KR20230108134A - Manufacturing method of cyclic sulfonic acid ester derivative compound - Google Patents

Abstract

The present invention is an invention to provide a manufacturing method capable of producing a cyclic sulfonic acid ester derivative compound with a yield equal to or higher than that of the conventional one under conditions in which toxic substances are excluded, (A) N-formylmorpholine (N-Formylmorpholine , NFM) reacting a compound represented by Formula 1 described herein with a thionyl halide under a catalyst to prepare a compound represented by Formula 2 described herein; and (B) hydrolyzing the compound represented by Formula 2 to prepare a compound represented by Formula 3 described herein.

Description

Manufacturing method of cyclic sulfonic acid ester derivative compound {MANUFACTURING METHOD OF CYCLIC SULFONIC ACID ESTER DERIVATIVE COMPOUND}

The present invention relates to a method for producing a cyclic sulfonic acid ester derivative compound.

1,3-propane sultone and 1,4-butane sultone are known as useful compounds as non-aqueous electrolyte additives in lithium secondary batteries. However, 1,3-propane sultone and 1,4-butane sultone have problems such as toxicity issues, gas generation, stability, etc. Therefore, studies on cyclic sulfonic acid ester derivative compounds that can be used as non-aqueous electrolyte additives are being actively conducted. . For example, a cyclic sulfonic acid ester derivative compound in which a substituent containing a hydroxyl group is introduced at the gamma position of 1,3-propane sultone (the carbon position next to oxygen in the ring structure) or the delta position of 1,4-butane sultone (the carbon position next to oxygen in the ring structure) When a cyclic sulfonic acid ester derivative compound introducing a substituent containing a hydroxyl group at the carbon position next to oxygen in ) is used as a non-aqueous electrolyte additive for a lithium secondary battery, it forms an electrode-electrolyte interface that is stable even at high temperatures and has low resistance, thereby forming a lithium secondary battery. Life characteristics of the battery can be improved.

Meanwhile, the cyclic sulfonic acid ester derivative compound may be prepared by, for example, reacting a sodium salt of sulfonic acid with thionyl chloride. At this time, since the reactivity of the sodium salt of sulfonic acid is low, dimethylformamide (Dimehtylformamide, DMF) is necessarily used as a catalyst. DMF is a toxic substance with strong reproductive toxicity, and cyclic sulfonic acid esters without using DMF to exclude toxic substances. There is a need for research on methods for preparing derivative compounds.

The present invention is to provide a method for preparing a cyclic sulfonic acid ester derivative compound under conditions in which toxic substances are excluded.

The present invention (A) preparing a compound represented by the formula (2) by reacting a compound represented by the formula (1) with a thionyl halide in the presence of an N-formylmorpholine (NFM) catalyst; and

(B) hydrolyzing the compound represented by Formula 2 to prepare a compound represented by Formula 3;

[Formula 1]

[Formula 2]

[Formula 3]

In Formulas 1 to 3,

m is 0 or 1;

R ₁ to R ₈ are each independently hydrogen; Or a substituted or unsubstituted C ₁ -C ₁₀ alkyl group,

X is a halogen group.

According to the present invention, by using NFM as a substitute for DMF, a cyclic sulfonic acid ester derivative compound can be produced with a yield equal to or higher than that of conventional compounds under conditions in which toxic substances are excluded.

1 is a ¹ H-NMR spectrum of the product prepared in Example 1.
2 is a ¹ H-NMR spectrum of the product prepared in Comparative Example 1.

Hereinafter, the present invention will be described in more detail to aid understanding of the present invention. At this time, the terms or words used in this specification and claims should not be construed as being limited to ordinary or dictionary meanings, and the inventor appropriately defines the concept of terms in order to explain his/her invention in the best way. It should be interpreted as meaning and concept consistent with the technical idea of the present invention based on the principle that it can be done.

The present invention relates to a method for producing a cyclic sulfonic acid ester derivative compound, wherein (A) a compound represented by Formula 1 is reacted with a thionyl halide in the presence of N-Formylmorpholine (NFM) catalyst to obtain Formula 2 Preparing a compound represented by; and (B) hydrolyzing the compound represented by Formula 2 to prepare a compound represented by Formula 3 below.

[Formula 1]

[Formula 2]

[Formula 3]

In Formulas 1 to 3,

m is 0 or 1;

R ₁ to R ₈ are each independently hydrogen; Or a substituted or unsubstituted C ₁ -C ₁₀ alkyl group,

X is a halogen group.

In the present invention, the substituent in the substituted alkyl group is deuterium, a halogen group, a hydroxyl group, -COOR group (R is an unsubstituted C ₁ -C ₆ alkyl group), -SO ₂ NR' ₂ group (R' is hydrogen or an unsubstituted C ₁ -C ₆ alkyl group), a cyano group, or a straight or branched C ₁ -C ₆ alkoxy group.

