Preparation method of perfluorobutylsulfonyl-containing acrylate

Abstract

The invention discloses a preparation method of perfluorobutyl sulfonyl-containing acrylate, which comprises the following steps: under normal pressure, heating perfluorobutyl sulfonyl fluoride, acetonitrile, ethylene glycol and acrylic acid to react in the presence of a solvent and alkali, and carrying out four-step reaction to obtain the perfluorobutyl sulfonyl-containing acrylate. According to the method, industrial products, namely the perfluorobutanesulfonyl fluoride, the acetonitrile, the ethylene glycol and the acrylic acid, are selected as raw materials, the method has the advantages of simplicity in operation, cheap and easily available reagents, environment friendliness and the like, the total yield of the five-step reaction can reach 70%, and industrial production is facilitated.

Description

Technical Field

[0001] The invention belongs to the technical field of fine chemical synthesis, and particularly relates to a preparation method of perfluorobutylsulfonyl acrylate. Background Art

[0002] Perfluorobutylsulfonyl acrylate is a new type of acrylate compound, and there are few research reports related to it.

[0003] According to our research, it has the following advantages compared to other acrylates:

[0004] 1. Can be used as a high-quality surfactant precursor;

[0005] 2. It contains both hydrophobic perfluoroalkyl groups and hydrophilic carbonyl groups, and is a natural surfactant with potential application value;

[0006] 3. Contains carbon-carbon double bonds and can be used as polymerization monomers to participate in polymerization reactions to prepare polymer materials.

[0007] Given the unique advantages of perfluorobutylsulfonyl acrylate, it is urgent to develop a method for synthesizing perfluorobutylsulfonyl acrylate. Summary of the Invention

[0008] The object of the present invention is to provide a method for preparing perfluorobutylsulfonyl acrylate in view of the above-mentioned problems.

[0009] The present invention provides a method for preparing a perfluorobutylsulfonyl acrylate, comprising the following steps:

[0010] Under normal pressure, perfluorobutylsulfonyl fluoride and acetonitrile undergo acylation reaction to generate intermediate A, which undergoes alkaline hydrolysis and acidification to generate intermediate B, which undergoes esterification reaction with ethylene glycol to generate intermediate C, which undergoes esterification reaction with acrylic acid to generate a perfluorobutylsulfonyl acrylate product, 2-(2-((perfluorobutyl)sulfonyl)acetoxy)ethyl acrylate. The reaction equation is shown in Formula 1:

[0011]

[0012] Preferably, the molar ratio of perfluorobutylsulfonyl fluoride to acetonitrile in Formula 1A is not higher than 1:1, more preferably 1:1.1-2; the usage ratio of ethyl acetoacetate to solvent is 1 mmol:1-4 mL, more preferably 1 mmol:1-1.5 mL.

[0013] Preferably, the solvent in Formula 1A is ethyl acetate, dichloromethane, chloroform, chlorobenzene, toluene, benzene, tetrahydrofuran or 1,2-dichloroethane.

[0014] Preferably, the base in Formula 1A is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, n-butyl lithium, sodium hydride, sodium amide or cesium carbonate, and the molar ratio of the base to perfluorobutylsulfonyl fluoride is not higher than 1:0.1, more preferably 1:0.1 to 2.

[0015] Preferably, the atmosphere of the heating reaction in Formula 1A is a protective atmosphere or an air atmosphere, and more preferably an air atmosphere.

[0016] Preferably, the heating reaction temperature in Formula 1A is 40-150° C.; and the heating reaction time is not less than 8 hours.

[0017] Preferably, after the reaction in Formula 1A is completed, the solvent must be removed by distillation under reduced pressure, and then the intermediate A can be obtained by extraction with methyl tert-butyl ether, concentration, and column chromatography.

[0018] Preferably, the ratio of the intermediate A to the solvent in Formula 1B is 1 mmol:1-3 mL, more preferably 1 mmol:1-1.5 mL.

[0019] Preferably, the solvent in Formula 1B is ethyl acetate, acetonitrile, dichloromethane, chloroform, chlorobenzene, toluene, benzene, tetrahydrofuran or 1,2-dichloroethane.

[0020] Preferably, the base in Formula 1B is sodium hydroxide or potassium hydroxide, and the molar ratio of the base to the intermediate A is not higher than 1:1, more preferably 1:1 to 2;

[0021] Preferably, the atmosphere of the heating reaction in Formula 1B is a protective atmosphere or an air atmosphere, and more preferably an air atmosphere.

