Compounds and methods for producing the same

Abstract

The present invention relates to a precursor compound that can be used in the production of a cyclic sulfonate derivative compound and a method for producing the same.

Description

[Technical Field]

[0001] This application claims the benefit of priority based on Korean Patent Application No. 10-2021-0107249, filed on August 13, 2021, and all contents disclosed in the documents of that Korean patent application are incorporated herein by reference.

[0002] The present invention relates to a precursor compound of a cyclic sulfonate ester derivative compound and a method for producing the same. [Background technology]

[0003] 1,3-propane sultone and 1,4-butane sultone are known to be useful compounds as non-aqueous electrolyte additives for lithium secondary batteries. However, 1,3-propane sultone and 1,4-butane sultone have problems such as toxicity, gas generation, and stability. Therefore, active research is being conducted on cyclic sulfonate ester derivative compounds that can be used as non-aqueous electrolyte additives in place of 1,3-propane sultone and 1,4-butane sultone. For example, active research is being conducted on cyclic sulfonate ester derivative compounds in which a derivative is introduced at the gamma position (the carbon atom next to the oxygen atom in the ring structure) of 1,3-propane sultone or at the delta position (the carbon atom next to the oxygen atom in the ring structure) of 1,4-butane sultone, which, when used as non-aqueous electrolyte additives for secondary batteries, are stable even at high temperatures, form a low-resistance electrode-electrolyte interface, and improve the life characteristics of lithium secondary batteries.

[0004] In this regard, in order to easily produce a cyclic sulfonate ester derivative compound in which a derivative is introduced at the gamma position of 1,3-propane sultone or a cyclic sulfonate ester derivative compound in which a derivative is introduced at the delta position of 1,4-butane sultone, that is, in order to easily produce a cyclic sulfonate ester derivative compound, research is needed on compounds that can be used as precursors in the production of these compounds. Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a compound that can be used as a precursor when producing a cyclic sulfonate ester derivative compound, and a method for producing the same. [Means for solving the problem]

[0006] In order to solve the above problems, the present invention provides a compound and a method for producing the same.

[0007] (1) The present invention provides a compound represented by the following chemical formula I:

[0008] [ka]

[0009] In the above chemical formula I, m is 0 or 1, R1 to R8 are each independently hydrogen; or substituted or unsubstituted C1-C 10 is an alkyl group.

[0010] (2) The present invention provides the compound according to (1) above, wherein R1 to R8 are each independently hydrogen or an unsubstituted C1-C6 alkyl group.

[0011] (3) The present invention provides the compound according to (1) or (2) above, wherein the compound represented by chemical formula I is a compound represented by the following chemical formula a or b:

[0012] [ka]

[0013] [ka]

[0014] (4) The present invention also provides a method for producing a compound represented by chemical formula I, comprising the steps of: (A) reacting a compound represented by the following chemical formula 1 with sodium metabisulfite (NaSO) or sodium hydrogen sulfite to produce a compound represented by the following chemical formula 2; (B) reacting the compound represented by the following chemical formula 2 with a thionyl halide to produce a compound represented by the following chemical formula 3; and (C) hydrolyzing the compound represented by the following chemical formula 3 to produce a compound represented by chemical formula I.

[0015] [ka]

[0016] [ka]

[0017] [ka]

[0018] 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 of the formula X is a halogen.

[0019] (5) The present invention provides a method for producing the compound according to (4) above, wherein R1 to R8 are each independently hydrogen or an unsubstituted C1-C6 alkyl group.

[0020] (6) The present invention provides a method for producing the compound according to (4) or (5) above, wherein the step (A) is carried out at a pH of 7.0 to 7.5.

[0021] (7) The present invention provides a method for producing the compound according to any one of (4) to (6) above, wherein step (A) is carried out at a temperature of 60°C to 70°C.

[0022] (8) The present invention provides a method for producing the compound according to any one of (4) to (7) above, wherein the step (B) is carried out at a temperature of 60°C to 70°C.

[0023] (9) The present invention relates to the above ( C The method for producing the compound according to any one of (4) to (8) above is provided, wherein step (a) is carried out at room temperature. [Effects of the Invention]

[0024] By using the compound represented by chemical formula I according to the present invention, a derivative can be stably introduced into the carbon position adjacent to oxygen in the ring structure of the cyclic sulfonate derivative compound. [Brief explanation of the drawings]

[0025] [Figure 1] This is the 1H-NMR spectrum of the compound represented by chemical formula a. DETAILED DESCRIPTION OF THE INVENTION

[0026] The present invention will now be described in more detail.

[0027] The terms and words used in this 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 idea of the present invention, based on the principle that the inventors can appropriately define the concepts of terms in order to best explain their inventions.

