JPH062728B2 - Formylalkylbenzenesulfonyl fluoride and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel formylalkylbenzenesulfonyl fluoride useful as a raw material for medicines, dyes, engineering plastics and the like, and a method for producing the same, and more specifically to a formyl group in alkylbenzene. And a novel compound in which two functional groups of sulfonyl group are simultaneously introduced and a method for producing the same.

2. Description of the Related Art Aromatic sulfonyl compounds are industrially important compounds as synthetic intermediates for drugs, dyes, etc., and as raw materials for producing transparent and highly heat-resistant polysulfone resins.

As a method for introducing a sulfone group into an aromatic compound, 4-chlorobenzene is reacted with chlorosulfonic acid to give 4-
A method for synthesizing chlorobenzenesulfonyl chloride is known in JP-A-59-141556, but a method for simultaneously introducing a formyl group is not known.

On the other hand, as a method of introducing a formyl group into alkylbenzene, a method of reacting with carbon monoxide in hydrogen fluoride-boron trifluoride is known as described in JP-B-39-29760. However, a sulfone group cannot be introduced in this reaction system.

Therefore, the present inventor has previously found a method for producing a formyldialkylbenzenesulfonyl halide by easily inserting a formyl group or a sulfonyl halide group into a dialkylbenzene such as m-xylene or o-xylene (Japanese Patent Application No. Sho-Kaisho). 63-230388). However, this method is limited to the case where a dialkylbenzene such as m-xylene or o-xylene is used, and under the same reaction conditions as described above, a monoalkylbenzene such as toluene or 1,4 such as p-xylene is used. When -dialkylbenzene, trialkylbenzene, tetraalkylbenzene or the like was used, the formyl group was easily inserted, but the sulfonyl halide group could not be inserted.

Means for Solving the Problems An object of the present invention is to synthesize a novel compound in which a formyl group and a fluorosulfonyl group are introduced into alkylbenzene.

The present inventor has conducted intensive studies on the sulfonation reaction of alkylbenzene and the carbonylation reaction, and as a result, by reacting alkylbenzene, fluorosulfonic acid, and carbon monoxide in the coexistence of 5-antimony fluoride, one step at room temperature and atmospheric pressure is performed. Through the reaction, they have found that a formyl group and a fluorosulfonyl group can be simultaneously introduced into alkylbenzene, and have completed the present invention.

That is, the present invention relates to the following compound and a method for producing the same: _{(Wherein, R 1, R 2, R} 3, R 4 is H or _C 1 -C
_{5 represents} an alkyl group. However, two of R _{1 to} R ₄ are H, and a formyl group and a fluorosulfonyl group are respectively located at the para position of the remaining two alkyl groups of R _{1 to} R ₄ . ) A formylalkylbenzenesulfonyl fluoride represented by:

Fluorosulfonic acid and the general formula in the presence of 5-antimony fluoride (In the formula, R ₁ , R ₂ , R ₃ and R ₄ represent a C _{1 to} C ₅ alkyl group.) And carbon monoxide are reacted with each other.

General formula _{(Wherein, R 1, R 2, R} 3, R 4 is H or _C 1 -C
_{5 represents} an alkyl group. However, two of R _{1 to} R ₄ are H, and a formyl group and a fluorosulfonyl group are respectively located at the para position of the remaining two alkyl groups of R _{1 to} R ₄ . ) A method for producing a formylalkylbenzenesulfonyl fluoride represented by:

The acid strength of the super strong acid obtained by mixing fluorosulfonic acid and antimony 5-fluoride is 100 times or more that of 100% sulfuric acid. Therefore, the reaction which was impossible with the conventional sulfuric acid or polyphosphoric acid system is performed. It will be possible. This is because various cations are stably present in the super strong acid, and the electrophilic substitution reaction to the aromatic compound is likely to occur.

A feature of the present invention is that even in a reaction solution in which the addition ratio of 5-antimony fluoride is increased to increase the acid strength as compared with the conventional method, a compound that has not conventionally reacted by performing the reaction is also fluoro. It is possible to insert a sulfonyl group.

