KR20090108934A - Process for preparing 1,3-propenesultone - Google Patents

Abstract

I) reacting an allylsulfonyl halide with a 1,3-dihalo-hydantoin compound and water to form a 2-halo-3-hydroxypropanesulfonyl halide;

ii) cyclizing the 2-halo-3-hydroxypropanesulfonyl halide to form 2-halo-1,3-propanesultone; And

iii) dehalogenating the 2-halo-1,3-propanesultone;

It relates to a method for producing 1,3-propenesultone which comprises a.

Description

Process for preparing 1,3-propenesultone {Process for preparing 1,3-propenesultone}

The present invention relates to a method for preparing 1,3-propenesultone, specifically i) by reacting allylsulfonyl halide with a 1,3-dihalo-hydantoin compound and water, Forming a 2-halo-3-hydroxypropanesulfonyl halide; ii) cyclizing the 2-halo-3-hydroxypropanesulfonyl halide to form 2-halo-1,3-propanesultone; And iii) dehalogenating the 2-halo-1,3-propanesultone; and relates to a method for producing 1,3-propenesultone.

1,3-propenesultone is a compound represented by the following general formula (1), and is a known compound used as an intermediate for pharmaceuticals, an additive for an electrolyte solution of a lithium ion secondary battery, and the like.

[Formula 1]

In Formula 1, R ^1, R ^2, and R ³ are each independently an alkyl group of hydrogen, halogen, or C ₁ ~ C ₁₂ alkyl group, or a halogen-substituted C ₁ ~ C _12.

Chem. Commun. 1997, 611 and Tetrahedron, 1999, 2245 (WH Lee et al.) Reported the use of 1,3-propenesultone from allyl bromide compounds for 2-bromo-1,3-propanesultone through sulfonation, bromination, and cyclization. A method of synthesizing and synthesizing 1,3-propenesultone is shown.

According to the above method, in order to synthesize 1,3-propenesultone, intermediate 2,3-dibromosulfonic acid should be synthesized and cyclized to produce 2-bromo-1,3-propanesultone. In this reaction step, a temperature of 130 ° C. or higher is required at a reduced pressure of 2 mmHg or less, but under this condition, 2,3-dibromosulfonic acid and the product 2-bromo-1,3-propanesultone are decomposed together, resulting in a severe decrease in yield. do. In particular, as the amount of reactants increases, the heating conditions intensify for a long time, and thus oligomers and polymers linked together in the form of sulfonesters appear to be produced together. From this, vacuum distillation of 2-bromo-1,3-propanesultone, a desired product It tends to be difficult. Therefore, there is a problem that this method is difficult to use industrially.

In addition, Synlett, 2002, 2019 (Peter Metz et al.) Proposes a synthesis method using ring closing metathesis from vinyl intermediates. However, the synthesis of vinyl intermediates is not very easy, and the catalysts used are expensive and are used industrially. Difficult to do

Therefore, there is a need for a new method for industrially producing 1,3-propenesultone easily through mild reaction conditions and simple processes.

It is an object of the present invention to provide a process for the easy production of 1,3-propenesultone in industrially available yields through mild reaction conditions and simple synthesis processes.

I) reacting an allylsulfonyl halide with a 1,3-dihalo-hydantoin compound and water to form a 2-halo-3-hydroxypropanesulfonyl halide;

ii) cyclizing the 2-halo-3-hydroxypropanesulfonyl halide to form 2-halo-1,3-propanesultone; And

iii) dehalogenating the 2-halo-1,3-propanesultone;

It provides a method for producing 1,3-propenesultone characterized in that it comprises a.

The method for producing 1,3-propenesultone of the present invention is characterized by easily producing 1,3-propenesultone in an industrially available yield through mild reaction conditions and a simple synthesis process. .

Method for producing 1,3-propenesultone according to the present invention can be represented by the following scheme 1.

Scheme 1

In step i), allylsulfonyl halide (Formula 2) is reacted with 1,3-dihalo-hydantoin compound (Formula 3) and water to form 2-halo-3hydroxypropanesulfonyl halide. Step.

