Preparation methods of fluorosulfonyl carboxylic acid esters, the esters prepared from them, and the uses of the esters.

Abstract

This invention relates to a method for preparing fluorosulfonyl carboxylic acid esters, the esters prepared therefrom, and the uses of the esters. It is used in the preparation of FSO2R. 1 C(O)OR 2 The method of representing an ester, the method comprising making acid FSO2R 1 COOH reacts with pentanoyl chloride, N,N'-carbonyl diimidazole, acetyl chloride, or acetic anhydride under alkaline conditions to generate the reactive intermediate acid anhydride, and the reactive intermediate acid anhydride reacts with alcohol R. 2 The OH reaction produces an ester represented by formula (I). By using the method of the present invention, the problems of unsafe raw materials, difficulty in use, low product yield, difficult reaction operation, and environmental pollution caused by the prior art are solved.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis technology, and more specifically, to a method for synthesizing a fluorosulfonyl carboxylic acid ester, the ester prepared therefrom, and the uses of the ester. Background Technology

[0002] With the trend towards lighter and smaller electronic products, the development of electrochemical devices such as high-energy-density lithium-ion rechargeable batteries is progressing. Furthermore, as the application areas of lithium-ion rechargeable batteries and other electrochemical devices expand, improvements in their performance are desired. In particular, the improvement of battery performance will become increasingly important in the future use of lithium-ion rechargeable batteries in automotive applications.

[0003] Sulfonyl fluorides and their derivatives are a topic worthy of in-depth research. The addition of a fluoride group (SO2F) to the sulfonyl group into the molecular system can lead to compounds that can be used as ion exchange resins, surfactants, and strong sulfonic acids.

[0004] Based on this, research on sulfonyl fluorides and their derivatives as additives for lithium-ion secondary batteries continues, and some compounds have shown good performance in lithium-ion secondary battery additives.

[0005] Given the excellent properties and wide range of applications of sulfonyl fluorides and their derivatives, they are well worth developing.

[0006] There are few synthetic methods for sulfonyl fluorides and their derivatives. Among them, Jilla Khalilolah, Javid Mohtasham et al. (Inorg. Chem, 1987, 26, 2307-2309) reported a preparation method. Using tetrafluoroethane-β-sulfonyl lactone as a starting material, the target product 2,2,2-trifluoroethyl-2,2-difluoro-2-(fluorosulfonyl)acetate was obtained through ring-opening with trifluoroethanol. The starting material, tetrafluoroethane-β-sulfonyl lactone, is a gas at room temperature, making it inconvenient to use and operate in the laboratory. The yield was 90%, and the synthetic route is as follows:

[0007]

[0008] Therefore, there is a need to provide a method for preparing fluorosulfonyl carboxylic acid esters to solve the problems of unsafe raw materials, difficulty in use, low yield of the obtained product, difficult reaction operation, and environmental pollution caused by the prior art. Summary of the Invention

[0009] The main objective of this invention is to provide a method for preparing fluorosulfonyl carboxylic acid esters, thereby solving the problems of unsafe raw materials, difficulty in use, low yield of the obtained product, difficult reaction operation, and environmental pollution caused by the prior art.

[0010] To achieve the above objectives, according to one aspect of the present invention, a method for preparing an ester represented by formula (I) is provided.

[0011] FSO2R 1 C(O)OR 2 (I)

[0012] in

[0013] R 1 is CF2, CF(CF3), C(CF3)2, CF2CF2, CF(CF3)CF2, C(CF3)2CF2, CF2CF(CF3), CF2C(CF3)2, CF(CF3)CF(CF3), or C(CF3)2C(CF3)2,

[0014] R 2 For CF3CH2, CF2(CF3)CH2, CF(CF3)2CH2, C(CF3)3CH2, CF3CF2CH2, CF2(CF3)CF2CH2, CF(CF3)2CF2CH2, C(CF3)3CF2CH2, CF3CF(CF3)CH2, CF3C(CF3)2CH2, CF 2(CF3)CF(CF3)CH2, CF(CF3)2CF(CF3)CH2, C(CF3)3CF(CF3)CH2, CF2(CF3)C(CF3)2CH2, CF(CF3)2C(CF3)2CH2, C(CF3)3C(CF3)2CH2, C(CF3)3, or (CF3)2CH,

[0015] The method includes: making acid FSO2R 1 COOH reacts with pentanoyl chloride, N,N'-carbonyldiimidazole, acetyl chloride, or acetic anhydride under alkaline conditions to generate the reactive intermediate acid anhydride, and the reactive intermediate acid anhydride reacts with alcohol R. 2 The OH reaction produces an ester represented by formula (I).