That is, the reaction in the present invention proceeds only in a solution in which antimony 5-fluoride is added to the fluorosulfonic acid in a molar ratio of 0.5 times or more (Hammett acidity function-Ho> 22.5).

The reaction process in the present invention is shown in the following formula.

As in the above formula, alkylbenzene is added to the super strong acid under the carbon monoxide atmosphere under the above-mentioned conditions, and the mixture is stirred at room temperature to introduce the sulfonyl group and the formyl group into the benzene nucleus, and to form 3-formyl-in one step. 2,4,6-Alkylbenzenesulfonyl fluoride is synthesized.

Table 1 shows the relationship between the addition amount of 5-antimony fluoride and the product in the reaction of the above reaction formula (3).

Examples of the alkylbenzene represented by the general formula (2) include monoalkylbenzene, dialkylbenzene, trialkylbenzene and tetraalkylbenzene. Examples of the monoalkylbenzene include compounds having one alkyl substituent in the benzene nucleus such as toluene, ethylbenzene, propylbenzene, butylbenzene, and pentylbenzene. Examples of the dialkylbenzene include
For example, para-xylene, 1,4-diethylbenzene, 1,
Compounds having two alkyl substituents on the benzene nucleus, such as 4-dipropylbenzene and 1,4-dibutylbenzene,
Examples of the trialkylbenzene include 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene,
Examples of compounds having three alkyl substituents in the benzene nucleus, such as 1,2,3-trimethylbenzene, 1,3,5-triethylbenzene, and 1,3,5-tripropylbenzene, and tetraalkylbenzene include, for example, 1,2. , 3, 4
-Compounds having four alkyl substituents on the benzene nucleus such as tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene and the like.

The synthetic method is generally carried out as follows.

When alkylbenzene is gradually added to the mixture of fluorosulfonic acid and 5-antimony fluoride in a carbon monoxide atmosphere, the sulfonation reaction and the carbonylation reaction easily proceed. The molar ratio of the raw material and the catalyst used in the reaction is preferably alkylbenzene: fluorosulfonic acid: 5-antimony fluoride = [0.05 to 0.4]: 1: [0.5 to 0.8]. Here, it is necessary that the molar ratio of antimony 5-fluoride is 0.5 times or more that of fluorosulfonic acid. The reaction temperature is preferably about 20 to 60 ° C. After transferring the reaction mixture to ice water, the desired formylalkylbenzenesulfonyl fluoride is separated by benzene extraction.

At this time, since the viscosity increases with the progress of the above reaction, the reaction proceeds favorably when trifluoroacetic acid, trichloroacetic acid, dichloroacetic acid, sulfuric acid, acetic anhydride, etc. are used as the solvent.

The structure of the product was confirmed by NMR, IR and mass spectroscopy.

EXAMPLES Next, the present invention will be described in more detail with reference to Examples.

Example 1 A three-necked flask connected to a carbon monoxide gas burette was replaced with carbon monoxide, and 20 ml of fluorosulfonic acid was added.
-Add 20 ml antimony fluoride. Gradually add 10.6 ml of toluene at 20 ° C. and stir to obtain carbon monoxide of 2.23.
Was consumed in the reaction. The molar ratio of toluene: fluorosulfonic acid: 5-antimony fluoride or the like is 1: 3.5:
It was 2.8.

After 6 hours the reaction mixture was transferred to ice water. The product was extracted with benzene and concentrated. The oily substance was analyzed by gas chromatography, NMR, IR, and mass spectrometry, and as a result, 9.09 g of 3-formyl-6-methylbenzenesulfonyl fluoride (yield 45
%) And 3-formyl-4-methylbenzenesulfonyl fluoride (3.03 g, yield 15%) were produced.

 Gender values are shown below.