In terms of ease of synthesis of Formula 3, R ₁ to R ₈ are each independently hydrogen; Or it may be an unsubstituted C ₁ -C ₆ alkyl group. Specifically, R ₁ to R ₈ may all be hydrogen in view of ease of synthesis and structural stability.

The compound represented by Formula 3 may be a compound represented by Formula a or b below.

[Formula a]

[Formula b]

.

Hereinafter, each step of the method for producing a cyclic sulfonic acid ester derivative compound will be described in detail.

(A) step

Step (A) is a step in which the two hydroxyl groups of the compound represented by Formula 1 form a ring containing -O-S(=O)-O- of the compound represented by Formula 2. In the present invention, by using NFM instead of DMF as a catalyst in step (A), a cyclic sulfonic acid ester derivative compound can be prepared under conditions in which toxic substances are excluded. In addition, the yield when the cyclic sulfonic acid ester derivative compound is prepared by the manufacturing method according to the present invention may be equal to or higher than the yield when the cyclic sulfonic acid ester derivative compound is prepared by the manufacturing method using DMF.

According to the present invention, the step (A) precipitates an inorganic salt as a by-product to increase the conversion rate of the compound represented by Formula 1 to the compound represented by Formula 2, and to facilitate the removal of the inorganic salt. It may be performed in a non-polar solvent.

According to the present invention, the non-polar solvent may be at least one selected from chloroform, dichloromethane, toluene and 1,2-dichlorobenzene. In this case, an inorganic salt as a by-product is not dissolved, but an organic salt as a reactant has an advantage in that it can be dissolved at a certain concentration.

According to the present invention, the step (A) may be performed at a temperature of 35 °C to 65 °C, specifically 45 °C to 55 °C. In this case, the compound represented by Formula 1 may be dissolved in a non-polar solvent at an appropriate effective concentration.

Step (A) may be performed for 2 to 10 hours to ensure a reaction conversion rate of 95% or more (conversion rate of the compound represented by Chemical Formula 1 to the compound represented by Chemical Formula 2).

Step (A) may be a step of reacting the compound represented by Formula 1 and the thionyl halide under a NFM catalyst at a temperature of 45 ° C to 55 ° C for 5 to 10 hours, and CHCl ₃ as a solvent. of non-polar solvents may be used. Meanwhile, the thionyl halide in step (A) may be thionyl fluoride or thionyl chloride.

According to the present invention, the equivalent ratio of the compound represented by Formula 1 and the N-formylmorpholine catalyst is 1:0.01 to 1:0.5, specifically 1:0.02 to 1:0.3, more specifically It may be 1:0.025 to 1:0.1. When the equivalent ratio of the compound represented by Formula 1 and the N-formylmorpholine catalyst is within the above range, the reaction conversion rate (conversion rate of the compound represented by Formula 1 to the compound represented by Formula 2) ) can be maintained high, and the amount of residual catalyst after the reaction can be minimized.

According to the present invention, the equivalent ratio of the compound represented by Formula 1 and the thionyl halide is 1:1.5 to 1:5, specifically 1:2 to 1:4, more specifically 1:2.5 to 1:3.5 can be When the equivalent ratio of the compound represented by Formula 1 and the thionyl halide is within the above range, the reaction conversion rate (the conversion rate of the compound represented by Formula 1 to the compound represented by Formula 2) can be maintained high, and the corrosive compound The amount of thionyl phosphorus halide used can be minimized.

(B) step

Step (B) is a step of injecting alcohol and/or water into the compound represented by Chemical Formula 2, which is a reaction intermediate, to form a sultone structure through a hydrolysis process (to form a compound represented by Chemical Formula 3). am.

According to the present invention, the step (B) may be performed under an acid catalyst to quickly decompose the sulfite ester structure present in the compound represented by Formula 2.

According to the present invention, the step (B) may be performed in a polar protic solvent to quickly decompose the sulfite ester structure present in the compound represented by Formula 2.

According to the present invention, the polar protic solvent may be at least one selected from distilled water, methanol, ethanol, propanol, and isopropanol. In this case, there is an advantage of easy removal of reaction by-products (eg, dialkyl sulfite esters).

According to the present invention, step (B) may be performed at a temperature of 0 ° C to 25 ° C, specifically 0 ° C to 15 ° C. In this case, decomposition of the compound represented by Chemical Formula 3 can be inhibited.

The step (B) may be performed for 1 hour to 5 hours to secure a reaction conversion rate (a conversion rate of the compound represented by Chemical Formula 2 to the compound represented by Chemical Formula 3).

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.