[Formula 2]

[Formula 3]

In Formulas 2 and 3, X ¹ and X ² are each independently an element selected from the group consisting of F, Cl, Br, and I, R ⁴ and R ⁵ are each independently hydrogen, or C ₁ ~ C ₆ is an alkyl group.

Step i) is a reaction of halogenating allylsulfonyl halide to form 2-halo-3-hydantoinylpropanesulfonyl halide by 1,3-dihalo-hydantoin compound as in Scheme 2; And a reaction to form 2-halo-3-hydroxypropanesulfonyl halide through nucleophilic substitution of water with the 2-halo-3-hydantoinylpropanesulfonyl halide, wherein 1-halo is a reaction byproduct. Hydantoin is produced.

Scheme 2

The allylsulfonyl halide used in step i) is not particularly limited and may be prepared by halogenating the allylsulfonate salt. In particular, in the present invention, it is preferable to increase the economical efficiency by preparing an allylsulfonyl halide of step i) by halogenating an inexpensive allylsulfonate salt with POCl ₃ in a high boiling point solvent.

J. Am. Chem. Soc. 1963. According to the method for preparing allylsulfonyl halide disclosed in 3231, an allylsulfonyl halide is prepared by reacting sodium allylsulfonate in an equivalent ratio of 1: 2 with POCl ₃ at 120 ° C. for 4 hours, in which case a solvent is not used. Therefore, it was difficult to stir, and the amount of POCl ₃ remaining after the completion of the reaction was large, which caused a problem in safety during quenching and was not suitable for commercial production. In this invention, reaction rate can be raised by making inexpensive allyl sulfonate salt and a halogenating agent react in a high boiling point solvent. According to an embodiment of the present invention, the halogenating agent (POCl ₃ ) using only 1.0 equivalent to 1.2 equivalents to the allylsulfonate salt (sodium allylsulfonate), not only the reaction was completed in 2 hours at 90 ℃ temperature In addition, the reaction yield also increased from 60% to 75%. In addition, the remaining amount of POCl ₃ remaining after the completion of the reaction was able to solve the safety problem when quenching POCl ₃ .

In preparing the allylsulfonyl halide according to the invention, the high boiling point solvent used is preferably a solvent having a boiling point of 80 ° C to 120 ° C. When a solvent having a boiling point of 80 ° C. or lower is used, the reaction rate is slow, and when a solvent having a boiling point of 120 ° C. or higher is used, POCl ₃ may evaporate during the reaction and react with moisture in the air to explode. Non-limiting examples of the solvent, toluene, benzene, chlorobenzene, acetonitrile, N, N-dimethyl formamide, 1,2-dichloro Ethane (1,2-dichloroethane), and these solvents may be used alone or in combination of two paper forms. In addition, the solvent is preferably used in the amount of 2 to 5 equivalents relative to the allylsulfonate salt. When used at 2 equivalents or less, stirring is not easy, and when used at 5 equivalents or more, the reaction rate becomes slow and it is difficult to remove the solvent after completion of the reaction.

Meanwhile, in step i), the 1,3-dihalo-hydantoin compound is preferably used in an equivalent ratio of 1 to 1.1 with respect to 1 equivalent of allylsulfonyl halide, and water may be used as a solvent.

Step i) may be performed under conventional solvents in the art, and non-limiting examples of such solvents include water, tetrahydrofuran (THF), diethyl ether, toluene, benzene (benzene), chlorobenzene acetonitrile, N, N-dimethyl formamide, 1,2-dichloroethane, diisopropyl ether ( diisopropyl ether). These may be used alone or in combination of two or more thereof. For example, a mixed solvent of water: diethyl ether = 1: 1 may be used.

On the other hand, step ii) is a step of cyclizing the 2-halo-3-hydroxypropanesulfonyl halide of step i) to form 2-halo-1,3-propanesultone. Is generated.

Steps i) and ii) may proceed continuously. In particular, 1-halo-hidatoin and hydrogen halide formed as reaction by-products in steps i) and ii) of the present invention may form a salt together to promote the cyclization reaction of step ii) (see Scheme 3 below). ).