3-Formyl-6-methylbenzenesulfonyl fluoride MS spectrum: M ⁺ (m / e) = 02 ¹ H NMR chemical shift δ (CCl ₄ ): 2.74 (3H, s) 7.50 (1H, d) 8 0.000 (1H, d) 8.30 (1H, s) 9.88 (1H, s) IR spectrum (cm ⁻¹ ): 1715, 1600, 1420, 1220, 77
0 3-formyl-4-methylbenzenesulfonyl fluoride MS spectrum: M ⁺ (m / e) = 202 ¹ H NMR chemical shift δ (CCl ₄ ) 2.78 (3H, s) 7.45 (1H, d) 7 .95 (1H, d) 8.22 (1H, s) 10.20 (1H, s) IR spectrum (cm ^-1 ): 1700, 1600, 1410, 1180, 89
0,735 Example 2 Fluorosulfonic acid 20 ml, 5-antimony fluoride 20
ml and n-pentylbenzene 8.6 ml were reacted in the same manner as in Example 1 in a carbon monoxide atmosphere with stirring. The molar ratio of n-pentylbenzene: fluorosulfonic acid: 5-antimony fluoride was 1: 7.0: 5.6. Reaction temperature 35 ° C, reaction time 8 hours, carbon monoxide consumption 450m
l. The reaction product was extracted and analyzed in the same manner as in Example 1,
It was confirmed that 5.16 g of 3-formyl-6-pentylbenzenesulfonyl fluoride was produced in a yield of 40% based on n-pentylbenzene.

The physical property values are shown below.

MS spectrum: M ⁺ (m / e) = 258 ¹ H NMR chemical shift δ (CCl ₄ ): 1.2 (3H, t) 1.7 (4H, m) 2.6 (4H, m) 7.0- 8.0 (3H, m) 9.9 (1H, s) IR spectrum (cm ^-1 ): 1710, 1410, 1220, 770 Example 3 A three-necked flask connected to a carbon monoxide gas buret was filled with carbon monoxide. Replace with 20 ml of fluorosulfonic acid, 5
20 ml antimony fluoride was added. Gradually add 7.2 ml of p-xylene at 25 ° C and stir to mix carbon monoxide 13
40 ml was consumed in the reaction. After 8 hours, the reaction mixture was transferred to ice water and the product was separated by benzene extraction and concentrated,
It was analyzed by gas chromatography, NMR, IR and mass spectrometry. 5.2 g of 3-formyl-2,5-dimethylbenzenesulfonyl fluoride were obtained in a yield of 40% based on p-xylene.

The physical property values are shown below.

MS spectrum: M ⁺ (m / e) = 216 ¹ H NMR chemical shift δ (CCl ₄ ): 2.60 (3H, s) 3.07 (3H, s) 8.23 (1H, s) 8.34 ( 1H, s) 10.80 (1H, s) IR spectrum (cm ⁻¹ ): 1690, 1600, 1460, 1380, 1230, 1200, 780 Example 4 A three-necked flask to which a carbon monoxide gas buret was connected was monoxide-oxidized. Replace with carbon, fluorosulfonic acid 20ml, 5
20 ml antimony fluoride and 10 ml trifluoroacetic acid were added. 1,3,5-trimethylbenzene 1 at 20 ℃
When 3.9 ml was gradually added and stirred, carbon monoxide was 2.24.
Was consumed in the reaction. The molar ratio of 1,3,5-trimethylbenzene: fluorosulfonic acid: 5-antimony fluoride was 1: 3.5: 2.8. After 8 hours, the reaction mixture was transferred to ice water. Extract the product with benzene,
Concentrated. The obtained oily substance was analyzed by gas chromatography, NMR, IR and mass spectrometry to find that the product was 3-formyl-2,4,6-trimethylbenzenesulfonyl fluoride (13.8 g, yield 60%). I confirmed that there is.

 The physical property values are shown below.

