JPH08198841A - Method for producing sulfonyl compound - Google Patents

Abstract

(57) [Summary] [Objective] Industrially, a novel sulfonyl compound expected to be useful as a developer for thermal recording materials, raw materials for various chemical industries, agriculture, pharmaceutical intermediates and polymer modifiers Manufacture advantageously. [Structure] General formula (2) With a phenolic compound of the general formula (3) By reacting the sulfonyl halide compound of the general formula (1) with a Lewis acid catalyst. [In the general formulas (1), (2) and (3), X represents a hydrogen atom or a lower alkyl group, Y represents a halogen atom, and R ₁ , R ₂
R ₃ 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 of is manufactured.

Description

Detailed Description of the Invention

[0001]

The present invention relates to the general formula (1)

[0002]

[Chemical 4]

[In the general formula (1), X is a hydrogen atom or lower
Represents an alkyl group, R₁, R₂And R ₃Are the same but different
, Hydrogen atom, halogen atom, low
It represents a primary alkyl group or a cycloalkyl group. ]
And a method for producing a novel sulfonyl compound. The present invention
The sulfonyl compounds relating to
Raw materials for various chemical industries, agriculture, pharmaceutical intermediates and polymer modification
It is highly expected to be useful as an additive.

[0004]

PRIOR ART AND PROBLEMS TO BE SOLVED BY THE INVENTION The sulfonyl compound represented by the above general formula (1) and the method for producing the same according to the present invention have not been published in the literature. The present inventors previously developed the sulfonyl compound represented by the above general formula (1) and a method for producing the same, and applied for a patent. However, the steps in the production method were complicated, and further rationalization was industrially required.

[0005]

Means for Solving the Problems The present inventors have arrived at the method of the present invention as a result of further studies on a more industrially advantageous method for producing the sulfonyl compound according to the present invention. That is, the production method of the present invention comprises the general formula (2)

[0006]

Embedded image

[In the general formula (2), X represents a hydrogen atom or a lower alkyl group. ] A phenolic compound represented by
General formula (3)

[0008]

[Chemical 6]

[In the general formula (3), Y represents a halogen atom, and 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. Represent ] The sulfonyl halide compound shown by these is reacted in the presence of a Lewis acid type catalyst, It is a manufacturing method of the sulfonyl compound shown by the said General formula (1).

Examples of the compound represented by the general formula (2) used in the production method of the present invention include phenol, m-cresol, m-ethylphenol and m-isopropylphenol. Examples of the sulfonyl halide compound represented by the general formula (3) used in the production method of the present invention include benzenesulfonyl chloride, tosyl chloride, 4-ethylbenzenesulfonyl chloride, and 4-ethylbenzenesulfonyl chloride.
Isopropylbenzenesulfonyl chloride, 2-methylbenzenesulfonyl chloride, 2,5-dimethylbenzenesulfonyl chloride, 2,4-dimethylbenzenesulfonyl chloride, 4-chlorobenzenesulfonyl chloride, 4-bromobenzenesulfonyl chloride, 3,4-dimethylbenzenesulfonyl Chloride,
2,4,6-trimethylbenzenesulfonyl chloride,
4-Cyclohexylbenzenesulfonyl chloride and the like and their bromides or iodides are exemplified, but a chloride compound is industrially preferable.

The amount of the compound represented by the general formula (3) used is 0.5 with respect to 1 mol of the compound represented by the general formula (2).
Mol to 10 mol, preferably 1.5 mol to 4.
It is 0 mol. 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. The amount of these used is 1 × with respect to 1 mol of the compound represented by the general formula (2).
It is from 10 ^-5 to 0.5 mol, preferably from 0.001 to 0.1 mol.

In the production method of the present invention, the sulfonyl halide compound represented by the general formula (3) used as a raw material may be used in excess as a solvent, or as a solvent, carbon tetrachloride, carbon disulfide, Chloroform,
Nitrobenzene, 1,2-dichloroethane, o-dichlorobenzene, p-dichlorobenzene, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,
1,2,2-Sym-tetrachloroethane, pentachloroethane, etc. may be used, and these solvents may be used as a mixture of two or more kinds. The amount used is the general formula (2)
And 0 to 10 times, preferably 0 to 5 times the total weight of the compound represented by the general formula (3).

