KR102489550B1 - Method for preparing cyclic 1,3-propene sultone - Google Patents

Abstract

The present invention relates to a method for producing cyclic 1,3-propene sultone useful as an electrolyte additive for lithium ion secondary batteries, and more specifically, sodium 2,3-dihydroxypropane sulfonate as a starting material Halogenation with phosgene and simultaneous cyclic esterification to obtain 2-hydroxy-1,3-propane sultone or 2-chloro-1,3-propane sultone as an intermediate product, followed by 2-hydroxy-1,3- A leaving group hydrogen removal reaction is performed under basic conditions by introducing a leaving group from propane sultone, or a halogen hydrogen removal reaction is performed under basic conditions with respect to 2-chloro-1,3-propane sultone to obtain the desired product. It relates to a method for obtaining phosphorus cyclic 1,3-propene sultone.

Description

Method for preparing cyclic 1,3-propene sultone {Method for preparing cyclic 1,3-propene sultone}

The present invention relates to a method for producing cyclic 1,3-propene sultone useful as an electrolyte additive for lithium ion secondary batteries, and more specifically, sodium 2,3-dihydroxypropane sulfonate as a starting material Halogenation with phosgene (triphosgene) and simultaneous cyclic esterification to obtain an intermediate product, 2-hydroxy-1,3-propane sultone or 2-chloro-1,3-propane sultone, followed by the 2-hydroxy-1 , 3-propanesultone is introduced with a leaving group (leaving group) to carry out the leaving group hydrogen elimination reaction under basic conditions, or the halogen hydrogen elimination reaction is carried out under basic conditions for the 2-chloro-1,3-propanesultone It relates to a method for obtaining the desired cyclic 1,3-propene sultone by proceeding.

Cyclic sulfonic acid esters are generally compounds represented by the following [Formula A], and are used as electrolyte additives for lithium ion secondary batteries, in order to improve the stability of the battery, in particular, suppression of the reduction reaction of the electrolyte, high-temperature keeping warm test or high cycle test. It is known as a useful organic electronic material that can affect the suppression of battery performance degradation and gas generation, and consequently improve battery performance.

[Formula A]

In [Formula A], R ₁ , R ₂ , and R ₃ are each independently hydrogen, a halogen, a C1-C5 alkyl group, or a halogen-substituted C1-C5 alkyl group.

Conventionally, Chem. Commun. 1997, 611 and Tetrahedron, 1999, 2245 (W. H. Lee et al.) obtained a 2-bromo-1,3-propane sultone ring by sulfonation, bromination, and ring formation of bromoaryl as a starting material, and from the following reaction A method for preparing 1,3-propene sultone is presented. However, in this production method, 2,3-dibromosulfonic acid is prepared by bromination and then reacted under reduced pressure conditions of 2 mmHg or less and high temperature conditions of 130° C. or higher to form a 2-bromo-1,3-propane sultone ring. There is a burden to do, and at this time, the ring-opening reaction of the sultone ring proceeds together to produce oligomers and polymers in the form of sulfone esters. Since these reaction by-products are not well soluble in organic solvents, purification is difficult and the yield gradually decreases. .

In addition, Synlett, 2002, 2019 (Peter Metz et al.) proposes a method for producing 1,3-propene sultone using Ring Closing Metathesis from a vinyl intermediate, but in this case, the synthesis of divinylsulfonic acid ester, an intermediate It is difficult, requires an excessive amount of solvent to suppress intermolecular metathesis, requires the use of an expensive Grubbs ruthenium catalyst, and requires a purification process to remove the catalyst after the reaction, so it is not industrially used. There is a difficult problem.

In addition, in Korean Patent Registration No. 10-0895191 (April 20, 2009), 1,3-propane sultone is reacted with AIBN/SOCl ₂ to prepare 2-chloro-1,3-propane sultone, which is de- A method for preparing 1,3-propene sultone by halogenation has been proposed, but this method has a disadvantage in that a by-product purification step is required because 3-chloro-1,3-propane sultone is produced in the reaction process.

