JP3234766B2 - Method for producing sulfonic acid halide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a sulfonic acid halide.

[0002]

In recent years, sulfonic acid halides have become industrially important as reaction intermediates for the production of pharmaceuticals and agricultural chemicals. As a method for producing a sulfonic acid halide, a method of chlorinating sulfonic acid with a chlorinating agent such as thionyl chloride or phosphorus pentachloride is generally used. For example, methanesulfonic acid chloride is produced from methanesulfonic acid and thionyl chloride. However, chlorinating agents such as thionyl chloride and phosphorus pentachloride are expensive, and there is a problem in treating sulfur oxides and phosphorus oxides and by-products generated by the reaction. Manufacturing on an industrial scale involves various disadvantages and difficulties. In industrial production of sulfonic acid chlorides, chlorosulfonic acid is frequently used. For example, p-toluenesulfonic acid chloride is industrially manufactured by toluene and chlorosulfonic acid, and benzenesulfonic acid chloride is industrially manufactured by benzene and chlorosulfonic acid. However, chlorosulfonic acid violently undergoes a decomposition reaction with water to be converted into hydrochloric acid and sulfuric acid, is highly corrosive, and has properties such as high toxicity.

As a halogenating agent for a primary hydroxyl group, 2-chloro-1,3-dimethylimidazolinium chloride is known (Japanese Patent Application Laid-Open No. Hei 4-308538). Not.

[0004]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the conventional method for producing a sulfonic acid halide, and the first object of the present invention is to provide an excellent economical method. The second objective is to propose a better method from an environmental point of view.

The inventors of the present invention have conducted intensive studies to achieve these objects, and as a result, have reached the present invention having the following structure. That is, the present invention relates to 1) sulfonic acids represented by the general formula (1)

Embedded image (Wherein R ¹ and R ² are the same or different and each represents a lower alkyl group, X represents a halogen atom, and n represents an integer of 2 or 3). A process for producing the corresponding sulfonic acid halide,

2) Sulfonic acids represented by the general formula (2)

Embedded image Wherein R ¹ and R ² are the same or different and each represents a lower alkyl group, and n represents an integer of 2 or 3. A urea compound represented by the formula (1) )

Embedded image Wherein R ¹ and R ² are the same or different and each represents a lower alkyl group, X represents a halogen atom, and n represents an integer of 2 or 3, and a haloiminium salt represented by the formula:
A method for producing a sulfonic acid halide, which comprises reacting the haloiminium salt with the carboxylic acid or sulfonic acid;

3) The method according to 2) above, wherein the cyclic urea compound is 1,3-dimethylimidazolidin-2-one, and 4) the above wherein the haloiminium salt is 2-chloro-1,3-dimethylimidazolinium chloride. Method 1).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The haloiminium salt used in the present invention is represented by the general formula (1). In the general formula (1), the lower alkyl groups represented by R ¹ and R ² are: , A methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an isobutyl group. Further, as the halogen atom represented by X, a fluorine atom,
Examples include a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is particularly preferred. Among the haloiminium salts represented by the general formula (1), preferred specific examples are 2-chloro-1,3-dimethylimidazolinium chloride (hereinafter abbreviated as DMC) and 2-chloro-1,3-diisopropyl. Imidazolinium chloride, 2-chloro-1,
Examples thereof include 3-dimethyl-3,4,5,6-tetrahydropyrimidinium chloride.

The haloiminium salt is, for example, a compound represented by the following general formula (2) which is known as an easily available solvent:

Embedded image (Wherein, R ¹ and R ² are the same or different and each represents a lower alkyl group, and n represents an integer of 2 or 3), to an oxalyl halide, phosphorus trihalide, a phosphorus halide, phosphorus oxyhalide, phosgene, are readily obtained by reacting the <br/> known halogenating agent such as trichloromethyl chloroformate. Of these, phosgene is used in the urethane industry in large quantities inexpensively, is economically advantageous, and is preferable because no industrial waste such as phosphorus compounds is produced.