In the production method of the present invention, the reaction temperature is generally 20 ° C to 270 ° C. Next, examples of embodiments of the method for producing a sulfonyl compound of the present invention will be described. 1 mol of the compound represented by the general formula (2) is added to a reactor, and in some cases, a solvent is added in an amount of 0.1 to 5 times the total weight of the compounds represented by the general formula (2) and the general formula (3). , 0.001 mol to 0.1 mol of the catalyst was charged, and the mixture was stirred at 60 ° C.
The reaction is continued while dropwise adding 1.5 to 4.0 mol of the compound represented by the general formula (3) while adjusting the temperature to 140 ° C, and after the dropping, the kettle temperature is gradually raised to 120 to 220 ° C. To complete the reaction. Next, the reaction product is washed with water and, if necessary, purified by a recrystallization method to obtain the compound represented by the general formula (1).

General formula (1) obtained by the production method of the present invention
Examples of the sulfonyl compound represented by are: (1) 2,4-bis (phenylsulfonyl) phenol, (2) 2,4-bis (4-methylphenylsulfonyl) phenol, (3)
2,4-bis (4-ethylphenylsulfonyl) phenol, (4) 2,4-bis (4-isopropylphenylsulfonyl) phenol, (5) 2,4-bis (2-methylphenylsulfonyl) phenol, (6 ) 2,4-bis (2,5-dimethylphenylsulfonyl) phenol,
(7) 2,4-bis (2,4-dimethylphenylsulfonyl) phenol, (8) 2,4-bis (4-chlorophenylsulfonyl) phenol, (9) 2,4-bis (4-bromophenylsulfonyl) Phenol, (10) 2,4-bis (3,4-dimethylphenylsulfonyl) phenol, (11) 2,4-bis (2,4,6-trimethylphenylsulfonyl) phenol, (12) 2,4-bis (4-cyclohexylphenylsulfonyl) phenol, (13) 2,
4-bis (phenylsulfonyl) -5-methylphenol, (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, (19) 2,4-bis (2,
4-Dimethylphenylsulfonyl) -5-methylphenol, (20) 2,4-bis (4-chlorophenylsulfonyl) -5-methylphenol, (21) 2,4-bis (4-
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, (31) 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, (42) 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-isopropylphenol, (47) 2,4-
Bis (2,4,6-trimethylphenylsulfonyl) -5
-Isopropylphenol, (48) 2,4-bis (4-cyclohexylphenylsulfonyl) -5-isopropylphenol and the like are exemplified. Of these, particularly preferred compounds are (1) to (4), (7), (8), (13) to (16), (19),
(20), (25) to (28), (31), (32) and the like.

[0015]

EXAMPLES The present invention will be described below with reference to examples. Example 1 A 1-liter reactor was charged with 94 gr of phenol and 1 gr of anhydrous ferric chloride, heated to 80 ° C. with stirring under a nitrogen gas atmosphere, and 370 gr of benzenesulfonyl chloride was added dropwise at the same temperature over 2 hours. . After the completion of dropping, hold at the same temperature for 5 hours and then slowly
The temperature was raised to 0 ° C., and the temperature was maintained for 24 hours to complete the reaction.

Next, the reaction solution obtained by the above method was poured into 1000 gr of a 5% sodium hydroxide aqueous solution, and the mixture was heated to 95 ° C.
After stirring for 2 hours, the mixture was filtered. The filtrate is then
The mixture was slowly added dropwise to 1000 gr of 6% dilute sulfuric acid adjusted to 0 ° C. with stirring to precipitate a crystal product. The crystals were filtered off and washed with 1 liter of water, and the crystals were dissolved in 1 liter of methyl isobutyl ketone with heating to give 1 part of water.
00 ml was added and the oil was washed with water.

The oil was collected, 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 to obtain 310 gr of white crystalline powder. 157 ° C. IR of this thing
From the results of analysis, H-NMR analysis and elemental analysis (Table 1), this product was confirmed to be 2,4-bis (phenylsulfonyl) phenol.

[0018]

[Table 1] The infrared absorption spectrogram of this product is shown in FIG.
In FIG. 1, the vertical axis represents transmittance (%) and the horizontal axis represents wave number (cm ⁻¹ ).

