JP2001233850A - Method of producing 2-(arylsulfonyl) ethanesulfonic acid salt - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of producing a 2-(arylsulfonyl)ethanesulfonic acid salt which is useful as intermediates for medicaments, agricultural chemicals, etc., and expressed by the general formula (2) [R1 and R2 may be the same to or different from each other, and are each H, a halogen, a lower alkyl, a lower alkoxyl, nitro, cyano, amino, a lower alkylamino, a di(lower alkyl)amino, acyl or an alkoxycarbonyl; and M is an alkali metal], capable of producing the product more efficiently than ever. SOLUTION: This method of producing the 2-(arylsulfonyl)ethanesulfonic acid salt expressed by the general formula (2) comprises reacting an aryl vinyl sulfone expressed by the general formula (1) with an alkali metal sulfite together with water in the presence of a solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing 2- (arylsulfonyl) ethanesulfonic acid salt.

[0002]

2. Description of the Related Art 2- (Arylsulfonyl) ethanesulfonic acid salt is useful as an intermediate for pharmaceuticals, agricultural chemicals and the like. For example, its production method is to prepare an aqueous solution of arylsulfonylethanol and ammonium hydrogen sulfite in the presence of ammonia. Reaction under high-temperature and high-pressure conditions and then alkali metal salification (DE3422671),
A method of reacting (arylsulfonyl) chloroethane with an aqueous solution of sodium sulfite under reflux conditions (J. Org.
Chem. , 43, 647 (1978)). However, the former method is not necessarily an industrial production method because it is necessary to react under high temperature and high pressure conditions, and the latter method has a problem that the reaction time is long and is not always efficient. It could not be said that it was a good manufacturing method.

[0003]

SUMMARY OF THE INVENTION
The present inventors have conducted intensive studies on a method for producing 2- (arylsulfonyl) ethanesulfonic acid salt more efficiently. As a result, by reacting arylvinylsulfone, alkali metal sulfite and water, the present invention can be easily carried out. The present inventors have found that sodium 2- (arylsulfonyl) ethanesulfonate can be obtained in good yield and have led to the present invention.

[0004]

That is, the present invention relates to a compound of the general formula (1) in the presence of a solvent: (Wherein R ¹ and R ² are the same or different and are each a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a nitro group, a cyano group, an amino group, a lower alkylamino group, a di (lower alkyl) An aryl group represented by an amino group, an acyl group or an alkoxycarbonyl group), an alkali metal sulfite, and water. (Wherein, R ¹ and R ² have the same meanings as above, and M represents an alkali metal.) The present invention provides a method for producing a 2- (arylsulfonyl) ethanesulfonic acid salt represented by the formula:

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. General formula (1) Wherein aryl vinyl sulfones represented in the substituents R ¹
And R ² are the same or different and each represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a nitro group, a cyano group, an amino group, a lower alkylamino group, a di (lower alkyl) amino group, an acyl group or Represents an alkoxycarbonyl group.

[0006] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the lower alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, a sec-butyl group and a tert-
Butyl group, isopentyl group, neopentyl group, tert
A straight-chain or branched alkyl group having 1 to 6 carbon atoms such as a pentyl group; and a lower alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group, and an isopropoxy group. Group, isobutoxy group, sec-butoxy group, tert-butoxy group, isopentoxy group, neopentoxy group, tert-
Examples thereof include linear or branched alkoxy groups having 1 to 6 carbon atoms such as pentoxy groups.

[0007] The lower alkylamino group is an amino group substituted with one lower alkyl group, and examples of the lower alkyl group are the same as those described above. Examples of such a lower alkylamino group include a methylamino group, an ethylamino group, and a tert-butylamino group. The di (lower alkyl) amino group is an amino group substituted with two lower alkyl groups. Examples of the lower alkyl group include the same as described above. Examples of the di (lower alkyl) amino group include: Dimethylamino group,
Diethylamino group, methylethylamino group, tert-
And a butylmethylamino group.

Examples of the acyl group include an aliphatic acyl group having 2 to 8 carbon atoms such as an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group and a trimethylacetyl group, and an aromatic acyl group such as a benzoyl group. And the like.

The alkoxycarbonyl group includes, for example, the above-mentioned lower alkoxy groups such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group and a tert-butoxycarbonyl group, and a carbonyl group. Things.

