JP2002053544A - Method for producing sulfonyl compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a sulfonyl compound, by which the sulfonyl compound having a high quality can be produced in a high yield in the reduced number of processes. SOLUTION: This method for producing the sulfonyl compound represented by the general formula (1) (X is H or a lower alkyl; R1 to R3 are each identically or differently H, a halogen, a lower alkyl or a cycloalkyl; R4 is a lower alkyl, or R4 and R4 together exhibit a tetramethylene group to form a ring), characterized by reacting a phenol compound represented by the general formula (2) with a sulfonyl halide compound represented by the general formula (3) in the presence of a Lewis acid-based catalyst in a sulfonyl compound represented by the general formula (4) as a solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a compound represented by the general formula (1):

[0002]

Embedded image (Wherein, X represents a hydrogen atom or a lower alkyl group,
R ₁ , R ₂ and R ₃ may be the same or different and each represents a hydrogen atom, a halogen atom, a lower alkyl group or a cycloalkyl group). The sulfonyl compound according to the present invention,
It is highly expected to be useful as a developer for heat-sensitive recording materials, a raw material for various chemical industries, an intermediate for agricultural chemicals and pharmaceuticals, and an additive for polymer modification.

[0003]

2. Description of the Related Art The present inventors have developed a sulfonyl compound represented by the above general formula (1) and a method for producing the same, and filed a patent application. In the production method described in JP-A-8-198841, solvents such as carbon tetrachloride, carbon disulfide, chloroform, nitrobenzene, 1,2-dichloroethane, o-dichlorobenzene, p-dichlorobenzene,
When 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-sym-tetrachloroethane or pentachloroethane is used, the reaction temperature tends to be insufficient because the boiling point is low. However, a large amount of unreacted substances remained and it was difficult to increase the yield of the desired product. In addition, it causes a large amount of waste. Furthermore, the process is complicated, such as removal of by-products and catalysts, and further industrialization has been required.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a high-quality, high-yield sulfonyl compound with a small number of steps.

[0005]

Means for Solving the Problems The present inventors have conducted various studies on the method for producing a sulfonyl compound according to the present invention, and as a result, have found that the object can be achieved by selecting a specific solvent and a catalyst. The method of the present invention has been reached.

[0006] That is, the production method of the present invention uses the general formula (2)

[0007]

Embedded image (Wherein, X represents a hydrogen atom or a lower alkyl group) and a phenol compound represented by the general formula (3):

[0008]

Embedded image Wherein Y represents a halogen atom, and R ₁ , R ₂ and R ₃ may be the same or different and each represent a hydrogen atom, a halogen atom, a lower alkyl group or a cycloalkyl group. A compound represented by the general formula (4):

[0009]

Embedded image (Wherein, R ₄ represents a lower alkyl group or a tetramethylene group in which R ₄ forms a ring), and the reaction is carried out in the presence of a Lewis acid catalyst using a sulfonyl compound represented by the formula: Equation (1)

[0010]

Embedded image (Wherein, X represents a hydrogen atom or a lower alkyl group,
R ₁ , R ₂ and R ₃ may be the same or different and each represents a hydrogen atom, a halogen atom, a lower alkyl group or a cycloalkyl group).

Further, a sulfonyl compound represented by the above general formula (1) is characterized in that a lower alcohol is added to the condensation reaction mixture to precipitate crystals to obtain the desired product in high purity and high yield. It is a manufacturing method of.

The alkyl group in the present invention includes a methyl group, an ethyl group and a propyl group having 1 to 3 carbon atoms, and the halogen atom includes a fluorine atom, a chlorine atom and a bromine atom.

[0013]

Embodiments of the present invention will be described below in detail.

The phenol compound represented by the general formula (2) used in the production method of the present invention includes phenol, m-cresol, m-ethylphenol, m-isopropylphenol and the like.

The sulfonyl halide compound represented by the general formula (3) used in the production method of the present invention includes:
Benzenesulfonyl chloride, tosyl chloride, 4
-Ethylbenzenesulfonyl chloride, 4-isopropylbenzenesulfonyl chloride, 2-methylbenzenesulfonyl chloride, 2,5-dimethylbenzenesulfonyl chloride, 2,4-dimethylbenzenesulfonyl chloride, 4-chlorobenzenesulfonyl chloride, 4-bromobenzenesulfonyl chloride, 3,
4-dimethylbenzenesulfonyl chloride, 2,4
Examples thereof include 6-trimethylbenzenesulfonyl chloride, 4-cyclohexylbenzenesulfonyl chloride, and the like, and bromides or iodides thereof. Industrially, chloride compounds are preferred.