Examples and Comparative Examples

Example 1

After dispersing 1.9 g (1 equivalent) of 3,4-dihydroxybutane-1-sulfonic acid sodium salt in 10 ml of chloroform, 0.08 ml (0.1 equivalent) of NFM was added. After adding 1.5ml (2 equivalents) of SOCl ₂ dropwise at room temperature, the mixture was stirred and reacted at 55° C. for 8 hours. After completion of the reaction, the reaction solution was cooled to room temperature, filtered to remove solid by-products, and the filtrate was concentrated by distillation under reduced pressure. 10ml of methanol and 0.8ml of 12M HCl were added to the concentrated solution at 0°C, followed by hydrolysis while stirring for 2 hours, and distillation under reduced pressure to remove the solvent. The unpurified product was dissolved in DCM (dichloromethane), 2 g of Celite was added, stirred for 30 minutes, and the filtrate was concentrated after filtering Celite to obtain 0.67 g of a compound represented by Formula a. (Yield: 44%) was obtained.

Comparative Example 1

After dispersing 1.9 g (1 equivalent) of 3,4-dihydroxybutane-1-sulfonic acid sodium salt in 10 ml of chloroform, 0.08 ml (0.1 equivalent) of DMF was added. After adding 1.5ml (2 equivalents) of SOCl ₂ dropwise at room temperature, the mixture was stirred and reacted at 55° C. for 8 hours. After completion of the reaction, the reaction solution was cooled to room temperature, filtered to remove solid by-products, and the filtrate was concentrated by distillation under reduced pressure. 10ml of methanol and 0.8ml of 12M HCl were added to the concentrated solution at 0°C, followed by hydrolysis while stirring for 2 hours, and distillation under reduced pressure to remove the solvent. The unpurified product was dissolved in DCM (dichloromethane), 2 g of Celite was added, stirred for 30 minutes, and the filtrate was concentrated after filtering the Celite to obtain 0.55 g of a compound represented by Formula a. (Yield: 36%) was obtained.

Experimental example

In each of Example 1 and Comparative Example 1, it was confirmed by TLC that all of the 3,4-dihydroxybutane-1-sulfonic acid sodium salt was exhausted, and 0.05 ml of the reaction-completed solution was diluted with 0.45 ml of DMSO-d6. Using a magnetic resonance spectrometer (B500 Bruker Avace Neo, Bruker Co.), ¹ H-NMR spectrum was obtained, which is shown in FIGS. 1 and 2, respectively.

Through ¹ H-NMR spectrum, it was confirmed that the compound represented by Formula (a) was prepared in both Example 1 and Comparative Example 1, and in the case of Example 1, the yield of the compound represented by Formula (a) was 44%. It was confirmed that the yield was higher than the yield (36%).

For reference, the peaks at 2.897 ppm and 2.738 pp in the NMR of Comparative Example are the peaks of residual DMF.

As a result, according to the present invention, it can be seen that a cyclic sulfonic acid ester derivative compound can be produced with a yield equal to or higher than that of conventional compounds under conditions in which toxic substances are excluded.

Claims (10)

(A) preparing a compound represented by Formula 2 by reacting a compound represented by Formula 1 with a thionyl halide in the presence of an N-formylmorpholine catalyst; and
(B) hydrolyzing the compound represented by Chemical Formula 2 to prepare a compound represented by Chemical Formula 3; Method for preparing a cyclic sulfonic acid ester derivative compound comprising:
[Formula 1]

[Formula 2]

[Formula 3]

In Formulas 1 to 3,
m is 0 or 1;
R ₁ to R ₈ are each independently hydrogen; Or a substituted or unsubstituted C ₁ -C ₁₀ alkyl group,
X is a halogen group.
The method of claim 1,
The step (A) is a method for producing a cyclic sulfonic acid ester derivative compound that is performed in a non-polar solvent.
The method of claim 2,
The method of producing a cyclic sulfonic acid ester derivative compound wherein the non-polar solvent is at least one selected from chloroform, dichloromethane, toluene and 1,2-dichlorobenzene.
The method of claim 1,
The step (A) is a method for producing a cyclic sulfonic acid ester derivative compound that is carried out at a temperature of 35 ℃ to 65 ℃.
The method of claim 1,
The equivalent ratio of the compound represented by Formula 1 and the N-formylmorpholine catalyst is 1:0.01 to 1:0.5. Method for producing a cyclic sulfonic acid ester derivative compound.
The method of claim 1,
A method for producing a cyclic sulfonic acid ester derivative compound in which the equivalent ratio of the compound represented by Formula 1 and the thionyl halide is 1:1.5 to 1:5.
The method of claim 1,
The step (B) is a method for producing a cyclic sulfonic acid ester derivative compound that is performed under an acid catalyst.
The method of claim 1,
The step (B) is a method for producing a cyclic sulfonic acid ester derivative compound that is performed in a polar protic solvent.
The method of claim 8,
The polar protic solvent is at least one selected from distilled water, methanol, ethanol, propanol and isopropanol. Method for producing a cyclic sulfonic acid ester derivative compound.
The method of claim 1,
The step (B) is a method for producing a cyclic sulfonic acid ester derivative compound that is carried out at a temperature of 0 ℃ to 25 ℃.