Method for producing benzenesulfonyl compounds

Abstract

This invention provides a highly productive manufacturing method that allows for the production of benzenesulfonyl compounds in extremely high yields, even through a simple process. [Solution] The present invention relates to a method for producing benzenesulfonyl compounds in the presence of a phase-transfer catalyst and an aqueous alkali metal hydroxide solution, and is capable of producing benzenesulfonyl compounds in high yield even under mild reaction conditions with excellent reaction rate.

Description

[Technical Field]

[0001] This disclosure relates to a method for producing benzenesulfonyl compounds. [Background technology]

[0002] Benzenesulfonyl compounds are known to form a uniform SEI layer on the electrode surface when applied as an electrolyte additive, thereby providing high battery stability. Research is being conducted on benzenesulfonyl compounds with diverse structures that have effective properties as electrolyte additives, but research on their synthesis methods is still insufficient.

[0003] Currently, the synthesis of benzenesulfonyl compounds is fraught with several technical difficulties, which increase production costs during mass production and limit commercial applicability. For example, the use of expensive catalysts makes mass production difficult. Attempting to switch to more commercially viable catalysts involves multi-step processes or slower reaction rates, leading to a significant increase in the amount of starting materials used compared to the product, resulting in lower yields and reduced productivity. [Prior art documents] [Patent Documents]

[0004] [Non-Patent Document 1] Bioorganic & Medicinal Chemistry Letters(2022),75,128956 [Overview of the project] [Problems that the invention aims to solve]

[0005] One embodiment aims to provide a highly productive manufacturing method that allows for the acquisition of benzenesulfonyl compounds in extremely high yields through a simple process. [Means for solving the problem]

[0006] One embodiment provides a method for producing a benzenesulfonyl compound, comprising the step of reacting a compound represented by the following chemical formula 2 with an n-valent alcohol in the presence of a phase transfer catalyst and an aqueous alkali metal hydroxide solution to produce a benzenesulfonyl compound represented by the following chemical formula 1.

[0007] [ka]

[0008] [ka] (In the above chemical formulas 1 and 2, R 1 ~R 5 These are, independently, hydrogen, halogen, C1-C7 alkoxy, or C1-C7 alkyl, X is an n-valent alcohol-derived residue, n is an integer between 1 and 4. Y is a halogen.

[0009] The alkali metal hydroxide aqueous solution may contain alkali metal hydroxide in an amount of 40 to 70 wt%.

[0010] The phase-transfer catalyst may be an ammonium-based catalyst.

[0011] For every 1 mole of the aforementioned n-valent alcohol, 0.3n to 1n moles of the compound represented by chemical formula 2 are used, where n may be an integer from 1 to 4.

[0012] For every 1 mole of the aforementioned n-valent alcohol, 0.3n to 0.8n moles of the compound represented by chemical formula 2 are used, and n may be an integer from 1 to 4.

[0013] For every mole of the compound represented by chemical formula 2, 1 to 5 moles of the alkali metal hydroxide may be used.

[0014] The alkali metal hydroxide and the phase transfer catalyst may be used in a molar ratio of 1:0.005 to 0.05.

[0015] In the method for producing the benzenesulfonyl compound according to one embodiment, the reaction may be carried out at a temperature of 20 to 40 °C for 1 to 10 hours.

[0016] In the method for producing the benzenesulfonyl compound according to one embodiment, the yield of the benzenesulfonyl compound may be 60% or more.

Advantages of the Invention

[0017] The method for producing a benzenesulfonyl compound according to one embodiment can provide a benzenesulfonyl compound in excellent yield by simple steps. Specifically, the production method according to one embodiment has an excellent reaction rate even under mild reaction conditions, has a short reaction time, and can produce a benzenesulfonyl compound in high yield using economical materials. Therefore, it has very excellent productivity and can be advantageously applied to the actual industrial site.

Modes for Carrying Out the Invention

[0018] Unless otherwise defined herein, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terms used in the description herein are for the purpose of effectively describing specific examples only and are not intended to limit the invention.

[0019] The singular forms used in the present invention are intended to include the plural forms as well, unless the context specifically indicates otherwise.

[0020] Throughout this specification, when an element is described as "comprising", "including", "containing", or "having", it means that it can further include other elements without excluding other elements, materials, or steps, unless otherwise stated to the contrary.