Examples 2 to 8 The same operations as in Example 1 were carried out except that the phenol, benzenesulfonyl chloride and methyl isobutyl ketone used in Example 1 were changed to the compounds and amounts shown in Table 2, respectively. The results are shown in Table 3.

[0020]

[Table 2]

[0021]

[Table 3] 2 to 8, the vertical axis represents transmittance (%) and the horizontal axis represents wave number (cm ⁻¹ ).

Comparative Example A 2-liter reactor was charged with 1-chlorobenzene-2,4-disulfonyl chloride (309 gr), benzene (20 gr) and anhydrous ferric chloride (2 gr), and the mixture was placed under a nitrogen gas atmosphere.
The temperature was raised to 150 ° C. with stirring, and 150 gr of benzene was added dropwise at the same temperature for 20 hours. Crystals began to form on the way. After completion of dropping, the mixture was aged at the same temperature for 2 hours, and then 500 gr of benzene was slowly charged. The crystals precipitated at room temperature were filtered off, and the crystals were collected with methanol 1
Washing with liters gave 280 gr of white crystalline powder.
Melting point 196 [deg.] C.

Next, 196 gr of the above white crystalline powder and 600 gr of a 10% sodium hydroxide aqueous solution were charged into an autoclave reactor, and the temperature was 200 ° C. and 15 kg / cm ^2.
The hydrolysis reaction was continued for 5 hours. After cooling, 10% diluted sulfuric acid was slowly added dropwise with stirring to adjust the pH to 4. The precipitated crystallized product was separated by filtration, and the crystallized product was recrystallized and purified with n-butanol to obtain 160 g of white crystalline powder. 157 ° C.

IR of white crystalline powder obtained by the above method
From the results of analysis, H-NMR analysis and elemental analysis, it was confirmed that the white crystalline powder obtained by the above method was 2,4-bis (phenylsulfonyl) phenol. As is clear from the comparison between the above-mentioned Examples and Comparative Examples, the production method of the present invention has fewer steps than the production method described in Comparative Examples, and the raw materials are industrially produced in large quantities and are inexpensive. It can be seen that the production method of the present invention is an industrially advantageous production method.

[0025]

By the production method of the present invention, a novel sulfonyl compound highly useful as a developer for heat-sensitive recording materials, various industrial raw materials, agriculture, pharmaceutical intermediates, polymer additives, etc.
Using inexpensive chemicals, with a small number of steps and high yield,
It is of high quality and can be produced industrially advantageously.

[Brief description of drawings]

1 is an infrared absorption spectrogram of the compound obtained in Example 1. FIG.

2 is an infrared absorption spectrogram of the compound obtained in Example 2. FIG.

3 is an infrared absorption spectrogram of the compound obtained in Example 3. FIG.

FIG. 4 is an infrared absorption spectrogram of the compound obtained in Example 4.

5 is an infrared absorption spectrogram of the compound obtained in Example 5. FIG.

6 is an infrared absorption spectrogram of the compound obtained in Example 6. FIG.

7 is an infrared absorption spectrogram of the compound obtained in Example 7. FIG.

8 is an infrared absorption spectrogram of the compound obtained in Example 8. FIG.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location // C07B 61/00 300

Claims (3)

[Claims] 1. A compound represented by the general formula (2): [In the general formula (2), X represents a hydrogen atom or a lower alkyl group. ] And a phenol compound represented by the general formula (3): [In the general formula (3), Y represents a halogen atom, and R ₁ , R
₂ and R _{3, which} may be the same or different, each represents a hydrogen atom, a halogen atom, a lower alkyl group or a cycloalkyl group. ] The sulfonyl halide compound represented by the formula [1] embedded image is reacted in the presence of a Lewis acid-based catalyst. [In the general formula (1), X, R ₁ , R ₂ and R ₃ have the same definitions as those in the general formulas (2) and (3). ]
The manufacturing method of the sulfonyl compound shown by these. 2. 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 production method according to claim 1, which is tosyl chloride, 4-ethylbenzenesulfonyl chloride or 4-isopropylbenzenesulfonyl chloride. 3. The Lewis acid catalyst is iron chloride, aluminum chloride, zinc chloride or magnesium chloride.
Or the manufacturing method according to 2.