[0016] Preferably, R 1 It is CF2, CF(CF3), or C(CF3)2, preferably, R 1 It is CF2.

[0017] Preferably, R 2 It is CF3CH2, CF2(CF3)CH2, CF(CF3)2CH2, or C(CF3)3CH2, preferably, R 2 It is CF3CH2.

[0018] Preferably, acid FSO2R 1 COOH reacts with pivaloyl chloride under alkaline conditions to form the reactive intermediate acid anhydride.

[0019] Acid FSO2R 1 COOH reacts with pivaloyl chloride at a temperature ranging from 0 to 5°C for 1 to 3 hours.

[0020] Preferably, the active intermediate acid anhydride and alcohol R 2 OH reacts at a temperature ranging from 0 to 5°C for 1 to 3 hours.

[0021] Preferably, acid FSO2R 1 COOH reacts with pivaloyl chloride under alkaline conditions to form the reactive intermediate acid anhydride, FSO2R. 1 The molar ratio of COOH to pivaloyl chloride is 1:(1.0–2.2); acid FSO2R 1 COOH and alcohol R 2 The molar ratio of OH is 1:(1.0~2.2); and the acid FSO2R 1 The molar ratio of COOH to the compound that provides alkaline conditions is 1:(1.0 to 2.2).

[0022] Preferably, the compound providing the alkaline conditions is an amine compound; the amine compound is selected from triethylamine, N,N-diisopropylethylamine, diethylamine, ethylamine, tert-butylamine, or N-tert-butylethylamine.

[0023] Preferably, the compound that provides alkaline conditions is triethylamine.

[0024] According to another aspect of the invention, an ester represented by formula (I) prepared by the method described above is provided.

[0025] According to another aspect of the invention, the use of an ester represented by formula (I) according to the above aspect as an additive for lithium-ion secondary batteries is provided.

[0026] This invention addresses the problems of unsafe and unusable raw materials, low product yield, difficult reaction operation, and environmental pollution in the preparation process of fluorosulfonyl carboxylic esters in the prior art. By selecting specific raw materials and preparation processes, this invention overcomes these problems. Attached Figure Description

[0027] The accompanying drawings, which form part of this application, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. In the drawings:

[0028] Figure 1The 1H NMR spectrum of 2,2,2-trifluoroethyl-2,2-difluoro-2-(fluorosulfonyl)acetate prepared according to Example 1 of the present invention is shown; and

[0029] Figure 2 The carbon NMR spectrum of 2,2,2-trifluoroethyl-2,2-difluoro-2-(fluorosulfonyl)acetic acid ester prepared according to Example 1 of the present invention is shown. Detailed Implementation

[0030] It should be noted that, unless otherwise specified, the embodiments and features described in this application can be combined with each other. The present invention will now be described in detail with reference to the accompanying drawings and embodiments.

[0031] The present application will be further described in detail below with reference to specific embodiments, which should not be construed as limiting the scope of protection claimed in the present application.

[0032] As described in the background section of this application, existing technologies suffer from problems such as unsafe and difficult-to-use raw materials, low product yields, difficult-to-operate reactions, and environmental pollution in the preparation process of fluorosulfonyl carboxylic esters. To address these issues, this application provides a method for preparing esters represented by formula (I).