Scheme 3

Whether the reaction of the steps i) and ii) can be confirmed by gas chromatography (GC), but can be confirmed by observing the color change more easily with the naked eye. For example, when using diethyl ether and water (H ₂ O) as the reaction solvent, the reaction material 1,3-halo-hydantoin compound of step i) is not dissolved in the solvent. However, after initiation of the reaction, the reaction intermediate, 2-halo-3-hydantoinylpropanesulfonyl halide, is dissolved in diethyl ether and the diethyl ether layer becomes dark reddish brown. In addition, as the reaction proceeds, the reddish brown color of the diethyl ether layer becomes gradually lighter, and at the end of the reaction, this color disappears completely and becomes colorless. According to the experiment of the present invention, the end of the continuous reaction step i) and ii) is about 4 to 5 hours after the start of the reaction at room temperature (25 ℃).

On the other hand, step iii) is a step of dehalogenating 2-halo-1,3-propanesultone of step ii) to form 1,3-propenesultone, the final target, and hydrogen halide using a base. Dehydrohalogenation reactions can be applied.

The base usable above is not particularly limited, and non-limiting examples thereof include an aqueous NaOH solution, an aqueous NaHCO ₃ solution, an aqueous Na ₂ CO ₃ solution, an aqueous KOH solution, and an aqueous KHCO ₃ solution. At this time, the basic aqueous solution is preferably a concentration of 0.1N to 2.0N. When using a basic aqueous solution of 0.1N or less, the hydrogen halide removal reaction may not proceed completely, and when using a basic aqueous solution of 2.0N or more, the ring opening reaction of 1,3-propenesultone may be decomposed. . .

In addition, the base is NR ⁶ R ⁷ R ⁸ At this time, each of R ⁶ to R ⁸ may be independently an aliphatic hydrocarbon having 1 to 12 carbon atoms, or an organic base such as primary amine, secondary amine, tertiary amine and pyridine. These may be used alone or in combination of two or more thereof. One example of the secondary amine is diisopropylamine, and one example of the tertiary amine is triethylamine.

Step iii) may be performed at 20 ° C. to 30 ° C., but when the amount of the reactants is increased, it is preferable to maintain the room temperature (25 ° C.) or less using a suitable cooling device. At a temperature above room temperature, the ring opening reaction may be performed by reaction between a base and a sulfonyl group as a side reaction.

As the solvent of step iii), an aromatic compound, ether, ester, and the like may be used. Non-limiting examples of aromatic compounds include benzene, toluene, and the like, examples of ethers include diethyl ether, tetrahydrofuran (THF), and examples of esters include ethyl acetate, dimethyl carbonate, and the like. Two or more kinds can be mixed and used.

Step iii) may be carried out by dropwise addition of a base to 2-halo-1,3-propanesultone dissolved in a solvent, which may be performed in place of the washing step of 2-halo-1,3-propanesultone. It may be.

Whether or not the reaction of step iii) can be confirmed by gas chromatography (GC). According to the experiment of the present invention, the reaction is performed as soon as the base is added dropwise to 2-halo-1,3-propanesultone, and the reaction is terminated. The time point is about 1 hour after the start of the reaction at room temperature (25 ° C).

Hereinafter, the present invention will be described in detail with reference to the following Examples. However, the following examples are merely to illustrate the present invention and the present invention is not limited by the following examples.

Example 1

Example 1-1 Preparation of Allylsulfonyl Chloride

In a 3L reactor equipped with a stirrer and a condenser, 400 g (2.78 mol) of sodium allylsulfonate, 760 g (8.26 mol) of toluene, and 460 g (3.0 mol) of POCl ₃ were added and stirred at room temperature. Oligo was stirred at 90 ° C. for 2 hours. After cooling to room temperature, 0.5 L of iced water was added to the reactor to quench the remaining POCl ₃ . The organic layer was extracted with chloroform (CHCl ₃ ), water was removed with anhydrous MgSO ₄ , filtered and the filtrate was concentrated under reduced pressure. The obtained crude compound was distilled at 3 mmHg and 70 ° C to give 292 g of a colorless liquid compound (75% yield).

 NMR and mass spectroscopy confirmed that the colorless liquid compound was allylsulfonyl chloride.