[0021] As used herein, numerical ranges include lower and upper limits, all values ​​within those ranges, increments logically derived from the form and width of the defined range, all double-limited values, and all possible combinations of upper and lower limits of numerical ranges limited in different forms. Unless otherwise defined in the specification of the present invention, values ​​outside the numerical range that may arise due to experimental error or rounding of values ​​are also included in the defined numerical range.

[0022] Unless otherwise defined herein, “approximately” may refer to values ​​up to 30%, 25%, 20%, 15%, 10%, or 5% of the specified value.

[0023] The following provides a detailed description of this disclosure. However, this is illustrative only and the disclosure is not limited to the specific embodiments described herein.

[0024] As used herein, the term "halogen" may mean a fluorine (F), chlorine (Cl), bromine (Br), or iodine (I) atom.

[0025] The term "alkyl" as used herein refers to an organic radical derived from an aliphatic hydrocarbon by the removal of one hydrogen atom, and may include both linear and branched forms. The alkyl may have 1 to 7 carbon atoms, specifically 1 to 5 carbon atoms, specifically 1 to 4 carbon atoms, or specifically 1 to 3 carbon atoms. Examples of the alkyl include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, and ethylhexyl.

[0026] The term "alkoxy" as used herein is denoted by *-O-alkyl, where alkyl is as defined above. Examples of such alkoxys include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, and t-butoxy.

[0027] One embodiment provides a method for producing benzenesulfonyl compounds that can simultaneously simplify the manufacturing process, improve yield, and increase productivity.

[0028] Specifically, a method for producing a benzenesulfonyl compound according to one embodiment may include the step of reacting a compound represented by the following chemical formula 2 with an n-valent alcohol in the presence of a phase transfer catalyst and an aqueous alkali metal hydroxide solution to produce a benzenesulfonyl compound represented by the following chemical formula 1.

[0029] [ka]

[0030] [ka] (In the above chemical formulas 1 and 2, R 1 ~R 5 These are, independently, hydrogen, halogen, C1-C7 alkoxy, or C1-C7 alkyl, X is an n-valent alcohol-derived residue, n is an integer between 1 and 4. Y is a halogen.

[0031] Conventional methods for producing benzenesulfonyl compounds have a problem in that when economical base catalysts such as alkali metal hydroxide are introduced to ensure cost-effectiveness, an excess of catalyst is used, resulting in a decrease in both reaction rate and yield. One embodiment of the production method uses a combination of a phase transfer catalyst and an aqueous alkali metal hydroxide solution, enabling the production of benzenesulfonyl compounds in high yield with excellent reaction rate even under mild reaction conditions.

[0032] The alkali metal hydroxide aqueous solution may contain alkali metal hydroxide in amounts of 20-80 wt%, 30-80 wt%, 40-80 wt%, 40-70 wt%, or 40-60 wt%, and can achieve a better yield.

[0033] The alkali metal hydroxide may be used in amounts of 0.1 to 10 moles, 1 to 10 moles, 1 to 8 moles, or 1 to 6 moles, 1 to 5 moles, or 1 to 3 moles, or 1.2 to 3 moles, or 1.5 to 3 moles, or 1.5 to 2 moles, per mole of the compound represented by chemical formula 2. When using an aqueous solution of alkali metal hydroxide within the above concentration range to satisfy the above molar ratio, better reaction rates and yields can be achieved.

[0034] The alkali metal hydroxide and the phase transfer catalyst may be used in a molar ratio of 1:0.001 to 0.1, 1:0.001 to 0.05, 1:0.005 to 0.05, 1:0.005 to 0.03, or 1:0.01 to 0.03.

[0035] The alkali metal hydroxide may be sodium hydroxide (NaOH) or potassium hydroxide (KOH).

[0036] The phase-transfer catalyst (PTC) may be an ammonium-based catalyst, and as an example, it may be an ammonium halide catalyst such as tetramethylammonium bromide, tetramethylammonium chloride, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium chloride, cetyltrimethylammonium bromide, benzyltriethylammonium chloride, or trioctylmethylammonium chloride.