In addition, in Korean Registered Patent No. 10-1135088 (April 03, 2012), allylsulfonyl halide is reacted with a 1,3-dihalo-hydantoin compound and water to obtain 2-halo-3-hydroxypropanesulfonyl forming a halide; forming 2-halo-1,3-propane sultone by cyclization of the 2-halo-3-hydroxypropanesulfonylhalide; and dehalogenating the 2-halo-1,3-propane sultone; A method for producing 1,3-propene sultone characterized by including a is introduced.

However, this method has the burden of using explosive POCl ₃ as a halogenating agent, and there is a problem in that safety must be secured separately when removing POCl ₃ remaining after the reaction is completed. In addition, it is necessary to go through various steps such as sulfonation, halogenation, 1,3-dihalo-hydantoin addition reaction, cyclization, and dehalogenation as a whole. In particular, the halogenation reaction must proceed at a relatively high temperature of 80 to 120 ° C, and the reaction by-products Since a purification step of removing the 1-halo-hydantoin formed from is required, there is a problem in that overall economic efficiency is low.

Finally, in US Patent Publication No. US 2014/0142324 (A1) (May 22, 2014), 3-chloro-1,2-diol propane is subjected to a substitution reaction in Na ₂ SO ₃ and water to obtain 1,2-dihydroxy propane Step 1 of preparing sodium sulfonate; Step 2 of reacting sodium 1,2-dihydroxypropanesulfonate with SOCl ₂ in DMF and toluene to obtain cyclic sulfite ester chloride; a third step of preparing 2-hydroxy-1,3-propanesultone by reacting the cyclic sulfite ester chloride with 12N HCl (aq) or alcohol; Step 4 of reacting the 2-hydroxy-1,3-propane sultone with an acid anhydride (Ac ₂ O) and an acid halide (MsCl) to convert the 2-hydroxy functional group into a leaving group; 5 steps of treating the obtained compound with a base to obtain 1,3-propene sultone; A method consisting of is introduced.

In this method, an excessive amount of SOCl ₂ is used to prepare the cyclic sulfite ester chloride, the molecular weight is reduced in the thioldiol deprotection and esterification step, and 1,3-propene sultone is obtained through a relatively long reaction step. Since it must be manufactured, there is a disadvantage in that efficiency is low for use on an industrial scale.

Korean Patent Registration No. 10-0895191 (April 20, 2009) Korean Patent Registration No. 10-1135088 (April 03, 2012) US Patent Publication US 2014/0142324(A1)(May 22,2014)

Albert. W. M. Lee, et. al., Chem. Commun. 1997, 611-612 L. H. Jiang, et. al., Tetrahedron, 1999, 55, 2245-2262. M. Peter, et. al., Synlett, 2002, 2019-2022

Therefore, the present invention is a new manufacturing method that can be mass-produced on an industrial scale through a milder reaction condition, a shorter and safer reaction step, and a more economical production process compared to the conventionally known manufacturing method of 1,3-propene sultone. is to provide a way

In order to achieve the above object, in the method for producing cyclic 1,3-propene sultone according to the present invention, sodium 2,3-dihydroxypropane sulfonate is mixed with an organic solvent at -5 ° C to 8 ° C for 3 to 10 hours. 0.33 ~ 0.66 equivalents of triphosgene over a period of time, and the mixture is heated to 10 ℃ ~ 40 ℃ over 3 ~ 10 hours to produce 2-hydroxy-1,3-propane sultone a first step; The 2-hydroxy-1,3-propane sultone is reacted with acetic anhydride (Ac ₂ O) in an organic solvent to obtain 2-acetoxy-1,3-propane sultone, or triethylamine (Et ₃ N) by reacting with methanesulfonyl chloride (MsCl) in the presence of 2-methanesulfoxy-1,3-propanesultone, the 2-acetoxy-1,3-propanesultone or the 2-methanesulfoxy-1,3 - A second step of reacting propane sultone with a base to produce 1,3-propene sultone; It is characterized in that it includes.