As the aryl vinyl sulfone,
For example, phenylvinyl sulfone, 4-chlorophenylvinylsulfone, 3,4-dichlorophenylvinylsulfone, 4-fluorophenylvinylsulfone, 4-bromophenylvinylsulfone, 3-iodophenylvinylsulfone, 4-methylphenylvinylsulfone, 2,4 −
Dimethylphenylvinylsulfone, 4-ethylphenylvinylsulfone, 4-isobutylphenylvinylsulfone, 4-tert-butylphenylvinylsulfone,
-Methoxyphenylvinylsulfone, 3,4-dimethoxyphenylvinylsulfone, 4-tert-butoxyphenylvinylsulfone, 3-aminophenylvinylsulfone, 3-methylaminophenylvinylsulfone, 3-
(Ethylamino) phenylvinylsulfone, 3- (dimethylamino) phenylvinylsulfone, 3,4-diethylaminophenylvinylsulfone, 3-nitrophenylvinylsulfone, 4-cyanophenylvinylsulfone,
3-acetylphenylvinylsulfone, 4-benzoylphenylvinylsulfone, 4-methoxycarbonylphenylvinylsulfone, and the like.

The aryl vinyl sulfone represented by the general formula (1) can be obtained, for example, by subjecting 2- (arylsulfonyl) chloroethane to a base treatment (J. Org. Che).
m. , 58, 4506 (1993), JP-A-10-25
No. 1219) and the like. Further, the substituent on the aromatic ring may be introduced after vinylation in some cases.

The alkali metal sulfites include, for example, lithium sulfite, sodium sulfite, potassium sulfite, rubidium sulfite, cesium sulfite and the like, and preferably sodium sulfite and potassium sulfite.
Such an alkali metal sulfite may be an anhydride or a hydrate.

As the alkali metal sulfite, a commercially available one may be used, or a known method, for example, a method of mixing an alkali metal bisulfite and an alkali metal hydroxide,
Those produced by a method of blowing sulfur dioxide into an aqueous alkali metal hydroxide solution or the like may be used.

The amount of the alkali metal sulfite used is usually at least 1 mole times the arylvinyl sulfone represented by the general formula (1), and the upper limit is not particularly limited.

The amount of water used is usually at least 1 mole times the aryl vinyl sulfone represented by the general formula (1), and the upper limit thereof is not particularly limited.
A large excess may be used. Such water may be previously added to the aryl vinyl sulfone and / or the alkali metal sulfite represented by the general formula (1). In addition,
When a hydrate of an alkali metal sulfite is used, the water of hydration in the hydrate also participates in the reaction, so the amount of water to be used may be determined, including the water of hydration. If the reaction proceeds sufficiently with the amount of water of hydration in the hydrate of the alkali metal sulfite, it is not necessary to use water separately.

This reaction is carried out in the presence of a solvent. Examples of the solvent include water, ether solvents such as dimethoxyethane, tetrahydrofuran and diethyl ether; aromatic hydrocarbon solvents such as toluene and xylene; , 1,2-dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, o-dichlorobenzene and other halogenated hydrocarbon solvents such as N, N-dimethylformamide, dimethylsulfoxide, acetonitrile and other aprotic polar solvents alone Alternatively, a mixed solvent may be used.

The amount of the solvent used is not particularly limited,
From the viewpoint of volumetric efficiency and the like, it is practically not more than 50 times the weight of aryl vinyl sulfone. The solvent is
It may be previously added to the aryl vinyl sulfone and / or the alkali metal sulfite.

This reaction is usually carried out by mixing the arylvinyl sulfone represented by the general formula (1), an alkali metal sulfite and water, and the mixing order is not limited.

The reaction temperature is usually in the range of 0 ° C. to 80 ° C., preferably in the range of 5 ° C. to 60 ° C.

After completion of the reaction, the general formula (2) (Wherein R ¹ and R ² have the same meanings as above, and M represents an alkali metal.) A reaction mixture containing 2- (arylsulfonyl) ethanesulfonic acid salt represented by the formula: By subjecting the mixture as it is or partially condensing, and then subjecting the mixture to a cooling treatment, the 2- (arylsulfonyl) ethanesulfonic acid salt represented by the general formula (2) can be obtained. When the reaction was carried out in the presence of an organic solvent, after separating and removing the organic layer,
It is preferable to perform the above processing. Depending on the conditions, 2- (arylsulfonyl) ethanesulfonic acid salt represented by the general formula (2) may be precipitated in the reaction mixture. In such a case, even if filtration treatment is performed as it is. After cooling, the mixture may be filtered.

The extracted 2- (2) represented by the general formula (2)
The (arylsulfonyl) ethanesulfonic acid salt may be further purified by, for example, recrystallization treatment.

The 2- (arylsulfonyl) ethanesulfonate thus obtained is, for example, sodium 2- (phenylsulfonyl) ethanesulfonate, 2- (4
Sodium chlorosulfonyl) ethanesulfonate, sodium 2- (3,4-dichlorophenylsulfonyl) ethanesulfonate, sodium 2- (4-fluorophenylsulfonyl) ethanesulfonate, 2- (4
Sodium bromophenylsulfonyl) ethanesulfonate, sodium 2- (3-iodophenylsulfonyl) ethanesulfonate, sodium 2- (4-methylphenylsulfonyl) ethanesulfonate, 2- (2,4-dimethylphenylsulfonyl) ethane Sodium sulfonate, sodium 2- (4-ethylphenylsulfonyl) ethanesulfonate, sodium 2- (4-isobutylphenylsulfonyl) ethanesulfonate, 2- (4-te
sodium rt-butylphenylsulfonyl) ethanesulfonate, sodium 2- (4-methoxyphenylsulfonyl) ethanesulfonate, sodium 2- (3,4-dimethoxyphenylsulfonyl) ethanesulfonate,
-(4-tert-butoxyphenylsulfonyl) ethanesulfonic acid sodium salt,

Sodium 2- (3-aminophenylsulfonyl) ethanesulfonate, sodium 2- [3- (methylamino) phenylsulfonyl] ethanesulfonate, 2- [3- (ethylamino) phenylsulfonyl]
Sodium ethanesulfonate, sodium 2- [3- (dimethylamino) phenylsulfonyl] ethanesulfonate, sodium 2- [3- (diethylamino) phenylsulfonyl] ethanesulfonate, 2- (3-nitrophenylsulfonyl) ethanesulfonic acid Sodium, 2-
Sodium (4-cyanophenylsulfonyl) ethanesulfonate, sodium 2- (3-acetylphenylsulfonyl) ethanesulfonate, sodium 2- (4-benzoylphenylsulfonyl) ethanesulfonate, 2-
Sodium (4-methoxycarbonylphenylsulfonyl) ethanesulfonate, and lithium (2- (arylsulfonyl) ethanesulfonate in which the "sodium" has been replaced by "lithium"; 2- (in which the "sodium" has been replaced by "potassium") Potassium arylsulfonyl) ethanesulfonate, rubidium 2- (arylsulfonyl) ethanesulfonate wherein "sodium" is replaced by "rubidium", "cesium" is "sodium"
And cesium 2- (arylsulfonyl) ethanesulfonate.

Further, 2-
The (arylsulfonyl) ethanesulfonic acid salt is subjected to an acid precipitation treatment to obtain a compound represented by the general formula (3): (Wherein, R ¹ and R ² each have the same meaning as described above.) Can be led to 2- (arylsulfonyl) ethanesulfonic acid represented by the formula:

The acid precipitation treatment is defined as the acid precipitation treatment represented by the general formula (2).
-(Arylsulfonyl) ethanesulfonic acid salt and an acid may be mixed and contacted. Examples of such an acid include mineral acids such as sulfuric acid and hydrochloric acid. It is usually at least 1 mole times the 2- (arylsulfonyl) ethanesulfonic acid salt shown.

As the 2- (arylsulfonyl) ethanesulfonate represented by the general formula (2), one obtained from the reaction mixture obtained after the completion of the above reaction may be used, or for example, the reaction mixture may be used as it is. Is also good. When the reaction is carried out in the presence of an organic solvent, it is preferable to separate and remove the organic layer from the reaction mixture, and then perform an acid precipitation treatment.

After the acid precipitation treatment, an organic solvent which is usually insoluble in water is added and subjected to an extraction treatment to obtain an organic layer containing 2- (arylsulfonyl) ethanesulfonic acid represented by the general formula (3). By concentrating the organic layer, 2- (arylsulfonyl) ethanesulfonic acid represented by the general formula (3) can be obtained. Such an organic solvent may be added during the acid precipitation treatment.