[0033] FSO2R 1 C(O)OR 2 (I)

[0034] in

[0035] R 1 is CF2, CF(CF3), C(CF3)2, CF2CF2, CF(CF3)CF2, C(CF3)2CF2, CF2CF(CF3), CF2C(CF3)2, CF(CF3)CF(CF3), or C(CF3)2C(CF3)2,

[0036] R 2 For CF3CH2, CF2(CF3)CH2, CF(CF3)2CH2, C(CF3)3CH2, CF3CF2CH2, CF2(CF3)CF2CH2, CF(CF3)2CF2CH2, C(CF3)3CF2CH2, CF3CF(CF3)CH2, CF3C(CF3)2CH2, CF 2(CF3)CF(CF3)CH2, CF(CF3)2CF(CF3)CH2, C(CF3)3CF(CF3)CH2, CF2(CF3)C(CF3)2CH2, CF(CF3)2C(CF3)2CH2, C(CF3)3C(CF3)2CH2, C(CF3)3, or (CF3)2CH.

[0037] The preparation method includes making acid FSO2R 1 COOH reacts with pentanoyl chloride, N,N'-carbonyldiimidazole, acetyl chloride, or acetic anhydride under alkaline conditions to generate the reactive intermediate acid anhydride, and the reactive intermediate acid anhydride reacts with alcohol R. 2 The OH reaction produces an ester represented by formula (I).

[0038] This application selects safe and easy-to-use acid FSO2R. 1 COOH and alcohol R 2 Using OH as a raw material makes the reaction easier to operate, reduces environmental pollution, and increases the yield of the product.

[0039] In a preferred embodiment, the alkaline condition is 8 < pH ≤ 12. Using an alkaline condition of 8 < pH ≤ 12 avoids waste of raw materials.

[0040] In a preferred embodiment, the R of the present invention 1 It is CF2, CF(CF3), or C(CF3)2, preferably, R 1 For CF2. By selecting R among them 1 It is CF2, CF(CF3), or C(CF3)2, preferably, R 1 FSO2R is an acid of CF2 1 The presence of COOH makes the reaction easy to operate and results in a high yield of the product.

[0041] In a preferred embodiment, R 2 It is CF3CH2, CF2(CF3)CH2, CF(CF3)2CH2, or C(CF3)3CH2, preferably, R 2 For CF3CH2. By selecting R... 2 It is CF3CH2, CF2(CF3)CH2, CF(CF3)2CH2, or C(CF3)3CH2, preferably, R 2 The alcohol R of CF3CH2 2 The presence of OH facilitates the reaction and results in a product with high thermal stability.

[0042] To achieve a higher yield, in a preferred embodiment, the acid FSO2R is... 1 COOH reacts with pivaloyl chloride under alkaline conditions to form the reactive intermediate acid anhydride, FSO2R. 1 COOH reacts with pivaloyl chloride at a temperature ranging from 0 to 5°C for 1 to 3 hours. It should be noted that the "active intermediate anhydride" refers to the anhydride with the molecular formula FSO₂R. 1 The acid anhydride of C(O)OC(O)C(CH3)3.

[0043] In a preferred embodiment, the active intermediate acid anhydride and alcohol R 2 Higher yields can be obtained by reacting OH at a temperature in the range of 0 to 5°C for 1 to 3 hours.

[0044] Preferably, R is used 1 FSO2R is an acid of CF2 1 COOH and R in it 2 The alcohol R of CF3CH2 2 The ester FSO2F2C(O)OCH2CF3 obtained by the OH reaction has a high yield.

[0045] In a preferred embodiment, acid FSO2R is used. 1 COOH reacts with pivaloyl chloride under alkaline conditions to form the reactive intermediate acid anhydride, FSO2R. 1 The molar ratio of COOH to pivaloyl chloride is 1:(1.0–2.2); acid FSO2R 1 COOH and alcohol R 2 The molar ratio of OH is 1:(1.0~2.2); and the acid FSO2R 1 The molar ratio of COOH to the compound providing basic conditions is 1:(1.0–2.2). This application uses the above molar ratio to make the acid FSO2R 1 Complete reaction of COOH increases the yield. If any molar ratio is outside the above range, the reaction will be incomplete, resulting in wasted raw materials and low product yield.

[0046] In order to make acid FSO2R 1 COOH reacts more readily with tert-valerate. In a preferred embodiment, the compound providing the basic conditions is an amine compound selected from triethylamine, N,N-diisopropylethylamine, diethylamine, ethylamine, tert-butylamine, or N-tert-butylethylamine.

[0047] In a preferred embodiment, the compound providing the basic conditions is triethylamine. This application uses triethylamine to provide the basic conditions, making the reaction easier to proceed.