In addition, in the method for producing cyclic 1,3-propene sultone according to another embodiment of the present invention, sodium 2,3-dihydroxypropane sulfonate is mixed with an organic solvent at -5 ° C to 8 ° C for 2 to 5 hours. A first step to produce 2-chloro-1,3-propane sultone by mixing with 0.67 to 2.0 equivalents of triphosgene over 1 to 3 hours, and heating the mixture to 20 ℃ to 50 ℃ over 1 to 3 hours. step; a second step of reacting the 2-chloro-1,3-propane sultone with a base to produce 1,3-propene sultone; It is characterized in that it includes.

Compared to conventional methods, the method for producing 1,3-propene sultone according to the present invention is carried out under relatively mild reaction conditions, the reaction process is short, and 1,3-propene sultone is obtained in high yield with high halogenation selectivity. can do. Therefore, there is an effect of mass-producing 1,3-porophene sultone used as an electrolyte additive for lithium ion secondary batteries simply and at low cost.

As shown in the following [Reaction Scheme 1], the method for producing 1,3-propene sultone according to the present invention is prepared by preparing 2-hydroxy-1,3-dihydroxypropane sulfonate from sodium 2,3-dihydroxypropane sulfonate. As shown in the first method of obtaining 1,3-propene sultone, the target material, through propane sultone, and the following [Scheme 2], 2-chloro- It is divided into a second method for obtaining 1,3-propene sultone, which is a target material, through 1,3-propane sultone.

[Scheme 1]

[Scheme 2]

First, in the first step process (A1) of the first method, sodium 2,3-dihydroxypropane sulfonate as a starting material is mixed with 0.33 to 0.66 equivalents of triphosgene and 3 at -5 ℃ to 8 ℃ with an organic solvent. After mixing over ~10 hours, the mixture is allowed to react while gradually warming to rise to 10°C~40°C over 3~10 hours.

In this way, the sodium 2,3-dihydroxypropane sulfonate is converted to 2,3-dihydroxypropane sulfonyl halide by a halogenation reaction with triphosgene, followed by a one-pot reaction. As a ring closing esterfication reaction occurs, 2-hydroxy-1,3-propane sultone is produced.

At this time, the completion of the halogenation and ring-forming esterification reaction is based on the amount of 2-hydroxy-1,3-propane sultone produced, which can be confirmed by gas chromatography (GC) based on the internal standard. can

In the second step (A2) of the first method, the 2-hydroxy-1,3-propane sultone is reacted with acetic anhydride (Ac ₂ O) in a solvent to obtain 2-acetoxy-1,3-propane sultone. , or reacted with methanesulfonyl chloride (MsCl) in the presence of triethylamine (Et ₃ N) to obtain 2-methanesulfoxy-1,3-propanesultone. Subsequently, the leaving group hydrogen is removed from the 2-acetoxy-1,3-propane sultone or the 2-methanesulfoxy-1,3-propane sultone under basic conditions to obtain 1,3-propene sultone as a target material. do.

Next, in the first step step (B1) of the second method, sodium 2,3-dihydroxypropane sulfonate as a starting material is mixed with an organic solvent at -5 ° C to 8 ° C for 2 to 5 hours at 0.67 to 50 ° C. It is mixed with 2.0 equivalents of triphosgene, and the mixture is heated to rise to 20 ° C to 50 ° C over 1 to 3 hours. Compared to the first step process (A1) of the first method, there is a difference in the equivalent weight of the triphosgene as the halogenating agent, the reaction temperature, and the heating rate.

In this way, the sodium 2,3-dihydroxypropane sulfonate is converted to 2,3-dihydroxypropane sulfonyl halide by a halogenation reaction with the triphosgene, followed by ring closing esterfication 2-hydroxy-1,3-propane sultone is produced by the reaction, and then 2-chloro-1,3-propane sultone is produced by reacting with triphosgene present in the reaction mixture.