[0022] Preferably, the heating reaction temperature in Formula 1B is 40-150° C.; and the heating reaction time is not less than 8 hours.

[0023] Preferably, the acid in Formula 1B is dilute sulfuric acid, and its concentration is 5% to 60%, more preferably 10% to 60%.

[0024] Preferably, after the reaction in Formula 1B is completed, the solvent must be removed by distillation under reduced pressure, and then the intermediate B can be obtained by extraction with methyl tert-butyl ether, concentration, and column chromatography.

[0025] Preferably, the molar ratio of the intermediate B to ethylene glycol in Formula 1C is not higher than 1:1, more preferably 1:1.1-2; the amount ratio of the intermediate B to the solvent is 1 mmol:1-4 mL, more preferably 1 mmol:1-1.5 mL.

[0026] Preferably, the solvent in Formula 1C is ethyl acetate, dichloromethane, chloroform, chlorobenzene, toluene, benzene, tetrahydrofuran or 1,2-dichloroethane.

[0027] Preferably, the acid in Formula 1C is concentrated sulfuric acid, methanesulfonic acid or trifluoromethanesulfonic acid.

[0028] Preferably, the atmosphere of the heating reaction in Formula 1C is a protective atmosphere or an air atmosphere, and more preferably an air atmosphere.

[0029] Preferably, the heating reaction temperature in Formula 1C is 40-150° C.; and the heating reaction time is not less than 8 hours.

[0030] Preferably, after the reaction in Formula 1C is completed, the solvent must be removed by distillation under reduced pressure, and then the intermediate C can be obtained by extraction with methyl tert-butyl ether, concentration, and column chromatography.

[0031] Preferably, the molar ratio of the intermediate C to acrylic acid in Formula 1D is not higher than 1:1, more preferably 1:1.1-2; the usage ratio of the intermediate C to the solvent is 1 mmol:1-4 mL, more preferably 1 mmol:1-1.5 mL.

[0032] Preferably, the solvent in Formula 1D is ethyl acetate, dichloromethane, chloroform, chlorobenzene, toluene, benzene, tetrahydrofuran or 1,2-dichloroethane.

[0033] Preferably, the acid in Formula 1D is concentrated sulfuric acid, methanesulfonic acid or trifluoromethanesulfonic acid.

[0034] Preferably, the atmosphere of the heating reaction in Formula 1D is a protective atmosphere or an air atmosphere, and more preferably an air atmosphere.

[0035] Preferably, the heating reaction temperature in Formula 1D is 40-150° C.; and the heating reaction time is not less than 8 hours.

[0036] Preferably, after the reaction described in Formula 1D is completed, the solvent must be removed by distillation under reduced pressure, and then the product containing perfluorobutylsulfonyl acrylate, 2-(2-((perfluorobutyl)sulfonyl)acetoxy)ethyl acrylate, can be obtained by extraction with methyl tert-butyl ether, concentration, and column chromatography.

[0037] Compared with the prior art, the present invention has the following beneficial effects:

[0038] The present invention uses industrially available raw materials, perfluorobutylsulfonyl fluoride, acetonitrile, acrylic acid, and ethylene glycol, and produces perfluorobutylsulfonyl acrylate through a five-step reaction process: acylation, hydrolysis, acidification, and two esterification steps. This process requires no catalyst, utilizes readily available, inexpensive raw materials, is simple to operate, and is environmentally friendly, making it suitable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 The liquid chromatography chromatogram of ethyl 2-(2-((perfluorobutyl)sulfonyl)acetoxy)acrylate in one example is shown. DETAILED DESCRIPTION

[0040] Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiments are only used to illustrate the present invention and are not used in limiting the scope of the present invention.In addition, should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall equally within the scope limited by the appended claims of the application.