[0048] According to another aspect of the present invention, an ester represented by formula (I) prepared by the aforementioned method is provided.

[0049] According to another aspect of the invention, the use of the ester represented by the aforementioned formula (I) as an additive for lithium-ion secondary batteries is provided.

[0050] The beneficial effects of the present invention will be further illustrated below with reference to embodiments.

[0051] Example 1

[0052] Preparation of 2,2,2-trifluoroethyl-2,2-difluoro-2-(fluorosulfonyl)acetic acid ester

[0053] Under an argon atmosphere, a mixture of 2-fluorosulfonyl difluoroacetic acid (20.0 g, 0.113 mol) and dichloromethane (200 mL) was added to a reaction flask, followed by triethylamine (13.0 g, 0.124 mol). The mixture was cooled to 0 °C, and pentanoyl chloride (15.0 g, 0.124 mol) was added dropwise while maintaining the temperature at 0 °C. After the addition was complete, the mixture was kept at the same temperature and stirred for 1 hour. Trifluoroethanol (13.6 g, 0.136 mol) was then added dropwise while maintaining the temperature at 0 °C. After the addition was complete, the mixture was kept at the same temperature and stirred for 1 hour. After the reaction was complete, the low-boiling solvent was distilled off under reduced pressure. Further distillation under reduced pressure yielded 29.2 g of a colorless liquid with a GC purity of 99.1% and a yield of 99.4%. Bp 57 ± 1 °C (54 mmHg). 1 H NMR (400MHz, CDCl3): δ (ppm): 8.47 (s, 2H). 13 C (MHz, CDCl3): C(1): 162.235ppm; C(2): 135.356ppm; C(3): 69.313ppm; C(4): 125.077ppm.

[0054]

[0055] MS: [M+H]: 261.11

[0056] Figure 1 The 1H NMR spectrum of 2,2,2-trifluoroethyl-2,2-difluoro-2-(fluorosulfonyl)acetate prepared according to Example 1 of the present invention is shown; and

[0057] Figure 2 The carbon NMR spectrum of 2,2,2-trifluoroethyl-2,2-difluoro-2-(fluorosulfonyl)acetic acid ester prepared according to Example 1 of the present invention is shown.

[0058] Example 2

[0059] Preparation of FSO2CF(CF3)C(O)OCH2(CF3)CF2 ester

[0060] Under an argon atmosphere, a mixture of FSO2CF(CF3)COOH (20.0 g, 0.0877 mol) in 200 ml of dichloromethane was added to a reaction flask, followed by the addition of triethylamine (9.7 g, 0.0962 mol). The mixture was cooled to 5 °C, and pentanoyl chloride (11.6 g, 0.0962 mol) was added dropwise at 5 °C. After the addition was complete, the mixture was kept at this temperature and stirred for 3 hours. Then, OHCH2(CF3)CF2 (15.9 g, 0.106 mol) was added dropwise at 5 °C. After the addition was complete, the mixture was kept at this temperature and stirred for 3 hours. After the reaction was complete, the low-boiling solvent was distilled off under reduced pressure. Further distillation under reduced pressure yielded 25.9 g of a colorless liquid with a GC purity of 99.1%, a yield of 82%, and a Bp of 89 ± 1 °C (54 mmHg).

[0061] Example 3

[0062] Preparation of FSO2CF(CF3)CF2C(O)OCH2(CF3)CFCF3 ester

[0063] Under an argon atmosphere, a mixture of FSO2CF(CF3)CF2COOH (20.0 g, 0.0719 mol) in 200 ml of dichloromethane was added to a reaction flask, followed by the addition of triethylamine (8.0 g, 0.0791 mol). The mixture was cooled to 0 °C, and pentanoyl chloride (9.5 g, 0.0791 mol) was added dropwise while maintaining the temperature at approximately 0 °C. After the addition was complete, the mixture was kept at this temperature and stirred for 1 hour. Then, HOCH2(CF3)CFCF3 alcohol (17.3 g, 0.086 mol) was added dropwise while maintaining the temperature at approximately 0 °C. After the addition was complete, the mixture was kept at this temperature and stirred for 1 hour. After the reaction was complete, the low-boiling solvent was distilled off under reduced pressure. Further distillation under reduced pressure yielded 26.2 g of a colorless liquid with a GC purity of 98.9% and a yield of 79%. Bp: 106 ± 1 °C (54 mmHg).