The 2- (arylsulfonyl) ethanesulfonic acid represented by the general formula (3) thus obtained is, for example, 2- (phenylsulfonyl) ethanesulfonic acid, 2- (4-chlorophenylsulfonyl) ethanesulfonic acid, -(3,4-dichlorophenylsulfonyl)
Ethanesulfonic acid, 2- (4-fluorophenylsulfonyl) ethanesulfonic acid, 2- (4-bromophenylsulfonyl) ethanesulfonic acid, 2- (3-iodophenylsulfonyl) ethanesulfonic acid, 2- (4-methylphenyl) Sulfonyl) ethanesulfonic acid, 2- (2,4-
Dimethylphenylsulfonyl) ethanesulfonic acid, 2-
(4-ethylphenylsulfonyl) ethanesulfonic acid,
2- (4-isobutylphenylsulfonyl) ethanesulfonic acid, 2- (4-tert-butylphenylsulfonyl) ethanesulfonic acid, 2- (4-methoxyphenylsulfonyl) ethanesulfonic acid, 2- (3,4-dimethoxyphenyl) Sulfonyl) ethanesulfonic acid, 2- (4-
tert-butoxyphenylsulfonyl) ethanesulfonic acid,

2- (3-aminophenylsulfonyl) ethanesulfonic acid, 2- [3- (methylamino) phenylsulfonyl] ethanesulfonic acid, 2- [3- (ethylamino) phenylsulfonyl] ethanesulfonic acid,
[3- (dimethylamino) phenylsulfonyl] ethanesulfonic acid, 2- [3- (diethylamino) phenylsulfonyl] ethanesulfonic acid, 2- (3-nitrophenylsulfonyl) ethanesulfonic acid, 2- (4-cyanophenylsulfonyl) ) Ethanesulfonic acid, 2- (3-acetylphenylsulfonyl) ethanesulfonic acid, 2- (4
-Benzoylphenylsulfonyl) ethanesulfonic acid,
2- (4-methoxycarbonylphenylsulfonyl) ethanesulfonic acid and the like.

[0030]

According to the method of the present invention, under mild conditions,
2- (arylsulfonyl) ethanesulfonic acid salt can be easily produced.

[0031]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 To 33.6 g of phenylvinyl sulfone was added 100 m of toluene.
L was added and dissolved, and then a solution of 25.3 g of anhydrous sodium sulfite dissolved in 100 mL of water was added thereto.
The mixture was stirred and maintained at an internal temperature of 40 ° C. for 1 hour. As a result of analysis by liquid chromatography, the conversion of phenylvinylsulfone was 100%. After the reaction, the solution was cooled to room temperature, and the precipitated crystals were separated by filtration. Crystals are cooled in cold water (5 ℃) 5
The column was washed with 0 mL, and further twice with 50 mL of acetone. Drying under reduced pressure gave 50.1 g of white crystals of sodium 2- (phenylsulfonyl) ethanesulfonate (yield: 92%).

Claims (4)

[Claims] 1. A compound of the formula (1) in the presence of a solvent (Wherein R ¹ and R ² are the same or different and are each a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a nitro group, a cyano group, an amino group, a lower alkylamino group, a di (lower alkyl) An aryl group represented by an amino group, an acyl group or an alkoxycarbonyl group), an alkali metal sulfite, and water. (Wherein, R ¹ and R ² have the same meanings as above, and M represents an alkali metal.) A method for producing a 2- (arylsulfonyl) ethanesulfonic acid salt represented by the formula: 2. The reaction of an aryl vinyl sulfone represented by the general formula (1), an alkali metal sulfite and water,
A 2- (arylsulfonyl) ethanesulfonic acid salt represented by the general formula (2) is obtained, and the 2- (arylsulfonyl)
General formula (3) characterized in that ethanesulfonate is subjected to acid precipitation treatment. (Wherein, R ¹ and R ² each have the same meaning as described above.) A method for producing 2- (arylsulfonyl) ethanesulfonic acid represented by the formula: 3. The method according to claim 1, wherein the alkali metal sulfite is sodium sulfite or potassium sulfite.
A method for producing (arylsulfonyl) ethanesulfonic acid salt. 4. The method according to claim 2, wherein the alkali metal sulfite is sodium sulfite or potassium sulfite.
A method for producing (arylsulfonyl) ethanesulfonic acid.