In this way, the first step process (B1) of the second method is all a three-step reaction, but proceeds as a one-pot reaction, and 2-hydroxy-1,3- Propane sultone and 2-chloro-1,3-propane sultone upon completion of the reaction are obtained together. However, in the first step process (B1), the 2-hydroxy-1,3-propane sultone is not separated, and the 2-chloro-1,3-propane sultone is passed as it is in the next step, the second step ( Put in B2).

In the second step step (B2) of the second method, halogen hydrogen is removed from the 2-chloro-1,3-propane sultone under basic conditions to obtain 1,3-propene sultone as a target material.

In the present invention, sodium 2,3-dihydroxypropane sulfonate can be prepared by subjecting 3-chloro-1,2-propane diol to sodium sulfite (Na ₂ SO ₃ ) to a substitution reaction.

In addition, organic solvents used in the halogenation reaction of the first step (A1, B1) include acetonitrile (MeCN), dimethylformamide (DMF), 1,4-dioxane, dimethyl sulfoxide (DMSO), and tetrahydrofuran. (THF), ethanol, methanol, isopropanol, benzene, toluene, nitrobenzene, 1,4-dioxane, methyl acetate, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, dichloromethane, dichloroethane, and chloroform. It can be used, and it is preferable to use acetonitrile (MeCN) and dimethylformamide (DMF) together.

In addition, when the reaction temperature is higher than the specified range in the first step process (A1, B1), the position selectivity of halogenation may be lowered, and by-products of the reaction may be generated or 2-hydroxy-1,3 as an intermediate product. - Decomposition or polymerization of propane sultone may occur, resulting in a decrease in the reaction yield of the target substance.

The base in the second step (A2, B2) is selected from K ₂ CO _{3 ,} Li ₂ CO ₃ , Na ₂ CO ₃ , Cs ₂ CO _{3 ,} NaHCO ₃ , KHCO _{3 and} triethylamine (Et ₃ N). Any one or more may be used, and in particular, it is preferable to use triethylamine (Et ₃ N) among the bases in the second step process (B2) of the second method.

Hereinafter, the present invention will be described in detail through examples. However, these examples do not limit the protection scope of the present invention.

[ reference example 1 ] 2,3-dihydroxypropane of sodium sulfonate Produce

After adding 107.2 g (970 mmol) of 3-chloro-1,2-propane diol to a solution of 120 g (924 mmol, content 98.0% of Daejeong Chemical) of sodium sulfite dissolved in 400 ml of water, the mixture was heated at 120 to 130 ° C for 1 hour. It was stirred under reflux. After completion of the reaction, 70-80% of the reaction solvent was concentrated, and then 800 ml of methanol was added to the residue remaining after concentration, and the resulting solid was filtered and the solid obtained was vacuum-dried to obtain 2,3-dihydroxy as white crystals. 190 g of sodium propane sulfonate (content 67%, 715 mmol, yield: 77.4%) was obtained. The content was obtained based on the internal standard material using ¹ H-NMR.

¹ H-NMR (400 MHz, D ₂ O) δ (ppm): 4.05 (m, 1H), 3.54 (m, 2H), 2.97 (m, 2H)

[Example 1] Preparation of 2-hydroxy-1,3-propane sultone

After adding 400 g of dried MeCN, 250 g of 67% pure sodium 2,3-dihydroxypropane sulfonate, and 72 g of DMF sequentially to a 2L reactor equipped with a stirrer and a cooling condenser, the reaction mixture was stirred at room temperature for 3 to 5 hours. So that the slurry was well dispersed in MeCN. After cooling the reaction mixture to 0° C., a previously prepared solution of 160 g of triphosgene dissolved in 400 g of MeCN was slowly added dropwise for 5 hours (2 ml/min) using a dropping funnel (500 ml). The degree of reaction was confirmed by the amount of carbon dioxide (CO ₂ ) generated by passing through an oil bubbler connected to a condenser. HCl gas generated in the reaction was neutralized in a base trap containing a saturated NaOH aqueous solution connected to the condenser and discharged into the air. After the dropwise addition was completed, the mixture was heated to reach 25° C. over 6 hours, and 100 g of methanol was added dropwise at room temperature to remove triphosgene or phosgene remaining in the reaction mixture, followed by stirring at room temperature for 1 hour. After completion of the reaction, MeCN was removed under reduced pressure at a temperature of 40 °C or lower. The resulting 2-hydroxy-1,3-propanesultone mixture was dissolved in 1.3 kg of EtOAc, and 700 g of cold water was slowly added dropwise thereto, followed by stirring for 20 minutes. After separating the organic layer, saturated NaHCO ₃ washed with 400 g. The solvent was removed under reduced pressure to obtain 60 g of 2-hydroxy-1,3-propane sultone (yield: 46%, purity: 97%). 2-hydroxy-1,3-propane sultone was confirmed by NMR spectroscopy.

1H ^- NMR (400MHz, DMSO-d ₆ )δ (ppm): 5.95 (d, 1H), 4.74 (m, 1H), 4.52 (m, 1H), 4.27 (m, 1H), 3.68 (m, 1H) ), 3.27(m, 1H)

[Example 2] Preparation of 2-chloro-1,3-propane sultone

Except for the matters described below, the same procedure as in Example 1 was performed. That is, a solution of 200 g of triphosgene prepared in advance in 450 g of MeCN was added dropwise using a dropping funnel (500 ml) at 0 ° C over 4 hours, and then the temperature of the reaction mixture was slowly heated to 30 ° C for 2 hours. do. After stirring at 30° C. for 5 hours, 100 g of methanol was added dropwise at room temperature to remove triphosgene or phosgene remaining in the reaction mixture, followed by stirring at room temperature for 1 hour.

After completion of the reaction, MeCN was removed under reduced pressure at a temperature of 40 °C or lower. The resulting 2-chloro-1,3-propane sultone mixture was dissolved in 1.3 kg of EtOAc, and 700 g of cold water was slowly added dropwise thereto, followed by stirring for 30 minutes. After separating the organic layer, saturated NaHCO ₃ washed with 400 g. The solvent was removed under reduced pressure to obtain 47 g (yield: 30%) of 2-chloro-1,3-propane sultone and 15 g (yield: 11%) of 2-hydroxy-1,3-propane sultone. 2-chloro-1,3-propane sultone was confirmed by NMR spectroscopy.

1H ^- NMR (400MHz, CDCl ₃ )δ (ppm): 4.84 (m, 1H), 4.72 (m, 1H), 4.45 (m, 1H), 3.80 (m, 1H), 3.46 (m, 1H)

[Example 3] Preparation of 1,3-propene sultone

After dissolving 10 g of 2-hydroxy-1,3-propane sultone obtained in Example 2 in 140 g of EtOAc in a reactor of 500 ml, 22.2 g of Ac ₂ O and K ₂ CO ₃ 20 g was added, and the reaction mixture was stirred at room temperature for 3 hours to confirm that 2-acetoxy-1,3-propane sultone had a yield of 90 to 95% and a purity of 95% or higher (GC peak area).

1H ^- NMR (400MHz, CDCl ₃ )δ (ppm): 5.62 (m, 1H), 4.65 (m, 1H), 4.48 (m, 1H), 3.63 (m, 1H), 3.35 (m, 1H), 2.16(s, 3H)

Subsequently, H ₂ O (5-10 g) was added without separation and purification, stirred at 40 ° C for 5 hours, cooled to room temperature, added 100 ml of water, stirred, and separated the organic layer, and then used a rotary evaporator. to remove the solvent. Subsequently, the reaction mixture was dissolved in chloroform and recrystallized to obtain 1,3-propene sultone as a white solid. It was recrystallized in the same manner to obtain 6 g of 1,3-propene sultone (yield: 67%, purity: 98.5%).

¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 7.01 (m, 1H), 6.82 (m, 1H), 5.12 (m, 2H).