MS spectrum: M ⁺ (m / e) = 230 ¹ H NMR chemical shift δ (CCl ₃ ): 2.50 (3H, s) 2.65 (3H, s) 2.71 (3H, s) 6.95 ( 1H, s) 10.58 (1H, s) IR spectrum (cm ⁻¹ ): 3000, 1700, 1590, 1400, 1205, 760 Example 5 20 ml of fluorosulfonic acid, 20 antimony fluoride 20
ml and 1,3,5-triethylbenzene (9.3 ml) were reacted in the same manner as in Example 1 in a carbon monoxide atmosphere with stirring.
The molar ratio of 1,3,5-triethylbenzene: fluorosulfonic acid: 5-antimony fluoride is 1: 7: 5.6.
Met. The reaction time was 8 hours, and the carbon monoxide consumption was 1.13. The reaction product was extracted and analyzed in the same manner as in Example 1 to obtain 4.08 g of 3-formyl-2,4,6-triethylbenzenesulfonyl fluoride.
It was confirmed that the product was produced in a yield of 30% based on 3,5-triethylbenzene.

 The physical property values are shown below.

MS spectrum: M ⁺ (m / e) = 272 ¹ H NMR chemical shift δ (CDCl ₄ ): 1.3 (9H, m) 2.0 (6H, m) 7.4 (1H, s) 10.1 ( 1H, s) IR spectrum (cm ⁻¹ ): 1700, 1410, 1200 Example 6 A three-necked flask connected to a carbon monoxide gas buret was replaced with carbon monoxide, and 20 ml of fluorosulfonic acid was added.
20 ml antimony fluoride was added. 1,2 at 20 ℃
When 4-trimethylbenzene (7.0 ml) was gradually added and stirred, carbon monoxide (1.10) was consumed in the reaction. 1,
3,5-trimethylbenzene: fluorosulfonic acid: 5
The molar ratio of antimony fluoride was 1: 7.0: 5.6. After 8 hours, the reaction mixture was transferred to ice water. The product was extracted with benzene and concentrated. As a result of analyzing the product by gas chromatography, NMR, IR and mass spectrometry, it was revealed that 1.15 g (yield 10%) of 3-formyl-2,5,6-trimethylbenzenesulfonyl fluoride was produced. Became.

The physical property values are shown below.

MS spectrum: M ⁺ (m / e) = 230 IR spectrum (cm ⁻¹ ): 3000, 1700, 1590, 1400, 1205 Example 7 20 ml fluorosulfonic acid, 20 antimony fluoride 20
In the same manner as in Example 1, 8 ml of 1,2,4,5-tetramethylbenzene was reacted under a carbon monoxide atmosphere at 1 atm and 20 ° C. The molar ratio of 1,2,4,5-tetramethylbenzene: fluorosulfonic acid: 5-antimony fluoride is
It was 1: 7: 5.5. Carbon monoxide 1.1 was consumed in the reaction. After 8 hours, the reaction mixture was transferred to ice water and the product was extracted with benzene. 4-formyl-2,
0.66 g of 3,5,6-tetramethylbenzenesulfonyl fluoride was produced in a yield of 5% based on 1,2,4,5-tetramethylbenzene.

The physical property values are shown below.

MS spectrum: M ⁺ (m / e) = 244 IR spectrum (cm ^-1 ): 2995, 1705, 1590, 1400, 1210

Claims (2)

[Claims] 1. A general formula _{(Wherein, R 1, R 2, R} 3, R 4 is H or _C 1 -C
_{5 represents} an alkyl group. However, two of R _{1 to} R ₄ are H, and a formyl group and a fluorosulfonyl group are respectively located at the para position of the remaining two alkyl groups of R _{1 to} R ₄ . ) A formylalkylbenzenesulfonyl fluoride represented by: 2. A fluorosulfonic acid and a general formula in the presence of 5-antimony fluoride. (In the formula, R ₁ , R ₂ , R ₃ and R ₄ represent a C _{1 to} C ₅ alkyl group.) A general formula characterized by reacting an alkylbenzene represented by the formula with carbon monoxide. _{(Wherein, R 1, R 2, R} 3, R 4 is H or _C 1 -C
_{5 represents} an alkyl group. However, two of R _{1 to} R ₄ are H, and a formyl group and a fluorosulfonyl group are respectively located at the para position of the remaining two alkyl groups of R _{1 to} R ₄ . ) A method for producing a formylalkylbenzenesulfonyl fluoride represented by: