Method for producing cyclic sulfonate ester derivative compounds

Abstract

The present invention provides a method for producing a cyclic sulfonate derivative compound, which can improve the yield and properties of the compound, and relates to a method for producing a cyclic sulfonate derivative compound, comprising the steps of: (A) reacting a compound represented by chemical formula 1 described herein with thioacetic acid to produce a compound represented by chemical formula 2 described herein; and (B) subjecting the compound represented by chemical formula 2 to an oxidative cyclization reaction to produce a compound represented by chemical formula 3 described herein.

Description

[Technical Field]

[0001] This application claims the benefit of priority based on Korean Patent Application No. 10-2022-0003553, filed on January 10, 2022, and all contents disclosed in the documents of this Korean patent application are incorporated herein by reference.

[0002] The present invention relates to a method for producing a cyclic sulfonate derivative compound. [Background technology]

[0003] 1,3-propane sultone and 1,4-butane sultone are known to be useful compounds as non-aqueous electrolyte additives in lithium secondary batteries. However, due to issues with 1,3-propane sultone and 1,4-butane sultone, such as toxicity, gas generation, and stability, active research has been conducted on cyclic sulfonate ester derivative compounds that can be used as non-aqueous electrolyte additives. For example, cyclic sulfonate ester derivative compounds incorporating a hydroxyl group-containing substituent at the gamma position (the carbon position adjacent to the oxygen atom in the ring structure) of 1,3-propane sultone, or cyclic sulfonate ester derivative compounds incorporating a hydroxyl group-containing substituent at the delta position (the carbon position adjacent to the oxygen atom in the ring structure) of 1,4-butane sultone, when used as non-aqueous electrolyte additives in lithium secondary batteries, form an electrode-electrolyte interface that is stable even at high temperatures and has low resistance, thereby improving the life characteristics of lithium secondary batteries.

[0004] Meanwhile, the cyclic sulfonate derivative compound is produced, for example, by a) hydrosulfonation and b) dehydration of 3-butene-1,2-diol. However, it is difficult to purify the sulfonate, which is the product of the hydrosulfonation of 3-butene-1,2-diol, from inorganic salt by-products, and the SOCl2 used in the dehydration reaction generates corrosive gases. In addition, due to purification issues in process a) and reactivity issues in process b), the overall yield tends to be low (less than 50%), and the product is often obtained in the form of a black tar (black gum).

[0005] Therefore, there is a need for research into a method for producing a cyclic sulfonate derivative compound that can solve the above-mentioned problems. Summary of the Invention [Problem to be solved by the invention]

[0006] The technical object of the present invention is to improve the production process, yield, product properties, etc. of cyclic sulfonate derivative compounds. [Means for solving the problem]

[0007] In order to solve the above problems, the present invention provides a method for producing a cyclic sulfonate derivative compound.

[0008] (1) The present invention provides a method for producing a cyclic sulfonate ester derivative compound, comprising the steps of: (A) reacting a compound represented by the following chemical formula 1 with thioacetic acid to produce a compound represented by the following chemical formula 2; and (B) subjecting the compound represented by the chemical formula 2 to an oxidative cyclization reaction to produce a compound represented by the following chemical formula 3.

[0009] [ka]

[0010] [ka]

[0011] [ka]

[0012] In the above Chemical Formulas 1 to 3, m is 0 or 1, R1 to R8 are each independently hydrogen; or substituted or unsubstituted C1-C 10 is an alkyl group.

[0013] (2) The present invention provides a method for producing a cyclic sulfonate ester derivative compound according to (1) above, wherein the equivalent ratio of the compound represented by Chemical Formula 1 to the thioacetic acid is 1:1 to 1:3.

[0014] (3) The present invention provides a method for producing a cyclic sulfonate ester derivative compound according to (1) or (2) above, wherein the step (A) is carried out in the presence of an acid catalyst.