[0041] Example 1:

[0042] A method for preparing perfluorobutylsulfonyl acrylate comprises the following steps:

[0043] S1. Under normal pressure, perfluorobutanesulfonyl fluoride and acetonitrile undergo acylation reaction to produce intermediate A, wherein the molar ratio of perfluorobutanesulfonyl fluoride to acetonitrile is 1 mmol:1 mL, the solvent is ethyl acetate, the base is sodium hydroxide, the molar ratio of the base to perfluorobutanesulfonyl fluoride is 1:0.1, the atmosphere of the heating reaction is air atmosphere, the heating reaction temperature is 100°C; the heating reaction time is 8 hours, and after the reaction is completed, the solvent must be removed by reduced pressure distillation, and then the intermediate A can be obtained after extraction with methyl tert-butyl ether, concentration, and column chromatography;

[0044] S2. Intermediate A undergoes alkaline hydrolysis and acidification to obtain intermediate B. The ratio of intermediate A to solvent is 1 mmol:1. The solvent is ethyl acetate. The base is sodium hydroxide. The molar ratio of base to intermediate A is 1:1. The atmosphere of the heating reaction is air atmosphere. The heating reaction temperature is 100°C. The heating reaction time is 8 hours. The acid is dilute sulfuric acid with a concentration of 60%. After the reaction, the solvent must be removed by reduced pressure distillation. Then, intermediate B is obtained after extraction with methyl tert-butyl ether, concentration, and column chromatography.

[0045] S3. Intermediate B undergoes esterification reaction with ethylene glycol to obtain intermediate C, wherein the molar ratio of intermediate B to ethylene glycol is 1:2; the amount ratio of intermediate B to solvent is 1 mmol:1 mL, the solvent is ethyl acetate, the acid is concentrated sulfuric acid, the atmosphere for heating reaction is air atmosphere, and the heating reaction temperature is 100°C; the heating reaction time is 8 hours. After the reaction is completed, the solvent must be removed by vacuum distillation, and then the intermediate C can be obtained after extraction with methyl tert-butyl ether, concentration, and column chromatography;

[0046] S4. Intermediate C reacts with acrylic acid to produce a product containing perfluorobutylsulfonylacrylate, namely 2-(2-((perfluorobutyl)sulfonyl)acetoxy)ethyl acrylate. The molar ratio of intermediate C to acrylic acid is 1:2, and the amount ratio of intermediate C to solvent is 1mmol:1mL. The solvent is ethyl acetate, and the acid is concentrated sulfuric acid. The atmosphere of the heating reaction is air atmosphere, and the heating reaction temperature is 100°C; the heating reaction time is 8. After the reaction is completed, the solvent must be removed by vacuum distillation, and then the product containing perfluorobutylsulfonylacrylate, namely 2-(2-((perfluorobutyl)sulfonyl)acetoxy)ethyl acrylate, can be obtained by extraction with methyl tert-butyl ether, concentration, and column chromatography. Its liquid chromatography Figure 1 As shown, the yield is 70% and the purity is 95%.

[0047] The present invention uses industrially available raw materials: perfluorobutylsulfonyl fluoride, acetonitrile, acrylic acid, and ethylene glycol. A five-step reaction process, including acylation, hydrolysis, acidification, and two esterification steps, produces a perfluorobutylsulfonyl acrylate. This process requires no catalyst, utilizes readily available, inexpensive raw materials, is simple to operate, and is environmentally friendly, making it suitable for industrial production.

[0048] Finally, it should be noted that those skilled in the art should understand that the present invention is not limited to the above-described embodiments. The above-described embodiments and descriptions are merely illustrative of the principles of the present invention. Various changes and modifications may be made to the present invention without departing from the spirit and scope of the present invention. Such changes and modifications are intended to fall within the scope of the present invention. The scope of protection claimed in the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing perfluorobutylsulfonyl acrylate, characterized in that: Under normal pressure, perfluorobutylsulfonyl fluoride, acetonitrile, ethylene glycol, and acrylic acid are heated to react in the presence of a solvent and an organic base, and a perfluorobutylsulfonyl acrylate is prepared through a five-step reaction. The reaction equation is shown in Formula 1:

2. The method for preparing perfluorobutylsulfonyl acrylate according to claim 1, characterized in that: The molar ratio of perfluorobutylsulfonyl fluoride to acetonitrile in Formula 1A is 1:1.1-2; the concentration of acetonitrile in the solvent is 1-1.5 mol / L.

3. The method for preparing perfluorobutylsulfonyl acrylate according to claim 1, characterized in that: The solvent used in Formula 1A is ethyl acetate, dichloromethane, chloroform, chlorobenzene, toluene, benzene, tetrahydrofuran or 1,2-dichloroethane.

4. The method for preparing perfluorobutylsulfonyl acrylate according to claim 1, characterized in that: The base used in Formula 1A is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, n-butyl lithium, sodium hydride, sodium amide or cesium carbonate.

5. The method for preparing perfluorobutylsulfonyl acrylate according to claim 1, characterized in that: The reaction temperature in Formula 1A is 40 to 150° C.; the reaction time is 8 to 48 hours.