[0064] Example 4

[0065] Preparation of FSO2C(CF3)2C(CF3)2C(O)OCH2(CF3)2C(CF3)2CF ester

[0066] Under an argon atmosphere, a mixture of FSO₂C(CF₃)₂C(CF₃)₂COOH (20.0 g, 0.0467 mol) in 200 mL of dichloromethane was added to a reaction flask. Then, triethylamine (5.2 g, 0.0514 mol) was added, and the mixture was cooled to 0 °C. Pteropenoyl chloride (6.2 g, 0.0514 mol) was added dropwise while maintaining the temperature at approximately 0 °C. After the addition was complete, the mixture was kept at this temperature and stirred for 1 hour. Then, HOCH₂(CF₃)₂C(CF₃)₂CF alcohol (19.6 g, 0.056 mol) was added dropwise while maintaining the temperature at approximately 0 °C. After the addition was complete, the mixture was kept at this temperature and stirred for 1 hour. After the reaction was complete, the low-boiling solvent was distilled off under reduced pressure. Further distillation under reduced pressure yielded 30.2 g of a colorless liquid with a GC purity of 98.7% and a yield of 85%. Bp 112 ± 1 °C (54 mmHg).

[0067] Example 5

[0068] Under an argon atmosphere, a mixture of 2-fluorosulfonyl difluoroacetic acid (20.0 g, 0.113 mol) in dichloromethane (200 mL) was added to a reaction flask, followed by the addition of triethylamine (13.0 g, 0.124 mol). The mixture was cooled to 10 °C, and pentanoyl chloride (15.0 g, 0.124 mol) was added dropwise while maintaining the temperature at approximately 10 °C. After the addition was complete, the mixture was kept at this temperature and stirred for 5 hours. Trifluoroethanol (13.6 g, 0.136 mol) was then added dropwise while maintaining the temperature at approximately 10 °C. After the addition was complete, the mixture was kept at this temperature and stirred for 5 hours. After the reaction was complete, the low-boiling solvent was distilled off under reduced pressure. Further distillation under reduced pressure yielded 27.3 g of a colorless liquid with a GC purity of 98.9% and a yield of 93%. Bp °C (54 mmHg).

[0069] Example 6

[0070] Under an argon atmosphere, a mixture of 2-fluorosulfonyl difluoroacetic acid (20.0 g, 0.113 mol) and dichloromethane (200 mL) was added to a reaction flask, followed by the addition of triethylamine (26.1 g, 0.249 mol). The mixture was cooled to 0 °C, and pentanoyl chloride (30.1 g, 0.249 mol) was added dropwise while maintaining the temperature at approximately 0 °C. After the addition was complete, the mixture was kept at this temperature and stirred for 1 hour. Trifluoroethanol (24.9 g, 0.249 mol) was then added dropwise while maintaining the temperature at approximately 0 °C. After the addition was complete, the mixture was kept at this temperature and stirred for 1 hour. After the reaction was complete, the low-boiling solvent was distilled off under reduced pressure. Further distillation under reduced pressure yielded 26.1 g of a colorless liquid with a GC purity of 98.9% and a yield of 89%. Bp °C (54 mmHg).

[0071] Example 7

[0072] Preparation of 2,2,2-trifluoroethyl-2,2-difluoro-2-(fluorosulfonyl)acetic acid ester

[0073] Under an argon atmosphere, a mixture of 2-fluorosulfonyl difluoroacetic acid (20.0 g, 0.113 mol) and dichloromethane (200 mL) was added to a reaction flask, followed by the addition of triethylamine (13.0 g, 0.124 mol). The mixture was cooled to 0 °C, and pentanoyl chloride (9.1 g, 0.075 mol) was added dropwise while maintaining the temperature at approximately 0 °C. After the addition was complete, the mixture was kept at this temperature and stirred for 1 hour. Trifluoroethanol (13.6 g, 0.136 mol) was then added dropwise while maintaining the temperature at approximately 0 °C. After the addition was complete, the mixture was kept at this temperature and stirred for 1 hour. After the reaction was complete, the low-boiling solvent was distilled off under reduced pressure. Further distillation under reduced pressure yielded 12.6 g of a colorless liquid with a GC purity of 97.9% and a yield of 43%. Bp °C (54 mmHg).