[0015] (4) The present invention provides a method for producing a cyclic sulfonate ester derivative compound according to any one of (1) to (3) above, wherein the step (A) is carried out in a polar aprotic solvent.

[0016] (5) The present invention provides the method for producing a cyclic sulfonate ester derivative compound according to (4) above, wherein the polar aprotic solvent is one or more selected from the group consisting of dichloromethane, chloroform, 1,2-dichloroethane, and acetonitrile.

[0017] (6) The present invention provides a method for producing a cyclic sulfonate ester derivative compound according to any one of (1) to (5) above, wherein the step (A) is carried out at a temperature of 20°C to 40°C.

[0018] (7) The present invention provides a method for producing a cyclic sulfonate ester derivative compound according to any one of (1) to (6) above, wherein the step (B) is carried out in the presence of an acid catalyst.

[0019] (8) The present invention provides a method for producing a cyclic sulfonate ester derivative compound according to any one of (1) to (7) above, wherein the step (B) is carried out in a polar protic solvent.

[0020] (9) The present invention provides the method for producing a cyclic sulfonate ester derivative compound according to (8) above, wherein the polar protic solvent is at least one selected from the group consisting of distilled water, methanol, ethanol, propanol, and isopropanol.

[0021] (10) The present invention provides a method for producing a cyclic sulfonate ester derivative compound according to any one of (1) to (9) above, wherein in step (B), the oxidative cyclization reaction is carried out in the presence of one or more oxidizing agents selected from H2O2, HOCl, NCS, NBS, and KHSO5·0.5KHSO4·0.5K2SO4.

[0022] (11) The present invention provides a method for producing a cyclic sulfonate ester derivative compound according to any one of (1) to (10) above, wherein the step (B) is carried out at a temperature of 0°C to 25°C. [Effects of the Invention]

[0023] According to the present invention, the process for producing a cyclic sulfonate ester derivative compound can be improved, the yield can be increased, and a product with improved properties can be obtained. [Brief explanation of the drawings]

[0024] [Figure 1] 1H-NMR spectrum of the product prepared in Example 1. [Figure 2] 1H-NMR spectrum of the product prepared in Comparative Example 1. [Figure 3](a) is a digital camera photograph of the compound represented by chemical formula a prepared in Example 1, and (b) is a digital camera photograph of the compound represented by chemical formula a prepared in Comparative Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0025] The present invention will be described in more detail below for easy understanding. In this regard, the terms and words used in the specification and claims should not be interpreted in a limited way to their ordinary or dictionary meanings, but should be interpreted in a way that is consistent with the technical concept of the present invention, based on the principle that the inventors can appropriately define the concepts of terms in order to best describe their invention.

[0026] The present invention relates to a method for producing a cyclic sulfonate derivative compound, which includes the steps of: (A) reacting a compound represented by the following chemical formula 1 with thioacetic acid to produce a compound represented by the following chemical formula 2; and (B) subjecting the compound represented by the chemical formula 2 to an oxidative cyclization reaction to produce a compound represented by the following chemical formula 3.

[0027] [ka]

[0028] [ka]

[0029] [ka]

[0030] In the above Chemical Formulas 1 to 3, m is 0 or 1, R1 to R8 are each independently hydrogen; or substituted or unsubstituted C1-C 10 is an alkyl group.

[0031] In the present invention, the substituent in the substituted alkyl group may be deuterium, a halogen group, a hydroxy group, a -COOR group (R is an unsubstituted C1-C6 alkyl group), a -SONR'2 group (R' is hydrogen or an unsubstituted C1-C6 alkyl group), a cyano group, or a linear or branched C1-C6 alkoxy group.

[0032] In terms of ease of synthesis of Chemical Formula 3, R1 to R8 may each independently be hydrogen or an unsubstituted C1-C6 alkyl group. Specifically, R1 to R8 may all be hydrogen in terms of ease of synthesis and structural stability.