[0037] For every mole of the aforementioned n-valent alcohol, the compound represented by chemical formula 2 may be used in amounts of 0.2n moles or more, 0.3n moles or more, 2n moles or less, 1.5n moles or less, or 1n mole or less. Specifically, it may be used in amounts of 0.2n to 2n moles, 0.3n to 1.5n moles, or 0.3n to 1.2n moles, or 0.3n to 1.0n moles, or 0.3n to 0.9n moles, or 0.3n to 0.8n moles. In this case, a better yield of the benzenesulfonyl compound can be achieved, and all possible combinations of the upper and lower limits of the numerical range may be included, where n may be an integer from 1 to 4 or an integer from 2 to 4.

[0038] The aforementioned n-valent alcohol means an alcohol having n hydroxyl groups (-OH), and may be a monovalent, divalent, trivalent, or tetravalent alcohol. As an example, the n-valent alcohol may be, but is not limited to, a monovalent alcohol selected from methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, etc., a divalent alcohol selected from ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, etc., a trivalent alcohol such as glycerol, trimethylolpropane, etc., or a tetravalent alcohol such as pentaerythritol, erythritol, etc.

[0039] For example, the n-valent alcohol may be a divalent alcohol, and the compound represented by chemical formula 2 may be used in amounts of 0.5 to 3 moles, 0.5 to 2 moles, 0.6 to 2.5 moles, 0.6 to 2 moles, 0.6 to 1.8 moles, or 0.6 to 1.6 moles per mole of the divalent alcohol, and may include all possible combinations of the upper and lower limits of the above numerical range.

[0040] For example, the n-valent alcohol may be a trivalent alcohol, and the compound represented by chemical formula 2 may be used in amounts of 0.5 to 4 moles, 0.5 to 3 moles, 1 to 3 moles, 1 to 2.5 moles, or 1 to 2 moles per mole of the trivalent alcohol, and may include all possible combinations of the upper and lower limits of the above numerical range.

[0041] As an example, R 1 ~R 5 Each of these may independently be hydrogen, halogen, C1-C4 alkoxy, or C1-C4 alkyl, and may be hydrogen, fluoro(-F), or methyl.

[0042] The manufacturing method according to one embodiment exhibits excellent reaction rate even under mild reaction conditions and can produce benzenesulfonyl compounds in high yield. For example, the reaction may be carried out at a temperature of 20 to 40°C for 1 to 10 hours, or 2 to 10 hours, or 3 to 8 hours, and the yield of the benzenesulfonyl compound may be 60% or more, or 70% or more, or 75% or more, or 80% or more, or 90% or more, with an upper limit of 99%.

[0043] The embodiments described above will be explained in more detail below with reference to examples. However, the following examples are for illustrative purposes only and do not limit the scope of the rights.

[0044] [Example 1] [ka] A round-bottom flask containing 0.15 mol of ethylene glycol, 0.005 mol of benzyltriethylammonium chloride (BnEt3NCl), and 30 mL of dichloromethane (DCM) was cooled to 0°C, and 0.2 mol of benzenesulfonyl chloride was added while stirring. Next, 0.3 mol of sodium hydroxide was added as a 50 wt% aqueous sodium hydroxide solution. The internal temperature was maintained below 30°C during the addition, and after the addition was complete, the mixture was stirred further at room temperature (25°C) for 5 hours. After the reaction was complete, the organic layer was washed twice with water, concentrated, and then recrystallized with methanol to obtain 1,2-bis(benzenesulfonyloxy)ethane (93%). 1 H-NMR (CDCl3,500MHz,ppm):7.87(4H,m),7.68(2H,m),7.56(4H,m),4.23(4H,s).

[0045] [Example 2] The procedure was carried out in the same manner as in Example 1, except that the amount of ethylene glycol used was changed to 0.13 mol.

[0046] [Example 3] The procedure was carried out in the same manner as in Example 1, except that the amount of ethylene glycol used was changed to 0.1 mol.

[0047] [Example 4] The procedure was carried out in the same manner as in Example 3, except that the amount of sodium hydroxide used was changed to 0.2 mol.

[0048] [Example 5] The procedure was carried out in the same manner as in Example 3, except that a 30 wt% sodium hydroxide aqueous solution was used instead of a 50 wt% sodium hydroxide aqueous solution.

[0049] [Example 6] The procedure was carried out in the same manner as in Example 1, except that the amount of benzyltriethylammonium chloride used was changed to 0.002 mol.