6. The method for preparing the perfluorobutylsulfonyl acrylate according to claims 1 to 5, characterized in that: The intermediate A in formula 1A can be separated and purified by the following steps: removing the solvent by distillation under reduced pressure, washing with water, extracting with tert-methyl ether, and then concentrating and separating with column chromatography to obtain the intermediate A.

7. The method for preparing perfluorobutylsulfonyl acrylate according to claim 1, characterized in that: The base selected in formula 1B is sodium hydroxide or potassium hydroxide.

8. The method for preparing perfluorobutylsulfonyl acrylate according to claim 1, characterized in that: The solvent used in Formula 1B is ethyl acetate, dichloromethane, chloroform, chlorobenzene, toluene, benzene, tetrahydrofuran or 1,2-dichloroethane.

9. The method for preparing perfluorobutylsulfonyl acrylate according to claim 1, characterized in that: The concentration of intermediate B in the solvent is 1-1.5 mol / L.

10. The method for preparing perfluorobutylsulfonyl acrylate according to claim 1, characterized in that: The reaction temperature in Formula 1B is 40 to 150° C.; the reaction time is 8 to 48 hours.

11. The method for preparing perfluorobutylsulfonyl acrylate according to claim 1, characterized in that: The acid selected in Formula 1B is dilute sulfuric acid, and its concentration is 10% to 60%.

12. The method for preparing perfluorobutylsulfonyl acrylate according to claims 7 to 11, characterized in that: The intermediate B in formula 1B can be separated and purified by the following steps: removing the solvent by distillation under reduced pressure, washing with water, extracting with tert-methyl ether, and then concentrating and separating with column chromatography to obtain the intermediate B.

13. The method for preparing perfluorobutylsulfonyl acrylate according to claim 1, characterized in that: The acid selected in formula 1C is concentrated sulfuric acid, methanesulfonic acid or trifluoromethanesulfonic acid.

14. The method for preparing perfluorobutylsulfonyl acrylate according to claim 1, characterized in that: The solvent used in Formula 1C is ethyl acetate, dichloromethane, chloroform, chlorobenzene, toluene, benzene, tetrahydrofuran or 1,2-dichloroethane.

15. The method for preparing perfluorobutylsulfonyl acrylate according to claim 1, characterized in that: The molar ratio of the intermediate B to ethylene glycol in Formula 1C is 1:1.1-1.2; the concentration of the intermediate B in the solvent is 1-1.5 mol / L.

16. The method for preparing perfluorobutylsulfonyl acrylate according to claim 1, characterized in that: The reaction temperature in Formula 1C is 40 to 150° C.; the reaction time is 8 to 48 hours.

17. The method for preparing perfluorobutylsulfonyl acrylate according to claims 13 to 16, characterized in that: The intermediate C in formula 1C can be separated and purified by the following steps: removing the solvent by distillation under reduced pressure, washing with water, extracting with tert-methyl ether, and then concentrating and separating with column chromatography to obtain the intermediate C.

18. The method for preparing perfluorobutylsulfonyl acrylate according to claim 1, characterized in that: The acid selected in formula 1D is concentrated sulfuric acid, methanesulfonic acid or trifluoromethanesulfonic acid.

19. The method for preparing perfluorobutylsulfonyl acrylate according to claim 1, characterized in that: The solvent used in Formula 1D is ethyl acetate, dichloromethane, chloroform, chlorobenzene, toluene, benzene, tetrahydrofuran or 1,2-dichloroethane.

20. The method for preparing perfluorobutylsulfonyl acrylate according to claim 1, characterized in that: The molar ratio of the intermediate C to acrylic acid in Formula 1D is 1:1.1-1.2; the concentration of the intermediate C in the solvent is 1-1.5 mol / L.

21. The method for preparing perfluorobutylsulfonyl acrylate according to claim 1, characterized in that: The reaction temperature in Formula 1D is 40 to 150° C.; the reaction time is 8 to 48 hours.

22. The method for preparing perfluorobutylsulfonyl acrylate according to claims 18 to 21, characterized in that: The intermediate C in formula 1D is separated and purified by the following steps: removing the solvent by distillation under reduced pressure, washing with water, extracting with tert-methyl ether, concentrating, and separating by column chromatography to obtain the final product, ethyl 2-(2-((perfluorobutyl)sulfonyl)acetoxy)acrylate.

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