[0033] The compound represented by Chemical Formula 3 may be a compound represented by Chemical Formula a or b below.

[0034] [ka]

[0035] [ka]

[0036] Each step of the method for producing a cyclic sulfonate ester derivative compound will be specifically described below.

[0037] (A) Step Step (A) is a step in which the double bond of the compound represented by Chemical Formula 1 reacts with thioacetic acid (i.e., a thiol-ene reaction between a terminal alkene and thioacetic acid) to form a thioacetate intermediate.

[0038] According to the present invention, the equivalent ratio of the compound represented by Chemical Formula 1 to the thioacetic acid may be 1:1 to 1:3, specifically 1:1 to 1:2.5, and more specifically 1:1 to 1:2. When the equivalent ratio of the compound represented by Chemical Formula 1 to the thioacetic acid is within the above range, there is an advantage that a conversion rate of 99% or more (the conversion rate of the compound represented by Chemical Formula 1 to the compound represented by Chemical Formula 2) can be achieved without the generation of other identifiable by-products.

[0039] According to the present invention, step (A) may be carried out in the presence of an acid catalyst to promote proton transfer in the reaction mechanism, such as trifluoroacetic acid (TFA), hydrochloric acid (HCl), or sulfuric acid (H2SO4).

[0040] According to the present invention, the step (A) may be carried out in a polar aprotic solvent so as to facilitate the generation of an appropriate amount of the radical intermediate.

[0041] According to the present invention, the polar aprotic solvent may be one or more selected from dichloromethane, chloroform, 1,2-dichloroethane, and acetonitrile, which has the advantage that the solvent does not participate in the reaction and the radical intermediate is efficiently produced.

[0042] According to the present invention, step (A) may be carried out at a temperature of 20° C. to 40° C., specifically 30° C. to 40° C. In this case, not only is the reaction rate of step (A) fast, but the thioacetate intermediate (compound represented by Chemical Formula 2) may not be decomposed.

[0043] The step (A) may be carried out for 2 to 8 hours to prevent decomposition of the thioacetate intermediate and maximize the reaction conversion rate.

[0044] (B) Step Step (B) is a step of adding an oxidizing agent to the compound represented by Chemical Formula 2, which is a reaction intermediate, to cause an oxidative cyclization reaction, thereby forming a compound represented by Chemical Formula 3.

[0045] According to the present invention, the step (B) may be carried out under an acid catalyst in order to maintain a pH that promotes the oxidation reaction. The acid catalyst in the step (B) may be added in an amount of 3 or more equivalents per equivalent of the compound represented by the chemical formula 2. When the acid catalyst in the step (B) is, for example, HCl, the acid catalyst and Cl may be added. - Can act as a source.

[0046] According to the present invention, the step (B) may be carried out in a polar protic solvent to ensure the solubility of the compound represented by Chemical Formula 2.

[0047] According to the present invention, the polar protic solvent may be one or more selected from distilled water, methanol, ethanol, propanol, and isopropanol, in which case the reaction can proceed in a homogeneous phase of the compound represented by Chemical Formula 2 (reactant), the oxidizing agent, and the acid catalyst.

[0048] According to the present invention, in step (B), the oxidative cyclization reaction may be carried out in the presence of one or more oxidizing agents selected from H2O2, HOCl, NCS, NBS, and KHSO5·0.5KHSO4·0.5K2SO4.

[0049] According to the present invention, the step (B) may be carried out at a temperature of 0° C. to 25° C., specifically 0° C. to 15° C. In this case, excessive oxidation reaction by the oxidizing agent can be controlled, and reaction stability can be ensured.

[0050] Step (B) can be carried out while controlling the temperature as follows to prevent side reactions caused by the oxidizing agent (e.g., decomposition of the oxidizing agent itself): Specifically, when the oxidizing agent is added in step (B), the temperature is maintained at 0°C to 10°C, and after the addition of the oxidizing agent is completed, the oxidative cyclization reaction can be carried out at a temperature of 0°C to 25°C.

