WO2022092834A1 - Method for preparing cyclic sulfonic acid ester compound - Google Patents

Abstract

The present invention relates to a method for preparing a cyclic sulfonic acid ester compound and has an effect of providing an economical method for preparing a cyclic sulfonic acid ester compound, in which by using a cyclizing agent alone under a catalyst-free condition, mass production is possible with high purity and high yield, and a reaction process is simple.

Description

Method for producing a cyclic sulfonic acid ester compound

The present invention relates to a method for producing a cyclic sulfonic acid ester compound, and more particularly, to a method for producing a cyclic sulfonic acid ester compound having excellent reaction stability, shortened reaction time, and simple and economical reaction process.

Cyclic sulfonic acid ester compounds are useful organic electronic materials and are represented by propene sultone-based compounds. A variety of methods are known, such as producing from a material.

First, an alkyl sulfonyl halide as a starting material is reacted with a 1,3-dihalo-hydantoin compound and water, and then a cyclization reaction and a dehalogenation reaction are sequentially performed. has been disclosed. However, this method not only needs to go through several steps such as 1,3-dihalo-hydantoin addition reaction, cyclization, and dehalogenation, but also requires a purification step to remove 1-halo-hydantoin formed as a reaction by-product, so it is economical overall. There is a problem with this falling.

In addition, 1,3-propanesultone as a starting material is reacted with AIBN (azobisisobutyronitrile)/SOCl ₂ to perform halogenation and then dehalogenation reaction sequentially. Domestic Registration Patent No. 10- 0895191. However, according to this method, there is a disadvantage that a purification step is required to remove 3-chloro-1,3-propane sultone generated as a by-product during the reaction process.

Therefore, a halogenation reaction using sodium prop-2-ene-1-sulfonate as a starting material, a cyclization reaction and a dehalogenation reaction in combination with NBS (N-bromosuccinimide) and AIBN (azobisisobutyronitrile) A reaction mechanism for sequentially performing is disclosed in Korean Patent Application Laid-Open No. 10-2009-0076617. However, the above-described method also has to go through several steps such as expensive chlorination, cyclization and dehalogenation, and because it uses AIBN, an expensive radical initiator, the process is complicated and economical is poor. am.

[Prior art literature]

[Patent Literature]

Korean Patent Registration No. 10-0895191

Korean Patent Publication No. 10-2009-0076617

In order to solve the problems of the prior art as described above, an object of the present invention is to provide a method for preparing a cyclic sulfonic acid ester compound.

The above and other objects of the present invention can all be achieved by the present invention described below.

In order to achieve the above object, the present invention

a halogenation step of halogenating one end of the compound represented by the following formula (1) in a hydrophobic solvent;

A catalyst-free cyclization step of synthesizing a cyclization compound by reacting the product of the halogenation step with a cyclizing agent in a mixed solvent of water and an organic solvent; and

A dehalogenation step of synthesizing a compound represented by the following formula (2) by dropwise addition of a strong base to the cyclized compound,

The non-catalytic cyclization step and the dehalogenation step provide a method for producing a cyclic sulfonic acid ester compound, characterized in that it proceeds continuously.

[Formula 1]

[Formula 2]

(In Formula 1, X is Li, Na, or K.)

The halogenation step may include: adding 1 to 1.5 equivalents of the halogenating agent based on 1 equivalent of the compound represented by Formula 1 in the hydrophobic solvent and stirring to obtain an unsaturated compound having one terminal substituted with a halogen; and removing the residual halogenating agent and solvent.

The cyclizing agent is preferably azo-free and peroxide-free N-halogenated succinimide.

The cyclizing agent is preferably added in an amount of 0.8 to 1.5 equivalents based on 1 equivalent of the product of the halogenation step.

In the cyclization step, water and the organic solvent are preferably added in an equivalent ratio of 1 to 2: 0.5 to 2 equivalents with respect to 1 equivalent of the product in the halogenation step.

The strong base may be an aqueous solution of NaOH, KOH, or Ca(OH) ₂ .

The strong base is preferably added in an amount of 2.0 to 2.5 equivalents based on 1 equivalent of the product of the halogenation step.

The reaction temperature of the strong base may be 0 ℃ to 40 ℃, preferably added dropwise under a temperature condition of 25 ℃ to 35 ℃.

The halogenation step, the non-catalytic cyclization step and the dehalogenation step are each preferably performed at room temperature.