In this reaction, one of the compound of the general formula (2) and the halogenating agent is dissolved in a suitable solvent such as carbon tetrachloride, and the other is added little by little. For several hours to several tens of hours. The haloiminium salt represented by the general formula (1) thus obtained can be isolated and used, but the reaction solution can be used for the reaction of the present invention without isolation.

A method for reacting a sulfonic acid with a haloiminium salt will be described. The amount of the haloiminium salt used relative to the sulfonic acid is at least a stoichiometric amount, preferably 1.
It is 0-1.5 times, but more preferably 1.1-1.
It is three times. After completion of the reaction, the haloiminium salt can be returned to the compound of the above general formula (2) and reacted again with a halogenating agent to obtain a haloiminium salt.

The sulfonic acid used in the present invention is, for example, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, 2,5-dimethylbenzenesulfonic acid, 3,4-dimethylbenzenesulfonic acid, m-xylene Sulfonic acids such as sulfonic acid, o-dichlorobenzene-4-sulfonic acid, 2,6-dichlorotoluene-4-sulfonic acid, and benzene-1,3-disulfonic acid, but are not limited thereto. .

The solvent used in the present invention has the general formula (1)
The solvent is not particularly limited as long as it does not react with the haloiminium salt represented by and is a known solvent used for producing a sulfonic acid halide. For example, benzene, toluene, xylene, hexane, heptane, hydrocarbon solvents such as cyclo-hexane, 1,2-dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, halogenated hydrocarbon solvents dichlorobenzene, ethyl acetate, Examples include ester solvents such as butyl acetate, but are not limited thereto.

The reaction temperature in the embodiment of the present invention depends on the reaction substrate and the solvent, but is generally from room temperature to 120 ° C.
Chosen between. For example, when the solvent is toluene, the temperature is preferably 105 to 110 ° C. The produced sulfonic acid halide can be obtained by subjecting the mixture after the completion of the reaction to a conventional method such as distillation or crystallization.

[0015]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Example 1 Synthesis of p-toluenesulfonic acid chloride To 9.72 g (0.0575 mol) of 2-chloro-1,3-dimethylimidazolinium chloride was added 83 g of toluene.
And then 8.61 g of p-toluenesulfonic acid
(0.05 mol) and reacted at 110 ° C. for 4 hours. The reaction mixture was analyzed by gas chromatography to find that p-toluenesulfonic acid chloride was 9%.
Obtained in a yield of 3.2%.

[0017]

According to the present invention, when a sulfonic acid halide is produced according to the present invention, the use of the haloiminium salt represented by the general formula (1) makes it possible to efficiently and economically and environmentally compare the conventional method. The desired compound can be obtained. The cyclic ureas of the general formula (2) formed by reacting the haloiminium salt of the general formula (1) with sulfonic acid are recovered and used again for synthesizing the haloiminium salt of the general formula (1). There are enormous advantages from an economical point of view.

Continuation of front page (56) References JP-A-4-308538 (JP, A) JP-A-8-59604 (JP, A) JP-A-4-308547 (JP, A) JP-A-5-25155 (JP) JP-A-8-97714 (JP, A) JP-A-9-67299 (JP, A) JP-A-56-138192 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB Name) C07C 309/78 C07C 303/02 C07C 309/86

Claims (4)

(57) [Claims] 1. A sulfonic acid having the general formula (1) (Wherein R ¹ and R ² are the same or different and each represents a lower alkyl group, X represents a halogen atom, and n represents an integer of 2 or 3). A method for producing a sulfonic acid halide. 2. A compound represented by the general formula (2): Wherein R ¹ and R ² are the same or different and each represents a lower alkyl group, and n represents an integer of 2 or 3. A urea compound represented by the formula (1) ) Wherein R ¹ and R ² are the same or different and each represents a lower alkyl group, X represents a halogen atom, and n represents an integer of 2 or 3, and a haloiminium salt represented by the formula:
A method for producing a sulfonic acid halide, which comprises reacting a sulfonic acid with the haloiminium salt. 3. The method according to claim 2, wherein the cyclic urea compound is 1,3-dimethylimidazolidin-2-one. 4. The method according to claim 1, wherein the haloiminium salt is 2-chloro-1,3.
-Dimethyl imidazolinium chloride.
the method of.