(3) standing the 2-methyl fluoroacrylate mother liquor for 12-24 h at-10-0 ℃;
(4) heating the 2-methyl fluoroacrylate mother liquor, and carrying out hot filtration on the 2-methyl fluoroacrylate mother liquor when the temperature reaches 40-60 ℃ to obtain 2-methyl fluoroacrylate filtrate;
(5) recrystallizing the 2-methyl fluoroacrylate filtrate in a salt bath at 0 ℃ to obtain a crude 2-methyl fluoroacrylate;
(6) rectifying the crude product of the 2-methyl fluoroacrylate, collecting fractions at the temperature of 90 ℃ to obtain a pure product of the 2-methyl fluoroacrylate, and simultaneously characterizing by GC and infrared.
The test data are as follows:
| serial number | Temperature/. degree.C | MA/mol | F 2 /mol | F 2 Concentration of | Acetonitrile/ml | Yield of |
| 1 | -10 | 1 | 1 | 10％ | 500 | 33.7％ |
| 2 | -15 | 1 | 1 | 10％ | 600 | 46.9％ |
| 3 | -20 | 1 | 1 | 10％ | 700 | 58.4％ |
| 4 | -25 | 1 | 1 | 10％ | 800 | 69.8％ |
| 5 | -30 | 1 | 1 | 10％ | 900 | 44.5％ |
| 6 | -10 | 1 | 1.2 | 10％ | 500 | 30.2％ |
| 7 | -20 | 1 | 1.2 | 10％ | 700 | 45.2％ |
| 8 | -30 | 1 | 1.2 | 10％ | 900 | 36.7％ |
| 9 | -25 | 1 | 1 | 20％ | 800 | 62.6％ |
| 10 | -30 | 1 | 1 | 20％ | 900 | 41.8％ |
From the experimental results it follows:
1. when the temperature is-25 ℃ and the volume of acetonitrile as a solvent is 800ml, the concentration of fluorine gas is 10 percent, acetonitrile is used as the solvent, and the reaction is carried out by standing for 12 to 24 hours at low temperature, so that the high-yield and high-purity methyl 2-fluoroacrylate can be obtained.
2. In comparison with n (MA: F) 2 ) Is 2, when n (MA: f 2 ) When the molar ratio is 1, the amount of by-products produced is small and the yield is high.
3. The activity of 20% fluorine gas is higher than 10%, and a large amount of byproducts are generated in the reaction process, and the reaction yield of the fluorine gas is lower than 10% under the same conditions.
The first embodiment is as follows:
(1) adding 1mol of methyl acrylate and 600ml of acetonitrile solvent into a 1L reaction kettle with a stirrer, controlling the reaction temperature in the reaction kettle to be-15 ℃, vacuumizing for 20min for replacement, and introducing 10% F at the flow rate of 4g/h while stirring 2 Until F is introduced 2 Has a mass of 38g, and after the reaction is finished, N is used 2 Purging the reaction kettle, and generating 2, 3-difluoro methyl propionate in the reaction kettle;
(2) raising the temperature in the reaction kettle to 35 ℃, adding 20g of NaF into the reaction kettle, and reacting for 3 hours while stirring to obtain a 2-methyl fluoroacrylate mother liquor;
(3) standing the 2-methyl fluoroacrylate mother liquor for 12-24 h at-10-0 ℃;
(4) carrying out hot filtration on the 2-methyl fluoroacrylate mother liquor at 50 ℃ to obtain 2-methyl fluoroacrylate filtrate;
(5) recrystallizing the 2-methyl fluoroacrylate filtrate in a salt bath at 0 ℃, filtering and collecting a 2-methyl fluoroacrylate crude product;
(6) rectifying the 2-methyl fluoroacrylate crude product, and collecting fractions at the temperature of 90 ℃ to obtain a 2-methyl fluoroacrylate product. At this time, the purity was 98% by GC, and the calculated yield was 46.9%.
Example two:
(1) adding 1mol MA and 800ml acetonitrile solvent into a 1L reaction kettle with stirring, controlling the reaction temperature in the reaction kettle at-25 ℃, vacuumizing for 20min, and introducing 10% F at the flow rate of 4g/h while stirring 2 Until F is introduced 2 Has a mass of 38 g. After the reaction is finished, N is used 2 Purging;
(2) raising the temperature in the reaction kettle to 30 ℃, adding 30g of NaF into the reaction solution, and reacting for 3 hours while stirring to obtain a 2-methyl fluoroacrylate mother liquor;
(3) standing the 2-methyl fluoroacrylate mother liquor for 12-24 h at-10-0 ℃;
(4) carrying out hot filtration on the 2-methyl fluoroacrylate mother liquor at 50 ℃ to obtain 2-methyl fluoroacrylate filtrate;
(5) recrystallizing the 2-methyl fluoroacrylate filtrate in a salt bath at 0 ℃, filtering and collecting a 2-methyl fluoroacrylate crude product;
(6) rectifying the crude product of the 2-methyl fluoroacrylate, and collecting fractions at the temperature of 90 ℃ to obtain a product of the 2-methyl fluoroacrylate. At this time, the purity was 98.7% by GC analysis, and the calculated yield was 69.8%.