The halogenation step may be performed for 1 to 2 hours, the non-catalytic cyclization step may be performed for 3 to 8 hours, and the dehalogenation step may be performed for 1 to 4 hours.

The dehalogenation step may be performed at 25°C to 35°C.

The compound represented by Formula 1 may be sodium prop-2-ene-1-sulfonate or potassium prop-2-ene-1-sulfonate, and the product of the non-catalytic cyclization step is prop-2- It may be an ene-1-sulfonyl halide, and the compound represented by Formula 2 may be 1,3-prop-1-ene sultone.

The method may further include a vacuum distillation step of continuously performing the non-catalytic cyclization step and the dehalogenation step, and then vacuum-distilling and distilling to remove volatiles.

The method may further include recrystallizing and purifying after the vacuum distillation step.

The compound represented by Formula 2 may have a yield of 80% by weight or more and a purity of 99% by weight or more.

According to the present invention, there is an effect of providing a method for producing a cyclic sulfonic acid ester compound with a simple and economical reaction process while allowing mass production with high purity and high yield.

Hereinafter, the manufacturing method of the cyclic sulfonic acid ester compound of this description is demonstrated in detail.

The present inventors have prepared N-bromosuccinimide as a non-catalytic cyclizing agent in synthesizing a desired cyclic sulfonic acid ester compound from an inexpensive alkali metal prop-2-ene-1-sulfonate compound as a starting material. When (NBS) is used alone and the cyclization step and the dehalogenation step are continuously performed, it is confirmed that the reaction process is simple and economical while allowing mass production with high purity and high yield, and based on this, to complete the present invention reached

In addition, the term "halogen" used in the present invention includes, for example, fluorine (F), bromine (Br), chlorine (Cl), iodine (I), and the like.

The method for preparing a cyclic sulfonic acid ester compound of the present invention includes, for example, a halogenation step of halogenating one end of the compound represented by the following formula (1) in a hydrophobic solvent; A catalyst-free cyclization step of synthesizing a cyclization compound by reacting the product of the halogenation step with a cyclizing agent in a mixed solvent of water and an organic solvent; and a dehalogenation step of synthesizing a compound represented by the following formula (2) by dropwise adding a strong base to the cyclized compound, wherein the catalyst-free cyclization step and the dehalogenation step are continuously performed, in this case While excellent in reaction stability, reaction time is shortened, and an improved yield is provided due to a small number of side reactions.

Hereinafter, each component necessary for preparing the cyclic sulfonic acid ester compound of the present invention will be described in detail.

starting material

In the present description, the starting material used for the halogenation reaction may be, for example, a compound represented by the following Chemical Formula 1.

[Formula 1]

Here, X may be, for example, Li, Na or K, preferably Na.

As a specific example, the compound represented by Formula 1 may be sodium prop-2-ene-1-sulfonate or potassium prop-2-ene-1-sulfonate.

product

In the present description, the product prepared by using the compound represented by Chemical Formula 1 described below in the halogenation step, the non-catalytic cyclization step and the dehalogenation step described below may be, for example, a compound represented by the following formula (2).

[Formula 2]

As a specific example, the compound represented by Formula 2 may be 1,3-prop-1-ene sultone.

halogenation reaction

The preparation method according to the present disclosure aims to obtain an unsaturated compound in which one terminal is substituted with a halogen by a halogenation reaction using the compound represented by the above formula (1) as a starting material.

As a specific example, the compound in which one terminal is substituted with a halogen group may be prop-2-ene-1-sulfonyl chloride.

The halogenation reaction will be described in detail with reference to the mechanism shown in the following reaction formula.

[Scheme 1]

Here, X is as shown in Formula 1, and Y is, for example, fluorine (F), bromine (Br), chlorine (Cl) or iodine (I), and preferably chlorine (Cl) or bromine (Br). there is.

As shown in Scheme 1, in the halogenation step, 1 to 1.5 equivalents of the halogenating agent, specific examples 1 to 1.3 with respect to 1 equivalent of the compound represented by Formula 1 (the compound on the left of Scheme 1, corresponding to the starting material) in a hydrophobic solvent An equivalent is added and stirred to obtain an unsaturated compound in which one terminal is substituted with a halogen.

The halogenating agent used at this time may be, for example, phosphoryl trichloride (POCl ₃ ), phosphorus trichloride (PCl ₃ ), phosphorus pentachloride (PCl ₅ ), or thionyl chloride (SOCl ₂ ), and in consideration of double halogenation reaction efficiency, phosphorus trichloride (PCl 3 ) It is preferred to use poryl.

The halogenating agent may be used in an amount of, for example, 1 to 1.5 equivalents, preferably 1 to 1.2 equivalents, based on 1 equivalent of the starting material (compound represented by Formula 1). When the above-mentioned range is satisfied, it is preferable that not only the halogen is effectively introduced only at one end of the starting material, but also the residual halogenating agent can be appropriately removed later.

The hydrophobic solvent is not limited thereto, but it is preferable to use a non-polar solvent having a boiling point of 80° C. or higher in consideration of the halogenation reaction efficiency. For example, toluene, xylene, chlorobenzene, etc. may be used, and these solvents may be used alone or in combination.

The hydrophobic solvent may be used in an amount of 1 to 2 equivalents, preferably 1 to 1.5 equivalents, based on 1 equivalent of the starting material (compound represented by Formula 1). When the above-described range is satisfied, the halogenation reaction is sufficiently performed, stirring is easy, and the residual solvent can be appropriately removed later, which is preferable.

The halogenation reaction may be performed, for example, by stirring under reflux at 60 to 90° C. for 0.5 to 3 hours, preferably at 75 to 85° C. for 1 to 2 hours.

In addition, the produced unsaturated compound (the compound on the right side of Scheme 1, corresponding to the first intermediate) is provided as a colorless product through a step of removing the residual halogenating agent and solvent.

Specifically, after completion of the reaction, the residual halogenating agent may be removed by cooling to 5° C. or less, preferably 0° C. or less, and adding distilled water dropwise by volume of 1-2 times the amount of the halogenating agent.

Then, the organic layer extracted with an organic solvent having a lower boiling point than the hydrophobic solvent is dried over magnesium sulfate, filtered, and the resulting filtrate is concentrated under reduced pressure to obtain a colorless product.

In this case, the colorless product may be prepared in a yield of, for example, 90% by weight or more.

The halogenation reaction of the present description uses a hydrophobic solvent and a halogenating agent having a specific boiling point range in consideration of the reactivity of the cyclizing agent to be introduced into the non-catalytic cyclization reaction described later to obtain an unsaturated compound in which halogen is introduced only at one terminal in high yield. It provides the effect of obtaining an intermediate of

Catalyst-free cyclization

The preparation method according to the present disclosure aims to synthesize a cyclized compound by adding a (non-catalyst) cyclizing agent to the intermediate obtained as a product of the aforementioned halogenation reaction in a mixed solvent of water and an organic solvent.

As a specific example, the cyclizing compound may be 2-halo-1,3-propane sultone.

The catalyst-free cyclization reaction will be described in detail with reference to the mechanism shown in the following reaction formula.

[Scheme 2]

Here, Y is as shown in Scheme 1 above.

Preferably, Y may be chlorine (Cl) or bromine (Br).

As shown in Scheme 2, bromine in NBS (N-bromosuccinimide), which is used alone as a cyclizing agent, is partially protonated to attack and cyclize the unsaturated end portion of the product of the above halogenation reaction as a nucleophile.

The term catalyst-free cyclization as used in the present invention refers to a catalyst-free, for example, azo-free and/or peroxide-free cyclization. it is preferable

Specifically, the cyclizing agent is preferably an N-halogenated succinimide alone under radical initiator-free conditions such as azo-free and peroxide-free.

For reference, in the case of a commonly used radical initiator such as AIBN (azobisisobutyronitrile) or hydrogen peroxide, it remains after completion of the reaction and affects post-process performance, and can generate chlorine-containing by-products. It is preferable not to use it in combination with

Furthermore, when AIBN (azobisisobutyronitrile) is mixed with N-halogenated succinimide, the reaction proceeds through radical initiation, and halogenation and non-catalytic cyclization through nucleophilic substitution in the present description proceed. It is different from the reaction mechanism.

The cyclizing agent may be added in an amount of, for example, 0.8 to 1.5 equivalents, preferably 1 to 1.1 equivalents, based on 1 equivalent of the product of the halogenation step. When the above-described range is satisfied, the catalyst-free cyclization reaction can be efficiently performed.

The organic solvent may be carried out under a conventional solvent, for example, the organic solvent may be a hydrophobic solvent. Non-limiting examples of the solvent include acetonitrile, dichloromethane, chloroform, benzene, methyl tertiary butyl ether, and the like. It is desirable to be able to remove it.

In the non-catalytic cyclization step, water and the organic solvent are, for example, in a ratio of 1-2:0.5-2 equivalents, preferably 1-2:0.5-1.5 equivalents, more preferably 1: with respect to 1 equivalent of the product of the halogenation step. It is preferable to input in a ratio of 1 equivalent. When the above-mentioned range is satisfied, it is preferable that the non-catalytic cyclization reaction can be efficiently performed as well as the residual organic solvent can be appropriately removed.

The catalyst-free cyclization may be carried out at room temperature, and the reaction time may be, for example, 3 to 8 hours, preferably 3 to 5 hours at room temperature, and more preferably 4.5 to 5 hours.

As shown in Scheme 2, the catalytic-free cyclization of the present invention does not generate by-products or use expensive radical initiators or catalysts, and is an azo-free and/or peroxide-free cyclizing agent, that is, azo-free and peroxide-free. By specifying a mixed solvent of water and an organic solvent while using NBS (N-bromosuccinimide) alone as a cyclizing agent for cyclization under conditions, it provides the effect of providing an improved yield with excellent reaction stability and fewer side reactions. .

dehalogenation reaction

The preparation method according to the present disclosure aims to obtain an unsaturated compound in which halogen is desorbed from one terminal thereof by dehalogenation of the aforementioned cyclization product.

As a specific example, the unsaturated compound from which a halogen is desorbed from one terminal may be a compound represented by Formula 2 below.

[Formula 2]

As a specific example, the unsaturated compound from which halogen is desorbed from one terminal may be 1,3-prop-1-ene sultone.

The dehalogenation reaction will be described in detail with reference to the mechanism shown in the following reaction formula.

[Scheme 3]

As shown in Scheme 3, the strong base attacks and desorbs the halogen end portion of the non-catalytic cyclization product (corresponding to the left side of Scheme 3), thereby creating an unsaturated structure.

In this case, the strong base used may be an aqueous solution of NaOH, KOH, or Ca(OH)2 to effectively perform the dehalogenation reaction. For reference, if a weak base such as sodium bicarbonate is used, the dehalogenation reaction time increases, and efficient dehalogenation cannot be performed, thereby reducing yield and purity.

The strong base may be added in an amount of, for example, 2.0 to 2.5 equivalents, preferably 2.2 to 2.3 equivalents, based on 1 equivalent of the product of the halogenation step. When the above-mentioned range is satisfied, the dehalogenation reaction can be efficiently performed, and at the same time, the residual acid generated in the non-catalytic cyclization reaction can be neutralized, thereby increasing the yield and purity of the target compound in the subsequent purification process. It is preferable to be able to

The temperature when the strong base is added dropwise is preferably 0° C. to 40° C., preferably 25° C. to 35° C., so that the above-described dehalogenation reaction can be efficiently performed.

The dehalogenation reaction can be performed by maintaining the dropwise temperature as it is, and the dehalogenation reaction can be carried out under a temperature condition of, for example, 25°C to 35°C.

The dehalogenation step may be performed, for example, at room temperature for 1 to 4 hours, preferably at room temperature for 1 to 2 hours. When the above-described range is satisfied, the resulting dehalogenated reactant (on the right side of Scheme 3, corresponding to the target compound) may not only improve the reaction yield but also provide reaction stability without side reactions.

As shown in Scheme 3, the dehalogenation reaction of the present invention does not use a weak base, which is difficult to control, but uses a strong base to remove the proton next to the SO ₂ group to form a double bond, and at the same time the dehalogenation reaction proceeds. It provides the effect of providing an improved output with excellent stability, reduced reaction time, and fewer side reactions.

Hereinafter, specific matters in the reaction of the present description will be looked at.

Continuous progress of non-catalytic cyclization and dehalogenation reactions

The effects of the cyclizing agent, dehalogenating agent, and solvent input in the above-described non-catalytic cyclization and dehalogenation reactions are very important, and even if all other conditions are the same, some reactions may not proceed depending on these reagents and solvents. , some reactions can proceed close to 100%.