[0050] [Example 7] The procedure was carried out in the same manner as in Example 1, except that the amount of ethylene glycol used was changed to 0.3 mol.

[0051] [Example 8] The procedure was carried out in the same manner as in Example 1, except that tetrabutylammonium bromide was used instead of benzyltriethylammonium chloride.

[0052] [Example 9] The procedure was carried out in the same manner as in Example 1, except that a 50 wt% potassium hydroxide aqueous solution was used instead of a 50 wt% sodium hydroxide aqueous solution.

[0053] [Comparative Example 1] The procedure was carried out in the same manner as in Example 4, except that benzyltriethylammonium chloride was not used.

[0054] [Comparative Example 2] The procedure was carried out in the same manner as in Example 4, except that 0.05 mol of triethylamine was used instead of benzyltriethylammonium chloride.

[0055] The molar ratios listed in Table 1 below represent the molar ratio to 1 mole of benzenesulfonyl chloride.

[0056] [Table 1]

[0057] [Example 10] [ka] The procedure of Example 1 was repeated, except that 4-fluorobenzenesulfonyl chloride was used instead of benzenesulfonyl chloride, to obtain (1,2-bis(4-fluorobenzenesulfonyloxy)ethane) (94%). 1 H-NMR (CDCl3, 500 MHz, ppm): 7.89 (4H, m), 7.23 (4H, m), 4.25 (4H, s).

[0058] [Example 11] [Chemical Formula] The procedure of Example 1 was repeated, except that 0.1 mol of glycerol was used instead of 0.15 mol of ethylene glycol, to obtain (1,2,3-tris(benzenesulfonyloxy)propane) (90%). 1 H-NMR (CDCl3, 500 MHz, ppm): 7.82 (6H, m), 7.68 (3H, m), 7.55 (6H, m), 4.74 (1H, p), 4.13 (4H, d).

[0059] As described above, in this specification, the disclosure has been described by specific matters and limited embodiments, but this is only provided for a more general understanding of the disclosure, and the disclosure is not limited to the above embodiments. Those with ordinary knowledge in the field to which the disclosure pertains can make various modifications and variations from such descriptions.

Claims

1. A method for producing a benzenesulfonyl compound, comprising the step of reacting a compound represented by the following chemical formula 2 with an n-valent alcohol in the presence of a phase transfer catalyst and an aqueous alkali metal hydroxide solution to produce a benzenesulfonyl compound represented by the following chemical formula 1. 【Chemistry 1】 【Chemistry 2】 (In the above chemical formulas 1 and 2, R １ ~R ５ These are, independently, hydrogen, halogen, C1-C7 alkoxy, or C1-C7 alkyl, X is an n-valent alcohol-derived residue, n is an integer between 1 and 4. Y is a halogen.

2. The method for producing a benzenesulfonyl compound according to claim 1, wherein the aqueous alkali metal hydroxide solution contains 40 to 70 wt% alkali metal hydroxide.

3. The method for producing a benzenesulfonyl compound according to claim 1, wherein the phase transfer catalyst is an ammonium-based catalyst.

4. A method for producing a benzenesulfonyl compound according to claim 1, wherein 0.3n to 1n moles of the compound represented by chemical formula 2 are used per mole of the n-valent alcohol, and the n is an integer from 1 to 4.

5. A method for producing a benzenesulfonyl compound according to claim 4, wherein 0.3n to 0.8n moles of the compound represented by chemical formula 2 are used per mole of the n-valent alcohol, and the value of n is an integer from 1 to 4.

6. A method for producing a benzenesulfonyl compound according to claim 1, wherein 1 to 5 moles of the alkali metal hydroxide are used per 1 mole of the compound represented by chemical formula 2.

7. The method for producing a benzenesulfonyl compound according to claim 6, wherein the alkali metal hydroxide and the phase transfer catalyst are used in a molar ratio of 1:0.005 to 0.

05.

8. The method for producing a benzenesulfonyl compound according to claim 1, wherein the reaction is carried out at a temperature of 20 to 40°C for 1 to 10 hours.

9. The method for producing a benzenesulfonyl compound according to claim 1, wherein the yield of the benzenesulfonyl compound is 60% or more.

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