[0028] The terms used in the present invention are merely used to describe specific embodiments and are not intended to limit the present invention. A singular expression includes a plural expression unless the context clearly indicates otherwise. In the present invention, the terms "comprise" or "have" and the like are intended to specify the presence of features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, and should not be understood to preclude the presence or possibility of addition of one or more other features, numbers, steps, operations, components, parts, or combinations thereof.

[0029] Compounds represented by formula I The present invention provides a compound represented by Formula I:

[0030] [ka]

[0031] In the above chemical formula I, m is 0 or 1, R1 to R8 are each independently hydrogen; or substituted or unsubstituted C1-C 10 is an alkyl group.

[0032] In the present invention, in the case of a substituted alkyl group, the substituent may be deuterium, a halogen group, a hydroxy group, an amino group, a thiol group, a cyano group, or a linear or branched C1-C6 alkoxy group.

[0033] The compound represented by the chemical formula I is a precursor of a cyclic sulfonate derivative compound, and can stably introduce a derivative into the carbon position adjacent to oxygen in the ring structure of the cyclic sulfonate derivative compound.

[0034] According to the present invention, in view of ease of synthesis of the compound of Chemical Formula I, R1 to R8 may each independently be hydrogen or an unsubstituted C1-C6 alkyl group. Specifically, in view of ease of synthesis and structural stability, R1 to R8 may all be hydrogen.

[0035] On the other hand, when m is 0, it is more advantageous in terms of reductive decomposition.

[0036] According to the present invention, the compound represented by the chemical formula I may be a compound represented by the following chemical formula a or b. Specifically, the compound represented by the chemical formula I may be a compound represented by the following chemical formula a.

[0037] [ka]

[0038] [ka]

[0039] Meanwhile, the compound represented by Formula I can be used as a precursor for preparing a cyclic sulfonate derivative compound, for example, the compound represented by Formula I can be used as a precursor for preparing a compound represented by Formula II below.

[0040] [ka]

[0041] In the above chemical formula II, m is 0 or 1, R1 to R8 are each independently hydrogen; or substituted or unsubstituted C1-C 10 is an alkyl group of the formula Y is -SOR', -SOR', -OC(=O)NHR', -OC(=S)NHR', The R' is a lithium salt or a substituted or unsubstituted C1-C10 is an alkyl group.

[0042] The compound represented by Formula II can be prepared by either i) reacting the hydroxy group of the compound represented by Formula I with SOCl2 to form a chlorosulfonate salt, followed by reaction with an alkyl alcohol, a fluoro alcohol, or a cyano alcohol, or ii) reacting the hydroxy group of the compound represented by Formula I with a halogen-containing compound, an isocyanate, or a thiocyanate functional group.

[0043] When the compound represented by Formula II is contained in a non-aqueous electrolyte, it can form a thin and stable SEI layer, thereby providing a lithium secondary battery with excellent high-temperature stability and life characteristics.

[0044] Methods for preparing compounds of formula I The present invention also provides a method for producing a compound, comprising the steps of: (A) reacting a compound represented by the following chemical formula 1 with sodium metabisulfite or sodium hydrogen sulfite to produce a compound represented by the following chemical formula 2; (B) reacting the compound represented by the following chemical formula 2 with a thionyl halide to produce a compound represented by the following chemical formula 3; and (C) hydrolyzing the compound represented by the following chemical formula 3 to produce a compound represented by chemical formula I.

[0045] [ka]

[0046] [ka]

[0047] [ka]

[0048] 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 of the formula X is a halogen.

[0049] According to the present invention, in terms of ease of synthesis, R1 to R8 may each independently be hydrogen or an unsubstituted C1-C6 alkyl group. Specifically, in terms of ease of synthesis and structural stability, R1 to R8 may all be hydrogen.

[0050] Step (A) is a step of adding sodium bisulfite to the alkene of the compound represented by Chemical Formula 1. At this time, the pH can be adjusted so that the main product (the compound represented by Chemical Formula 2) is the product of sodium bisulfite being added to the carbons to which R5 and R6 are attached.

[0051] According to the present invention, step (A) may be carried out at a pH of 7.0 to 7.5, specifically, 7.0 to 7.3, so that the compound represented by Chemical Formula 2 is produced as a main product, and the pH may be adjusted using sodium hydroxide or the like.

[0052] According to the present invention, step (A) may be carried out at 60 to 70° C. Specifically, step (A) may be a step of reacting the compound represented by Chemical Formula 1 with sodium metabisulfite or sodium hydrogen sulfite at 60 to 70° C. for 5 to 10 hours, and water can be used as the solvent.

[0053] The step (B) is a step in which the two hydroxy groups of the compound represented by the chemical formula 2 form a ring containing —OS(═O)—O— of the compound represented by the chemical formula 3.

[0054] According to the present invention, step (B) may be carried out at 60 to 70°C. Specifically, step (B) may be a step of reacting the compound represented by Chemical Formula 2 with thionyl halide at 60 to 70°C for 5 to 10 hours. A non-polar solvent such as CHCl3 can be used as the solvent. Meanwhile, the thionyl halide in step (B) may be thionyl fluoride or thionyl chloride. Step (B) may be carried out in the presence of a catalyst such as N,N-dimethylformamide.