Therefore, in the method for preparing the cyclic sulfonic acid ester compound according to the present disclosure, the selection of the cyclizing agent, the dehalogenating agent and the solvent and the selection of the input order are very important.

Preferably, the use of NBS (N-bromosuccinimide) alone as the cyclizing agent improves the production efficiency so that the cyclization can proceed without a catalyst under azo-free and peroxide-free conditions while using the cyclizing agent. , and by-products can be minimized.

In addition, the dehalogenating agent uses a basic material, but forms a double bond by removing the proton next to the SO ₂ group, and at the same time the dehalogenation reaction proceeds, preferably using a strong base in an aqueous solution state also improves production efficiency and by-products can be minimized.

On the other hand, the cyclizing agent is added under a mixed solvent of water and an organic solvent, and in this case, using a solvent with a low boiling point as the organic solvent not only improves the efficiency of the catalytic cyclization reaction, but also dehalogenates the dehalogenating agent without a solvent without a purification process. It can be added and continuously proceeded to the dehalogenation reaction and then purified, thereby improving production efficiency and minimizing the problem of by-products.

That is, according to one embodiment of the present invention, the above-described non-catalytic cyclization reaction and dehalogenation reaction are characterized in that it proceeds continuously, and in this case, the cyclization reaction and the cyclization reaction without using an expensive radical initiator or catalyst Since the dehalogenation reaction can be carried out in a one-step process, it is possible to reduce costs and provide simple synthesis, as well as provide the target compound in high yield and high purity.

Actually, according to the method for producing a cyclic sulfonic acid ester compound according to the present disclosure, the purity of the compound represented by Formula 2 may be, for example, 99% by weight or more, preferably 99.5% by weight or more.

In addition, according to the method for producing a cyclic sulfonic acid ester compound according to the present disclosure, the yield of the compound represented by Formula 2 may be, for example, 80% by weight or more, preferably 80 to 85% by weight.

According to the method for producing a cyclic sulfonic acid ester compound according to the present disclosure, the reaction may further include removing volatiles by vacuum and distillation.

In addition, the reaction may further include the step of recrystallization and purification.

For example, in the purification step, the organic layer is extracted, dried over magnesium sulfate, and the filtrate obtained by filtration may be recrystallized from a concentrated solution under reduced pressure using water or isopropyl alcohol.

Hereinafter, preferred examples are presented to help the understanding of the present invention, but the following examples are merely illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention, It goes without saying that such variations and modifications fall within the scope of the appended claims.

[Example]

Preparation Example 1: Preparation of prop-2-ene-1-sulfonyl chloride

A halogenation reaction was carried out according to Scheme 1, and from sodium prop-2-ene-1-sulfonate, prop-2-ene-1-sulfonyl chloride (prop- 2-ene-1-sulfonyl chloride) was prepared.

Specifically, 1000 g (6.94 mol, 1 eq) of sodium prop-2-ene-1-sulfonyl chloride, 713 ml of phosphoryl chloride (7.63 mol, 1.1 eq), and 700 ml of toluene were prepared using a 5000 mL reactor with a reflux system. and stirred under reflux for 3 hours.

After completion of the reaction, the reaction was cooled to 0°C, distilled water 1L was added dropwise to remove residual phosphoryl chloride, and then extracted twice using dichloromethane, the organic layer was dried over MgSO ₄ , filtered, and the filtrate obtained by filtration was concentrated under reduced pressure to form a colorless product 794 g was obtained in a yield of 82% by weight.

Preparation 2

Prop-2-ene-1-sulfonyl chloride synthesized in Preparation Example 1 was purchased from Sigma Aldrich and prepared.

Example 1

Using the colorless product (prop-2-ene-1-sulfonyl chloride) obtained in Preparation Example 1, the catalyst-free cyclization reaction and dehalogenation reaction were continuously performed according to Schemes 2 and 3, and 2 -Bromo-1,3-propane sultone 1,3-prop-1-ene sultone as the target compound (compound represented by Formula 2) was prepared through the intermediate.

With respect to Scheme 2, specifically 40.0 g (284.5 mmol, 1eq) of the halogenated product obtained in Preparation Example 1 using a 500 mL three-necked flask equipped with a reflux system, 50.6 g (284.5 mmol, 1eq) of NBS, dichloromethane 280 ml of phosphorus and 280 ml of distilled water were added and stirred at room temperature for 4 hours to obtain a solution containing 2-bromo-1,3-propane sultone intermediate (right side of Scheme 2, Y = bromo).