[0074] Comparative Example 1

[0075] Preparation of 2,2,2-trifluoroethyl-2,2-difluoro-2-(fluorosulfonyl)acetic acid ester

[0076] Trifluoroethanol (12.3 g, 0.123 mol) and sodium fluoride (10.0 g, 0.238 mol) were added to a high-pressure reactor. The reactor lid was closed, and a vacuum was applied. The reactor was purged with nitrogen three times. Tetrafluoroethane-β-sulfonolactone (20.1 g, 0.113 mol) was then introduced. After the addition was complete, the mixture was stirred at room temperature for 3 days. After the reaction was completed, 20.0 g of a colorless liquid was obtained by vacuum distillation, with a GC purity of 98.5% and a yield of 68%.

[0077] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A process for preparing an ester represented by formula (I), ###0001### (I) wherein R1 is a C1-C6 alkyl group; R2 is a C1-C6 alkyl group; R3 is a C1-C6 alkyl group; R4 is a C1-C6 alkyl group; R5 is a C1-C6 alkyl group; R6 is a C1-C6 alkyl group; R7 is a C1-C6 alkyl group; R8 is a C1-C6 alkyl group; R9 is a C1-C6 alkyl group; R10 is a C1-C6 alkyl group; R11 is a C1-C6 alkyl group; R12 is a C1-C6 alkyl group; R13 is a C1-C6 alkyl group; R14 is a C1-C6 alkyl group; R15 is a C1-C6 alkyl group; R16 is a C1-C6 alkyl group; R17 is a C1-C6 alk FSO2R 1 C(O)OR 2 (I) ​ R 1 CF2, CF(CF3), C(CF3)2, CF2CF2, CF(CF3)CF2, C(CF3)2CF2, CF2CF(CF3), CF2C(CF3)2, CF(CF3)CF(CF3), or C(CF3)2C(CF3)2, R 2 CF3CH2, CF2(CF3)CH2, CF2(CF3)CF2CH2, CF(CF3)2CF2CH2, C(CF3)3CF2CH2, CF3CF(CF3)CH2, CF3C(CF3)2CH2, CF2(CF3)CF(CF3)CH2, CF(CF3)2CF(CF3)CH2, C(CF3)3CF(CF3)CH2, CF2(CF3)C(CF3)2CH2, CF(CF3)2C(CF3)2CH2, C(CF3)3C(CF3)2CH2, C(CF3)3, or (CF3)2CH, characterized in that ​ FSO2R 1 COOH with pivaloyl chloride under basic conditions to form the active intermediate anhydride, and reacting the active intermediate anhydride with an alcohol R 2 OH to form an ester represented by formula (I); wherein the acid FSO2R 1 COOH is reacted with pivaloyl chloride at a temperature in the range of 0 to 5 °C for 1 to 3 hours, the acid FSO2R 1 COOH and the pivaloyl chloride is in the range of 1 : (1.0 to 2.2), the acid FSO2R 1 COOH and the compound providing the basic conditions is in the range of 1 : (1.0 to 2.2); the active intermediate anhydride has the formula FSO2R 1 C(O)OC(O)C(CH3)3; said active intermediate anhydride with said alcohol R 2 OH at a temperature in the range of 0 to 5 °C for 1 to 3 hours; said acid FSO2R 1 COOH and said alcohol R 2 OH in a molar ratio of 1 : (1.0 to 2.2).

2. The method of claim 1, wherein, R 1 CF2, CF(CF3), or C(CF3)2.

3. The method of claim 2, wherein, R 1 is CF2.

4. The method of claim 1, wherein, R 2 CF3CH2, CF2(CF3)CH2, CF(CF3)2CH2, or C(CF3)3CH2.

5. The method of claim 4, wherein, R 2 CF3CH2.

6. The method according to any one of claims 1 to 5, characterized in that, ​ ​ 7. The method according to any one of claims 1 to 5, characterized in that, ​

Images