Example three:
(1) adding 1mol MA and 500ml methanol solvent into a 1L reaction kettle with a stirrer, controlling the reaction temperature in the reaction kettle at-10 deg.C, vacuumizing for 20min, and introducing 10% F at a flow rate of 4g/h while stirring 2 Until F is introduced 2 Has a mass of 45.6g, and after the reaction is finished, N is used 2 Purging;
(2) raising the temperature in the reaction kettle to 30 ℃, adding 30g of NaF into the reaction solution, and reacting for 3 hours while stirring to obtain a 2-methyl fluoroacrylate mother liquor;
(3) standing the 2-methyl fluoroacrylate mother liquor for 12-24 h at-10-0 ℃;
(4) carrying out hot filtration on the 2-methyl fluoroacrylate mother liquor at 50 ℃ to obtain 2-methyl fluoroacrylate filtrate;
(5) recrystallizing the 2-methyl fluoroacrylate filtrate in a salt bath at 0 ℃, filtering and collecting a 2-methyl fluoroacrylate crude product;
(6) rectifying the 2-methyl fluoroacrylate crude product, and collecting fractions at the temperature of 90 ℃ to obtain a 2-methyl fluoroacrylate product. At this time, the purity was 96.5% by GC analysis, and the calculated yield was 43.2%.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention.
Claims (7)
1. A preparation method of 2-fluoro methyl acrylate is characterized in that: the method comprises the following steps:
(1) adding a solvent into a reaction kettle, wherein the solvent is any one of acetonitrile, methanol and dimethyl sulfoxide, dissolving a raw material methyl acrylate into the solvent, purging a reaction device with nitrogen, evacuating, controlling the reaction temperature in the reaction kettle to be-30 to-10 ℃, introducing fluorine gas with the concentration of 10-20% while stirring, performing addition reaction, and then purging with nitrogen to discharge tail gas in the reaction kettle;
(2) raising the temperature in the reaction kettle to 30-40 ℃, and eliminating HF under an alkaline condition to obtain a 2-methyl fluoroacrylate mother liquor;
(3) standing the 2-methyl fluoroacrylate mother liquor at-10-0 ℃;
(4) heating the reaction kettle, raising the temperature of the 2-methyl fluoroacrylate mother liquor to 40-60 ℃, and then carrying out thermal filtration on the 2-methyl fluoroacrylate mother liquor to obtain 2-methyl fluoroacrylate filtrate;
(5) recrystallizing the 2-methyl fluoroacrylate filtrate in a salt bath at 0 ℃ to obtain a crude product of 2-methyl fluoroacrylate;
(6) rectifying the crude product of the 2-methyl fluoroacrylate, and collecting fractions at the temperature of 90 ℃ to obtain a pure product of the 2-methyl fluoroacrylate.
2. The process according to claim 1, wherein the reaction is carried out in the presence of a catalyst selected from the group consisting of: the purity of the raw material methyl acrylate in the step (1) is not less than 99%.
3. The process according to claim 1, wherein the reaction is carried out in the presence of a catalyst selected from the group consisting of: in the step (1), the molar ratio of the raw material methyl acrylate to the fluorine gas is 1: 1-1: 2.
4. The process according to claim 1, wherein the reaction is carried out in the presence of a catalyst selected from the group consisting of: the reaction temperature in the reaction kettle in the step (1) is-25 ℃ to-10 ℃.
5. The process according to claim 1, wherein the reaction is carried out in the presence of a catalyst selected from the group consisting of: the method for removing HF in the step (2) under the alkaline condition is to add sodium hydroxide and sodium fluoride into a reaction kettle.
6. The process according to claim 1, wherein the reaction is carried out in the presence of a catalyst selected from the group consisting of: the standing time in the step (3) is 12-24 h.
7. The process according to claim 1, wherein the reaction is carried out in the presence of a catalyst selected from the group consisting of: and (4) heating the reaction kettle in the step (4), raising the temperature of the 2-methyl fluoroacrylate mother liquor to 50 ℃, and then carrying out thermal filtration on the 2-methyl fluoroacrylate mother liquor to obtain 2-methyl fluoroacrylate filtrate.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103717567A (en) * | 2011-06-27 | 2014-04-09 | 瑞立普萨公司 | Fluorination of acrylate esters and derivatives |
| CN104718198A (en) * | 2012-10-09 | 2015-06-17 | 索尔维公司 | Preparation of purified fluorosubstituted organic carbonates |
| CN108033943A (en) * | 2017-12-19 | 2018-05-15 | 苏振东 | A kind of preparation method of fluorinated ethylene carbonate |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103717567A (en) * | 2011-06-27 | 2014-04-09 | 瑞立普萨公司 | Fluorination of acrylate esters and derivatives |
| CN104718198A (en) * | 2012-10-09 | 2015-06-17 | 索尔维公司 | Preparation of purified fluorosubstituted organic carbonates |
| CN108033943A (en) * | 2017-12-19 | 2018-05-15 | 苏振东 | A kind of preparation method of fluorinated ethylene carbonate |
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