Examples of the sulfonyl compound represented by the general formula (4) used in the production method of the present invention include dimethyl sulfone, diethyl sulfone, and sulfolane. Particularly preferred is sulfolane.

The lower alcohol used in the production method of the present invention includes methanol, ethanol, isopropanol and the like, and particularly preferably methanol.

The amount of the compound represented by the general formula (3) is 0.5 to 1 mol of the compound represented by the general formula (2).
It is from 10 mol to 10 mol, preferably from 1.5 mol to 4.0 mol.

The amount of the compound represented by the general formula (4) is 0.1 to 5 times, preferably 0.1 to 5 times the total weight of the compounds represented by the general formulas (2) and (3). 1 to
Double the amount.

As the Lewis acid catalyst used in the production method of the present invention, iron chloride, aluminum chloride, zinc chloride, magnesium chloride and the like are preferable. These usages are
1 × 10 1 mol per 1 mol of the compound represented by the general formula (2)
^-5 mol to 0.5 mol, preferably 0.001 mol to
0.1 mol.

In the production method of the present invention, the reaction temperature is usually from 20 ° C. to 200 ° C., and the reaction time is from 5 hours to 35 hours, although it varies depending on the type and amount of the raw materials and the solvent used.

Next, an embodiment of the method for producing a sulfonyl compound according to the present invention will be described.

In a reactor, the compound represented by the general formula (3) is used in an amount equivalent to 1.5 to 4 mol, and the compound represented by the general formula (4) is used as a solvent by the general formula (2) or (3). 0.1 to 5 times the total weight of the indicated compound, 0.001 mol to 0.1 mol equivalent of a Lewis acid-based catalyst,
The reaction is continued while dropping an equivalent of 1 mol of the compound represented by the general formula (2) while adjusting the temperature to 60 ° C. to 140 ° C. with stirring. The reaction is completed while checking the reaction status by the method described above. Next, the compound represented by the general formula (1) is obtained without recrystallization by adding a lower alcohol to the reaction product.

The general formula (1) obtained by the production method of the present invention
The sulfonyl compound represented by (1) 2,4-
Bis (phenylsulfonyl) -5-methylphenol,
(2) 2,4-bis (phenylsulfonyl) phenol, (3) 2,4-bis (4-methylphenylsulfonyl) phenol, (4) 2,4-bis (4-ethylphenylsulfonyl) phenol, (5 ) 2,4-bis (4
-Isopropylphenylsulfonyl) phenol,
(6) 2,4-bis (2-methylphenylsulfonyl)
Phenol, (7) 2,4-bis (2,5-dimethylphenylsulfonyl) phenol, (8) 2,4-bis (2,4-dimethylphenylsulfonyl) phenol,
(9) 2,4-bis (4-chlorophenylsulfonyl)
Phenol, (10) 2,4-bis (4-bromophenylsulfonyl) phenol, (11) 2,4-bis (3,4-dimethylphenylsulfonyl) phenol,
(12) 2,4-bis (2,4,6-trimethylphenylsulfonyl) phenol, (13) 2,4-bis (4
-Cyclohexylphenylsulfonyl) phenol,
(14) 2,4-bis (4-methylphenylsulfonyl) -5-methylphenol, (15) 2,4-bis (4-ethylphenylsulfonyl) -5-methylphenol, (16) 2,4-bis (4-isopropylphenylsulfonyl) -5-methylphenol, (17) 2,
4-bis (2-methylphenylsulfonyl) -5-methylphenol, (18) 2,4-bis (2,5-dimethylphenylsulfonyl) -5-methylphenol, (1
9) 2,4-bis (2,4-dimethylphenylsulfonyl) -5-methylphenol, (20) 2,4-bis (4-chlorophenylsulfonyl) -5-methylphenol, (21) 2,4-bis (5-bromophenylsulfonyl) -5-methylphenol, (22) 2,4-bis (3,4-dimethylphenylsulfonyl) -5-methylphenol, (23) 2,4-bis (2,4,6 -Trimethylphenylsulfonyl) -5-methylphenol, (24) 2,4-bis (4-cyclohexylphenylsulfonyl) -5-methylphenol, (25) 2,
4-bis (phenylsulfonyl) -5-ethylphenol, (26) 2,4-bis (4-methylphenylsulfonyl) -5-ethylphenol, (27) 2,4-bis (4-ethylphenylsulfonyl)- 5-ethylphenol, (28) 2,4-bis (4-isopropylphenylsulfonyl) -5-ethylphenol, (29) 2
4-bis (2-methylphenylsulfonyl) -5-ethylphenol, (30) 2,4-bis (2,5-dimethylphenylsulfonyl) -5-ethylphenol, (3
1) 2,4-bis (2,4-dimethylphenylsulfonyl) -5-ethylphenol, (32) 2,4-bis (4-chlorophenylsulfonyl) -5-ethylphenol, (33) 2,4-bis (4-bromophenylsulfonyl) -5-ethylphenol, (34) 2,4-bis (3,4-dimethylphenylsulfonyl) -5-ethylphenol, (35) 2,4-bis (2,4,6 -Trimethylphenylsulfonyl) -5-ethylphenol, (36) 2,4-bis (4-cyclohexylphenylsulfonyl) -5-ethylphenol, (37) 2,
4-bis (phenylsulfonyl) -5-isopropylphenol, (38) 2,4-bis (4-methylphenylsulfonyl) -5-isopropylphenol, (39)
2,4-bis (4-ethylphenylsulfonyl) -5
Isopropylphenol, (40) 2,4-bis (4-
Isopropylphenylsulfonyl) -5-isopropylphenol, (41) 2,4-bis (2-methylphenylsulfonyl) -5-isopropylphenol, (4
2) 2,4-bis (2,5-dimethylphenylsulfonyl) -5-isopropylphenol, (43) 2,4-
Bis (2,4-dimethylphenylsulfonyl) -5-isopropylphenol, (44) 2,4-bis (4-chlorophenylsulfonyl) -5-isopropylphenol, (45) 2,4-bis (4-bromophenylsulfonyl) ) -5-isopropylphenol, (46) 2,4
-Bis (3,4-dimethylphenylsulfonyl) -5-
Isopropyl phenol, (47) 2,4-bis (2,
4,6-trimethylphenylsulfonyl) -5-isopropylphenol, and (48) 2,4-bis (4-cyclohexylphenylsulfonyl) -5-isopropylphenol. Among these, particularly preferred compounds are (1) to (5), (8), (9), (14),
(15), (16), (19), (20), (25)-
(28), (31), and (32).