[0051] Step (B) may be carried out for 4 to 24 hours to maximize the yield while preventing isomerization of the compound represented by Chemical Formula 3 (product).

[0052] Meanwhile, in step (B), the oxidizing agent is added in excess, and after the reaction is completed, sodium sulfite (NaSO) may be added to quench the remaining oxidizing agent, thereby preventing the remaining oxidizing agent from exploding.

[0053] Although the present invention may be embodied in various different forms, it is not intended to be limited to the embodiments set forth herein, and the present invention is not limited to the embodiments set forth herein.

[0054] Examples and Comparative Examples Example 1 [ka] A round-bottom flask was charged with 52.8 g (1 equiv.) of 3-butene-1,2-diol, 91.3 g (2 equiv.) of thioacetic acid, 34.2 g (0.5 equiv.) of trifluoroacetic acid (TFA), and 100 mL of dichloromethane, and the mixture was refluxed for 5 hours. After vacuum removal of volatile organic compounds, 93.9 g (95.3% yield) of the thioacetate intermediate (S-(3,4-dihydroxybutyl)-1-yl thioacetate) was obtained as a pale yellow liquid.

[0055] A new round-bottom flask (hereinafter referred to as the reactor) was charged with 42 g of the thioacetate intermediate and 100 mL of MeOH and cooled to 0°C. The reactor's internal temperature was maintained at 0°C, and 68 mL of a 35% by weight aqueous HCl solution was slowly added, followed by 84 mL of a 30% by weight aqueous HO solution. After the addition of the HO solution, the mixture was stirred at 0°C for 4 hours, then heated to 25°C and stirred at 25°C for 4 hours. Then, 15 g of NaSO was added and stirred for an additional hour. The product was extracted with 200 mL of ethyl acetate (the organic layer was separated), and the product was further extracted from the aqueous layer (three times with 100 mL of ethyl acetate). The organic layer was collected, dehydrated with MgSO, and then distilled under reduced pressure to obtain 26.3 g (yield: 76.7%) of the compound represented by formula (a) in the form of a colorless solution.

[0056] Comparative Example 1 [ka] A round-bottom flask was charged with 20 g of 3-butene-1,2-diol and 90 ml of deionized water. Then, with vigorous stirring at 65 °C, an aqueous solution of NaSO (59.4 g of NaSO dissolved in 100 ml of deionized water) neutralized with 20 g of NaOH was added over 5 minutes. While stirring, the pH was maintained at 7.3-7.6 using 6 M aqueous HSO. Once all the 3-butene-1,2-diol was consumed, the solvent was removed by vacuum distillation. 250 ml of MeOH was added to the white solid residue and stirred for 2 hours. The undissolved inorganic materials were filtered, and the solid inorganic salts were washed with 2500 ml of MeOH. The filtrate was distilled under reduced pressure to obtain 42 g (yield: 94%, purity: 55%) of a sulfonate intermediate (3,4-dihydroxybutane-1-sulfonic acid sodium salt) containing inorganic salts.

[0057] 1.9 g of the sulfonate intermediate was dispersed in 10 mL of chloroform, followed by the addition of 0.08 mL (0.1 equivalents) of DMF. 1.5 mL (2 equivalents) of SOCl2 was added dropwise at room temperature, followed by stirring at 55°C for 8 hours. After the reaction was complete, the reaction solution was cooled to room temperature and filtered to remove solid by-products. The filtrate was concentrated by vacuum distillation. 10 mL of methanol and 0.8 mL of 12 M HCl were added to the concentrated solution at 0°C, stirred for 2 hours to hydrolyze the product, and then the solvent was removed by vacuum distillation. The crude product was dissolved in DCM (dichloromethane), added with 2 g of Celite, stirred for 30 minutes, filtered, and the filtrate was concentrated to obtain 0.55 g (36% yield) of the compound represented by formula a as a black gum.