Then, with respect to Scheme 3, 327.2 ml (654.4 mmol, 2.3eq) of a 2M aqueous NaOH solution as a strong base was added dropwise to the solution containing the intermediate 2-bromo-1,3-propane sultone for 0.5 hour, followed by stirring for 1 hour and the reaction was carried out. ended.

Then, the mixture was extracted twice with dichloromethane, and the organic layer was dried over MgSO ₄ , filtered, and the resulting filtrate was concentrated under reduced pressure to obtain a white solid compound.

The obtained solid compound was recrystallized from isopropyl alcohol to obtain 14 g of a solid compound in a yield of 85% by weight. As a result of verification using gas chromatography, it was confirmed that 1,3-prop-1-ene sultone was 99.7 wt% pure.

Example 2

The same as in Example 1, except that the colorless product of Preparation Example 1 used in Example 1 was replaced with the prop-2-ene-1-sulfonyl chloride product of Preparation Example 2 purchased from Sigma Aldrich. As a result of repeating the process, it was confirmed that a yield of 80% by weight and a purity of 99.5% by weight of the target compound were obtained.

Comparative Example 1

As a result of repeating the same process as in Example 1 except that the use of NBS alone was replaced with the use of AIBN + NBS in combination (1:1 equivalent) in the experiment related to Scheme 2 of Example 1, the compound represented by Formula 2 With respect to phosphorus 1,3-prop-1-ene sultone, it was confirmed that the yield was 60% by weight and the purity was 85% by weight, so it was confirmed that the reaction according to Scheme 2 did not proceed effectively to the target product.

Comparative Example 2

In relation to Scheme 3 of Example 1, the same process as in Example 1 was repeated except that the aqueous NaOH solution used as a strong base was replaced with an aqueous solution of sodium hydrogen carbonate as a weak base. -Prop-1-enesultone was confirmed to have a yield of 40% by weight and a purity of 92% by weight, confirming that the reaction according to Scheme 2 did not effectively dehalogenate to the target product.

Comparative Example 3

In relation to Scheme 3 of Example 1, as a result of repeating the same process as in Example 1, except that 5.0 equivalents exceeding 2.3 equivalents of 2M NaOH aqueous solution used as a strong base was added dropwise, the compound represented by Formula 2 With respect to 1,3-prop-1-ene sultone, it was confirmed that the yield was 50% by weight and the purity was 95% by weight, so it was confirmed that the reaction according to Scheme 2 did not proceed effectively due to the decrease in yield and purity to the target product.

Reference Example 1

In Example 1, instead of proceeding with Reaction Scheme 2 and Scheme 3 continuously, Scheme 2 was performed, followed by extraction with dichloromethane twice, the organic layer was dried over magnesium sulfate, filtered, and the resulting filtrate was concentrated under reduced pressure. As a result of repeating the same process as in Example 1 except that Scheme 3 was carried out using the obtained solid compound, the yield of 1,3-prop-1-enesultone, which is the compound represented by Formula 2, was 40 wt. % and purity 98% by weight, and it was confirmed that the 2-bromo-1,3-propane sultone intermediate had a yield of 70% by weight and a purity of 90% by weight.

As can be seen from the experimental results, in the case of Examples 1 and 2 in which NBS was used alone as a cyclizing agent, the yield of the product reached 80 to 85% by weight, and the purity was also confirmed to be 99.5 to 99.7% by weight.

On the other hand, in the case of Comparative Example 1 in which the non-catalytic condition was not applied by using AIBN in combination, it was confirmed that the yield and purity were lowered.

In addition, in the case of Comparative Example 2, in which a weak base was replaced with a strong base for the dehalogenation reaction continuously proceeding with the non-catalytic cyclization reaction, it was confirmed that the reaction progressed slowly and the yield and purity of the target compound were lowered.

In addition, in the case of Comparative Example 3 in which an excessive amount of a strong base to be added to the dehalogenation reaction proceeding continuously with the non-catalytic cyclization reaction was added, it was confirmed that the yield decreased.

Furthermore, in the case of Reference Example 1 in which the non-catalytic cyclization reaction and the dehalogenation reaction are sequentially performed, it was confirmed that the yield was decreased due to material loss in the intermediate process.