[0025]

The present invention will be described below in more detail with reference to examples.

Example 1 In a 1 liter reactor, 370 gr of benzenesulfonyl chloride and 80 of sulfolane were added.
gr and anhydrous ferric chloride (1 gr) were charged, and the temperature was raised to 140 ° C. while stirring under a nitrogen gas atmosphere.
-108 gr of cresol were added dropwise over 3 hours.
After the completion of the dropwise addition, the temperature was maintained at the same temperature for 24 hours to complete the reaction.

Next, nitrogen gas was blown into the reaction solution obtained by the above method to remove acid gas, and then 190 g of sulfolane was added.
270 g of methanol while stirring and dissolving with heating.
r was slowly added dropwise to precipitate crystals. The solution thus obtained was cooled, and the precipitated crystals were separated by filtration, washed with methanol, and dried to obtain 330 gr of white crystal powder. The yield was 85% based on m-cresol (theory, the same applies hereinafter), the melting point was 190 ° C., and the purity was 99.7% (the same applies hereinafter by liquid chromatography). I of this one
From the results of R analysis, H-NMR analysis and elemental analysis (Table 1), the product was found to be 2,4-bis (phenylsulfonyl) -5-
It was confirmed to be methylphenol.

[0028]

[Table 1]

Examples 2 to 8 Example 1 was repeated except that m-cresol and benzenesulfonyl chloride used in Example 1 were changed to the compounds and amounts shown in Table 2, respectively.
The same operation was performed. Table 3 shows the results.

[0030]

[Table 2]

[0031]

[Table 3]

(Comparative Example 1) 370 gr of benzenesulfonyl chloride, 100 gr of 1,2-dichloroethane and 1 gr of anhydrous ferric chloride were charged into a 1-liter reactor, and heated to 90 ° C. while stirring in a nitrogen gas atmosphere. At the same temperature, 108 gr of m-cresol was added dropwise over 3 hours. After completion of the dropwise addition, the reaction was maintained at the same temperature for 24 hours to complete the reaction.

Next, in order to hydrolyze the ester compound by-produced in the reaction solution obtained by the above-mentioned method, the solution was poured into 1,000 g of a 5% aqueous sodium hydroxide solution at 95 ° C. for 2 hours.
After stirring for an hour, the mixture was filtered. The filtrate was slowly dropped into 1000 gr of 6% diluted sulfuric acid adjusted to 90 ° C. while stirring to precipitate crystals. The crystal is filtered off,
After washing with 1 liter of water, the crystal was heated and dissolved in 500 ml of methyl isobutyl ketone, and 100 ml of water was added to remove the catalyst, and the oil was washed with water.

The oil was separated, and the oil was washed twice with 100 ml of water. Next, water in the oil was removed by azeotropic dehydration, and then decolorized using 3 gr of activated carbon and 1 gr of activated clay. The solution thus obtained was cooled, and the precipitated crystals were separated by filtration and dried to obtain 150 gr of white crystalline powder. The yield was 39% based on m-cresol, melting point 190
° C., purity 99.7%.