[0058] Experimental example In each Example 1 and Comparative Example 1, it was confirmed by TLC that the thioacetate intermediate or sulfonate intermediate had been completely consumed. 0.05 ml of the reaction solution was diluted with 0.45 ml of DMSO-d6 and analyzed using a nuclear magnetic resonance spectrometer (B500 Bruker Avace Neo, Bruker). 1 H-NMR spectra were obtained and are shown in Figures 1 and 2, respectively.

[0059] 1 From the H-NMR spectrum, it was confirmed that the compound represented by formula a was produced in both Example 1 and Comparative Example 1. The yield of the compound represented by formula a in Example 1 was 76.7%, which was higher than the yield (36%) in Comparative Example 1.

[0060] This shows that the yield is improved when a cyclic sulfonate derivative compound is produced by the production method according to the present invention.

[0061] For reference, the NMR peaks at 2.897 ppm and 2.738 ppm in the comparative example are peaks of residual DMF.

[0062] Furthermore, referring to Figure 3 (Figure 3(a) is a digital camera photograph of the compound represented by chemical formula a prepared in Example 1, and Figure 3(b) is a digital camera photograph of the compound represented by chemical formula a prepared in Comparative Example 1), which shows the properties of the product, it can be seen that when a cyclic sulfonate ester derivative compound is prepared by the preparation method of the present invention, the properties (color purity) of the compound are improved.

Claims

1. (A) reacting a compound represented by the following Chemical Formula 1 with thioacetic acid to prepare a compound represented by the following Chemical Formula 2: (B) subjecting the compound represented by Chemical Formula 2 to an oxidative cyclization reaction to produce a compound represented by Chemical Formula 3: 【Chemical 1】 【Chemistry 2】 【Chemistry 3】 (In the above Chemical Formulas 1 to 3, m is 0 or 1; R １ ~R ８ are each independently hydrogen; or substituted or unsubstituted C １ -C １０ is an alkyl group represented by the formula:

2. The method for producing a cyclic sulfonate derivative compound according to claim 1, wherein the equivalent ratio of the compound represented by Chemical Formula 1 to the thioacetic acid is 1:1 to 1:

3.

3. The method for producing a cyclic sulfonate ester derivative compound according to claim 1 , wherein the step (A) is carried out in the presence of an acid catalyst.

4. The method for producing a cyclic sulfonate ester derivative compound according to claim 1 , wherein the step (A) is carried out in a polar aprotic solvent.

5. 5. The method for producing a cyclic sulfonate ester derivative compound according to claim 4, wherein the polar aprotic solvent is one or more selected from the group consisting of dichloromethane, chloroform, 1,2-dichloroethane, and acetonitrile.

6. The method for producing a cyclic sulfonate ester derivative compound according to claim 1, wherein the step (A) is carried out at a temperature of 20°C to 40°C.

7. The method for producing a cyclic sulfonate ester derivative compound according to claim 1 , wherein the step (B) is carried out in the presence of an acid catalyst.

8. The method for producing a cyclic sulfonate ester derivative compound according to claim 1 , wherein the step (B) is carried out in a polar protic solvent.

9. 9. The method for producing a cyclic sulfonate ester derivative compound according to claim 8, wherein the polar protic solvent is at least one selected from the group consisting of distilled water, methanol, ethanol, propanol, and isopropanol.

10. In the step (B), the oxidative cyclization reaction is carried out by H ２ O ２ , HOCl, NCS, NBS, and KHSO ５ ・0.5KHSO ４ ・0.5K ２ SO ４ The method for producing a cyclic sulfonate derivative compound according to claim 1, wherein the method is carried out in the presence of one or more oxidizing agents selected from the group consisting of:

11. The method for producing a cyclic sulfonate ester derivative compound according to claim 1, wherein the step (B) is carried out at a temperature of 0°C to 25°C.

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