[0055] Step (C) is a step of adding alcohol or water to the intermediate compound of Formula 3 to form a sultone structure through hydrolysis.

[0056] According to the present invention, the step (C) may be carried out at room temperature, for example, at 20° C. to 30° C. Specifically, the step (C) may be a step of reacting the compound represented by Chemical Formula 3 with water or an alcohol at room temperature for 1 hour to 5 hours, and the alcohol may be, for example, methanol, ethanol, etc.

[0057] The present invention will be described in more detail below with reference to specific examples. However, the following examples are merely illustrative for understanding the present invention and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the present description and technical concept, and it goes without saying that such changes and modifications fall within the scope of the appended claims.

[0058] Example Example 1. Preparation of a compound represented by formula a

[0059] [ka]

[0060] 32 g (368 mmol) of 3-butene-1,2-diol was dissolved in 200 ml of deionized water (DI water) and 576 g (404 mmol) of NaSO was added. Sodium hydroxide was added to the mixture to maintain the pH at 7.0, and the mixture was reacted at 65°C for 7 hours. After the reaction was complete, the reaction solution was cooled to room temperature and subjected to vacuum distillation. When the solution began to turn opaque and milky-colored, the vacuum distillation was stopped and methanol was added. The reaction solution was then filtered, and the filtered solution was vacuum distilled to precipitate a white solid, which was then dried in a vacuum oven at 60°C, yielding 77 g of sodium 3,4-dihydroxybutanesulfonate (purity: 90%).

[0061] 30 g (160 mmol, 90% purity) of sodium 3,4-dihydroxybutanesulfonate was suspended in 200 ml of CHCl3, 0.58 g (10 mmol, Aldrich) of N,N-dimethylformamide (DMF) was added, and 37.57 g (320 mmol, Aldrich) of thionyl chloride was added dropwise in small portions, followed by a reaction at 65°C for 7 hours. After completion of the reaction, the reaction solution was cooled to room temperature and filtered, and the filtered solution was concentrated under reduced pressure.

[0062] To the solution concentrated under reduced pressure, 50 g of methanol (1.57 mol, Aldrich) was added, and the mixture was allowed to react at room temperature for 2 hours.

[0063] After the reaction was completed, the reaction solution was concentrated under reduced pressure, and then 50 ml of ethyl acetate and 30 ml of water were added to the resulting concentrated solution and stirred. The organic layer (ethyl acetate layer) was extracted, washed with water, and then further concentrated to obtain 20 g (yield: 83%) of a transparent liquid compound represented by chemical formula a (5-(hydroxymethyl)-1,2-oxathiolane-2,2-dioxide).

[0064] The compound represented by the chemical formula a 1 The H-NMR data is as follows: 1 The H-NMR spectrum is shown in Figure 1. 1H-NMR (Acetonitrile-d3): δ 4.67(1H), δ 3.6-3.8(2H), δ 3.2-3.4(2H), δ 2.3-2.6(2H)

Claims

1. A compound represented by the following chemical formula I: 【Chemical 1】 (wherein, in the above chemical formula I, m is 0 or 1; R １ ~R ８ are each independently hydrogen; or unsubstituted C １ -C １０ is an alkyl group represented by the formula:

2. The R １ ~R ８ are each independently hydrogen; or unsubstituted C １ -C ６ 2. The compound of claim 1, wherein the alkyl group is:

3. The compound according to claim 1, wherein the compound represented by chemical formula I is a compound represented by the following chemical formula a or chemical formula b: 【Chemistry 2】

4. (A) reacting a compound represented by the following chemical formula 1 with sodium metabisulfite or sodium hydrogen sulfite to produce a compound represented by the following chemical formula 2: (B) reacting a compound represented by the following chemical formula 2 with thionyl halide to produce a compound represented by the following chemical formula 3: (C) hydrolyzing a compound represented by the following chemical formula 3 to produce a compound represented by chemical formula I: 【Chemistry 3】 (In the above Chemical Formulas 1 to 3, m is 0 or 1; R １ ~R ８ are each independently hydrogen; or unsubstituted C １ -C １０ is an alkyl group of the formula X is a halogen.

5. The R １ ~R ８ are each independently hydrogen; or unsubstituted C １ -C ６ The method for producing the compound according to claim 4, wherein the alkyl group is

6. The method for producing the compound according to claim 4, wherein the step (A) is carried out at a pH of 7.0 to 7.

5.

7. The method for producing the compound according to claim 4, wherein the step (A) is carried out at 60°C to 70°C.

8. The method for producing the compound according to claim 4, wherein the step (B) is carried out at a temperature of 60°C to 70°C.

9. The method for producing the compound according to claim 4, wherein step (C) is carried out at room temperature.

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