The IR of the white crystalline powder obtained by the above method
From the results of the analysis, H-NMR analysis and elemental analysis, it was confirmed that the white crystal powder obtained by the above method was 2,4-bis (phenylsulfonyl) -5-methylphenol.

As is clear from the comparison between the above Examples and Comparative Examples, the production method of the present invention has fewer steps than the production method described in Comparative Example 1, and a high-yield, high-quality target product can be obtained. Obtained, and there is little need to treat wastes such as wastewater, and it is understood that this is an industrially advantageous production method.

[0037]

According to the production method of the present invention, a novel sulfonyl compound having high utility as a color developer for heat-sensitive recording materials, various industrial raw materials, intermediates for agricultural chemicals and pharmaceuticals, and polymer additives can be prepared in a small number of steps. , And can be produced industrially advantageously with high yield and high quality.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Ryoichi Fujii 671 Mizuashi, Noguchi-cho, Kakogawa-shi, Hyogo Pref. Harima Chemicals Central Research Laboratory (72) Inventor Shigeru Oda 1-10-24, Itikaichi, Ibaraki-shi, Osaka No. Sanko Co., Ltd., Factory Product Business Unit Research Laboratory (72) Inventor Eiji Kawabata 1-10-24, Itokaichi, Ibaraki-shi, Osaka Prefecture Sanko Co., Ltd. Factory Product Business Headquarters Research Laboratory (72) Inventor Masayuki Takaguchi, Ikka City, Osaka Prefecture 1-10-24, Sanko Co., Ltd., Factory Product Business Headquarters Research Laboratory (72) Inventor Takaaki Mori 1-10-24, Itikaichi, Ibaraki-shi, Osaka Sanko Co., Ltd. Factory Product Business Headquarters Research Laboratory F-term (reference) 4H006 AA02 AC62 AD15 BA06 BA07 BA19 BA37 BA67 BB14 TA02 TB13 TB42 TC32 4H039 CA80 CD20 CL25

Claims (5)

[Claims] 1. A compound of the general formula (2) (Wherein, X represents a hydrogen atom or a lower alkyl group) and a phenol compound represented by the general formula (3): Wherein Y represents a halogen atom, and R ₁ , R ₂ and R ₃ may be the same or different and each represent a hydrogen atom, a halogen atom, a lower alkyl group or a cycloalkyl group. The compound is represented by the general formula (4): (Wherein, R ₄ represents a lower alkyl group or a tetramethylene group in which R ₄ forms a ring), and the reaction is carried out in the presence of a Lewis acid catalyst using a sulfonyl compound represented by the formula: Formula (1) (Wherein, X represents a hydrogen atom or a lower alkyl group,
R ₁ , R ₂ and R ₃ may be the same or different and each represent a hydrogen atom, a halogen atom, a lower alkyl group or a cycloalkyl group). 2. A compound of the general formula (2) (Wherein X represents a hydrogen atom or a lower alkyl group) and a phenol compound represented by the general formula (3): Wherein Y represents a halogen atom, and R ₁ , R ₂ and R ₃ may be the same or different and each represent a hydrogen atom, a halogen atom, a lower alkyl group or a cycloalkyl group. The compound is represented by the general formula (4): (Wherein R ₄ represents a lower alkyl group or a tetramethylene group in which R ₄ forms a ring) with a condensation reaction mixture obtained by reacting a sulfonyl compound as a solvent in the presence of a Lewis acid catalyst. Wherein the desired compound is precipitated by adding a lower alcohol to the compound of the general formula (1). (Wherein, X represents a hydrogen atom or a lower alkyl group,
R ₁ , R ₂ and R ₃ may be the same or different and each represent a hydrogen atom, a halogen atom, a lower alkyl group or a cycloalkyl group). 3. The phenol compound represented by the general formula (2) is phenol, m-cresol, m-ethylphenol or m-isopropylphenol, and the sulfonyl halide compound represented by the general formula (3) is benzenesulfonyl chloride. The sulfonyl compound according to claim 1, wherein the sulfonyl compound is tosyl chloride, 4-ethylbenzenesulfonyl chloride or 4-isopropylbenzenesulfonyl chloride, and the sulfonyl compound represented by the general formula (4) is sulfolane, dimethyl sulfone or diethyl sulfone. Method. 4. The Lewis acid-based catalyst is iron chloride, aluminum chloride, zinc chloride or magnesium chloride.
3. The method for producing a sulfonyl compound according to any one of 3. 5. The method for producing a sulfonyl compound according to claim 2, wherein the lower alcohol is methanol, ethanol, or isopropanol.