In conclusion, N-bromosuccinimide (NBS) as a cyclizing agent in synthesizing a desired cyclic sulfonic acid ester compound from a low-cost alkali metal prop-2-ene-1-sulfonate compound as a starting material ) alone and the catalyst-free cyclization step and dehalogenation step are continuously performed, mass production with high purity and high yield is possible, and the reaction process is simple and economical.

Claims (15)

1. a halogenation step of halogenating one end of the compound represented by the following formula (1) in a hydrophobic solvent;

   A cyclization step of synthesizing a cyclization compound by reacting the product of the halogenation step with a cyclizing agent in a mixed solvent of water and an organic solvent; and

   A dehalogenation step of synthesizing a compound represented by the following formula (2) by dropwise addition of a strong base to the cyclized compound,

   The non-catalytic cyclization step and the dehalogenation step are characterized in that continuously

   Method for producing a cyclic sulfonic acid ester compound:

   [Formula 1]

   

   [Formula 2]

   

   (In Formula 1, X is Li, Na, or K.)
2. The method of claim 1,

   The halogenation step may include: adding 1 to 1.5 equivalents of the halogenating agent to 1 equivalent of the compound represented by Formula 1 in the hydrophobic solvent and stirring to obtain an unsaturated compound having one terminal substituted with a halogen; and

   and removing residual halogenating agent and solvent.

   A method for producing a cyclic sulfonic acid ester compound.
3. The method of claim 1,

   The cyclizing agent is azo-free and / or peroxide-free (peroxide-free) N- halogenated succinimide, characterized in that

   A method for producing a cyclic sulfonic acid ester compound.
4. The method of claim 1,

   The cyclizing agent is characterized in that 0.8 to 1.5 equivalents are added with respect to 1 equivalent of the product of the halogenation step

   A method for producing a cyclic sulfonic acid ester compound.
5. The method of claim 1,

   In the non-catalytic cyclization step, water and the organic solvent are each added in an equivalent ratio of 1 to 2: 0.5 to 2 equivalents with respect to 1 equivalent of the product in the halogenation step.

   A method for producing a cyclic sulfonic acid ester compound.
6. The method of claim 1,

   The strong base is NaOH, KOH or Ca(OH) ₂ characterized in that the aqueous solution

   A method for producing a cyclic sulfonic acid ester compound.
7. The method of claim 1,

   The strong base is characterized in that 2.0 to 2.5 equivalents are added with respect to 1 equivalent of the product of the halogenation step.

   A method for producing a cyclic sulfonic acid ester compound.
8. The method of claim 1,

   The dropwise addition temperature of the strong base is characterized in that 0 to 40 ℃

   A method for producing a cyclic sulfonic acid ester compound.
9. The method of claim 1,

   The halogenation step, the non-catalytic cyclization step and the dehalogenation step are each performed at room temperature, characterized in that

   A method for producing a cyclic sulfonic acid ester compound.
10. The method of claim 1,

    The halogenation step is performed for 1 to 2 hours, the cyclization step is 3 to 8 hours, and the dehalogenation step is performed for 1 to 4 hours.

    A method for producing a cyclic sulfonic acid ester compound.
11. The method of claim 1,

    The dehalogenation step is characterized in that carried out at 25 to 35 ℃

    A method for producing a cyclic sulfonic acid ester compound.
12. The method of claim 1,

    The compound represented by Formula 1 is sodium prop-2-ene-1-sulfonate or potassium prop-2-ene-1-sulfonate,

    The product of the non-catalytic cyclization step is prop-2-ene-1-sulfonyl halide,

    The compound represented by Formula 2 is 1,3-prop-1-ene sultone, characterized in that

    A method for producing a cyclic sulfonic acid ester compound.
13. The method of claim 1,

    After continuously performing the catalyst-free cyclization step and the dehalogenation step, the method further comprises a reduced pressure distillation step to remove volatiles by reduced pressure and distillation.

    A method for producing a cyclic sulfonic acid ester compound.
14. 14. The method of claim 13,

    After the vacuum distillation step, recrystallization further comprising the step of purifying

    A method for producing a cyclic sulfonic acid ester compound.

    manufacturing method.
15. The method of claim 1,

    Characterized in that the yield of the compound represented by Formula 2 is 80% by weight or more and the purity is 99% by weight or more

    A method for producing a cyclic sulfonic acid ester compound.