¹³ C-NMR (100 MHz, CDCl ₃ ): 137.3, 124.5, 72.6

[Example 4] Preparation of 1,3-propene sultone

In 500 ml of the reactor, 14 g (0.10 mol) of 2-hydroxy-1,3-propane sultone obtained in Example 2 was dissolved in 200 g of EtOAc, the reaction solution was cooled to 0 ° C, and 24.3 g of Et ₃ N was added. , 14 g of MsCl was added slowly. The reaction mixture was stirred at 0° C. for 5 hours, cooled water (100 ml) was added, stirred, and the organic layer was separated, and then the solvent was removed using a rotary evaporator. Subsequently, the reaction mixture was dissolved in chloroform and recrystallized to obtain 1,3-propene sultone as a white solid. By recrystallization in the same manner, 8.5 g of 1,3-propene sultone (yield: 71%, purity: 96%) was obtained.

[Example 5] Preparation of 1,3-propene sultone

In a reactor of 100 ml, 3 g (19 mmol) of 2-chloro-1,3-propane sultone obtained in Example 3 was dissolved in 30 g of toluene. 2.3 g of Et ₃ N was added to the reaction mixture, stirred at room temperature for 4 hours, cooled water (20 ml) was added, stirring and organic layer separation were performed, and the solvent was removed using a rotary evaporator. Subsequently, the reaction mixture was dissolved in chloroform and recrystallized to obtain 1,3-propene sultone as a white solid. By recrystallization in the same manner, 2.1 g of 1,3-propene sultone (yield: 92%, purity: 96%) was obtained.

Claims (5)

Sodium 2,3-dihydroxypropane sulfonate was mixed with 0.33 to 0.66 equivalents of triphosgene at -5℃ to 8℃ over 3 to 10 hours with an organic solvent, and the mixture was stirred for 3 to 10 hours. a first step of generating 2-hydroxy-1,3-propane sultone by heating the temperature to 10° C. to 40° C.;
The 2-hydroxy-1,3-propane sultone is reacted with acetic anhydride (Ac ₂ O) in an organic solvent to obtain 2-acetoxy-1,3-propane sultone, or triethylamine (Et ₃ N) by reacting with methanesulfonyl chloride (MsCl) in the presence of 2-methanesulfoxy-1,3-propanesultone, the 2-acetoxy-1,3-propanesultone or the 2-methanesulfoxy-1,3 - A second step of reacting propane sultone with a base to produce 1,3-propene sultone;
Method for producing cyclic 1,3-propene sultone comprising a.
Sodium 2,3-dihydroxypropane sulfonate was mixed with 0.67 to 2.0 equivalents of triphosgene with an organic solvent at -5℃ to 8℃ over 2 to 5 hours, and the mixture was stirred for 1 to 3 hours. A first step of generating 2-chloro-1,3-propane sultone by heating the temperature to 20° C. to 50° C. over a period of time;
a second step of reacting the 2-chloro-1,3-propane sultone with a base to produce 1,3-propene sultone;
Method for producing cyclic 1,3-propene sultone comprising a.
The method of claim 1 or 2, wherein the organic solvent of the first step is acetonitrile (MeCN), dimethylformamide (DMF), 1,4-dioxane, dimethyl sulfoxide (DMSO), tetrahydrofuran ( THF), ethanol, methanol, isopropanol, benzene, toluene, nitrobenzene, 1,4-dioxane, methyl acetate, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, dichloromethane, dichloroethane, and chloroform. A method for producing cyclic 1,3-propene sultone, characterized in that it is used.
The method of claim 3, wherein acetonitrile (MeCN) or dimethylformamide (DMF) is used as the organic solvent.
The method of claim 1 or 2, wherein the base of the second step is K ₂ CO _{3 ,} Li ₂ CO ₃ , Na ₂ CO ₃ , Cs ₂ CO _{3 ,} NaHCO ₃ , KHCO _{3 ,} triethylamine (Et ₃ A method for producing cyclic 1,3-propene sultone, characterized in that using at least one selected from N).