¹ H NMR (400 MHz, CDCl ₃ ): δ 5.99 (m, 1H), 5.68 (t, J = 13.5 Hz, 2H), 4.33 (d, J = 9.0 Hz, 2H).

¹³ C NMR (100 MHz, CDCl ₃ ): δ 125.3, 117.2, 71.7.

MS (EI, 70 eV) m / z (140, 105, 89, 73, 41, 27).

Example 2: Preparation of 1,3-propenesultone

In a 2L reactor equipped with a stirrer and a condenser, 100 g (0.71 mol) of allylsulfonyl chloride prepared in Example 1-1, and 203 g (0.71 mol) of 1,3-dibromo-5,5-dimethylhydantoin ), 0.5 L of diethyl ether, and 0.5 L of water were added thereto, followed by stirring at room temperature (25 ° C). After stirring for 5 hours, 0.5 L of ethyl acetate was added, and the organic layer was separated. The separated organic layer was washed with 0.5 L of 1.0 N NaOH, dried with anhydrous MgSO ₄ , filtered, and the filtrate was concentrated under reduced pressure to give 99.9 g of a white solid compound (70% yield). Purity was confirmed by gas chromatography to show 97% purity. After dissolving the white solid compound in chloroform, the white crystal obtained by recrystallization at 4 degreeC conditions was 99.8% of purity.

 NMR and mass spectroscopy confirmed that the white solid compound was 1,3-propenesultone.

¹ H NMR (400 MHz, DMSO-d ₆ ): δ 7.45-7.43 (m, 1H), 7.40-77.38 (m, 1H), 5.25-5.24 (t, 2H).

¹³ C NMR (100 MHz, DMSO-d ₆ ): δ 139.6, 123.2, 73.5.

MS (EI, 70 eV) m / z (120, 101, 91, 86, 66, 58, 48, 39, 29, 27).

Claims (11)

i) reacting the allylsulfonyl halide with a 1,3-dihalo-hydantoin compound and water to form a 2-halo-3-hydroxypropanesulfonyl halide; ii) cyclizing the 2-halo-3-hydroxypropanesulfonyl halide to form 2-halo-1,3-propanesultone; And iii) dehalogenating the 2-halo-1,3-propanesultone; 1,3-propenesultone production method characterized in that it comprises a. The method of claim 1, wherein steps i) and ii) are continuously performed. The method for preparing 1,3-propenesultone according to claim 1, wherein the allylsulfonyl halide: 1,3-dibromo-hydantoin compound is used in an equivalent ratio of 1: 1 to 1: 1.1. The method for preparing 1,3-propenesultone according to claim 1, wherein the allylsulfonyl halide is prepared by halogenating an allylsulfonate salt. The method for preparing 1,3-propenesultone according to claim 4, wherein the allylsulfonyl halide is prepared by reacting an allylsulfonate salt: halogenating agent in a ratio of 1: 1 to 1: 1.2 equivalents. The method for preparing 1,3-propenesultone according to claim 4, wherein the allylsulfonyl halide is prepared by halogenating allylsulfonate salt in a solvent having a boiling point of 80 ° C to 120 ° C. The method of claim 6, wherein the solvent is one or more selected from the group consisting of toluene, benzene, chlorobenzene, acetonitrile, N, N-dimethyl formamide, 1,2-dichloroethane, etc. Method for preparing 3-propenesultone. The method of claim 1, wherein step iii) is performed using a base. The method of claim 8, wherein the base is a basic aqueous solution selected from the group consisting of aqueous NaOH solution, aqueous NaHCO ₃ solution, aqueous Na ₂ CO ₃ solution, aqueous KOH solution, and aqueous KHCO ₃ solution. . 10. The method of claim 9, wherein the basic aqueous solution has a concentration of 0.1N to 2.0N. The compound of claim 8, wherein the base is NR ⁶ R ⁷ R ⁸ (R ⁶ to R ⁸ are each independently an aliphatic hydrocarbon having 1 to 12 carbon atoms or H) and pyridine (pyridine) characterized in that the production method of 1,3-propenesultone.