JPS6027665B2 - Method for producing anhydrous 4-chlorobenzenesulfonyl chloride - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing anhydrous 4-chlorobenzenesulfonyl chloride.

4-Chlorobenzenesulfonyl chloride is an important raw material for 4,4'-dichlorodiphenylsulfone, which is a monomer of polysulfone resins with excellent heat resistance.

It is particularly well known that 4,4'-dichlorodiphenylsulfone is produced by the Fnedel-C It's reaction of 4-chlorobenzenesulfonyl chloride and chlorobenzene using anhydrous ferric chloride as a catalyst (for example, U.S. Pat. 146 (1967), etc.).

However, it is important to carry out this method that 4-chlorobenzesosulfonyl chloride must be used in the form of bran water. Conventionally, it is known to produce 4-chlorobenzenesulfonyl chloride by reacting chlorobenzene with chlorosulfonic acid in excess of the theoretical amount and then discharging it into ice water (for example, F.UI1
Mann et al., Techr. 40, Nezumi 2 (1907), J. M.
Dumont et al., B Blood. Soc. Chim. Mance
, 1962, 1213, etc.).

This method also produces 4,4'-dichlorodiphenyl sulfone as a by-product, so after discharging the reaction mixture into ice water, 4-chlorobenzenesulfonyl chloride and 4
・Also includes a method for producing 4,4'-dichlorodiphenylsulfone by hydrolyzing 4-chlorobenzenesulfonyl chloride to 4-chlorobenzenesulfonic acid by heating the mixture with 4'-dichlorodiphenylsulfone to 9 picoC. [U.S. Pat. No. 28601]
68 (1958)]. In this way, 4-chlorobenzenesulfonyl chloride is hydrolyzed to form 4-chloride. Since the reaction mixture is easily converted to lobenzene sulfonic acid, after the reaction is completed, the reaction mixture is discharged into ice water, heated in an oven, and dried under reduced pressure to make it anhydrous.
fed into the iedel-CrafG reaction. Considering these known techniques, when producing 4-chloro'penzenesulfonyl chloride by the reaction of chlorobenzene and chlorosulfonic acid, after the reaction, it is discharged into ice water, filtered through an oven, taken out, and dried to form an anhydrous state. This method cannot be said to be industrially satisfactory in terms of manufacturing process and economic efficiency. Also, as mentioned above, 4-chlorobenzenesulfonyl chloride can be produced by reacting chlorobenzene with a stoichiometric excess of chlorosulfonic acid. Conventional production methods include, for example, reacting 1 mole of chlorobenzene with 3 moles of chlorosulfonic acid with a yield of 72 to 73%, and using 8 moles of chlorosulfonic acid with a yield of 80%. AM. produces 4-chlorobenzenesulfonyl chloride. Grigor
ovskiy et al., Kongshan. Priklad. Khim. 2
8616-21 (1955): Chem. Aptr. 5
0 3279 (1956)]. Furthermore, the desired product was produced with a yield of 70% by reacting 4 moles of chlorosulfonic acid with 1 mole of chlorobenzene at a temperature of 600 mm [J
．． M. Dmmont et al., Bull. S.M. ChimFr
ance. 1962, 1213-18]. in this way,
By the reaction between chlorobenzene and chlorosulfonic acid,
In order to produce 4-chlorobenzenesulfonyl chloride with a yield of 80% or more, a large excess of chlorosulfonic acid is required, so it is difficult to implement this process economically and especially in terms of environmental protection. From this point of view, this is a major drawback.
In the reaction between aromatic compounds and chlorosulfonic acid,
In addition to the desired aromatic sulfonyl chloride, aromatic sulfonic acids and diarylsulfones are created. For example, when chlorobenzene is reacted with chlorosulfonic acid at a molar ratio of 3, in addition to 4-chlorobenzenesulfonyl chloride (61% yield), 4.4-
Dichlorodiphenyl sulfone was used [F. Hada lma Hada et al., Ber 40, Nezumi 1 (1907)], previously described A
M. ○ In the literature of Rovskiv et al., 3
When a molar ratio of chlorosulfonic acid is used, 4-chlorobenzenesulfonic acid (20% yield) and 4,4'-dichlorodiphenylsulfone (8% yield) are produced as by-products. In general, it is considered best to use chloroform or carbon tetrachloride to suppress side reactions in the reaction between aromatic compounds and chlorosulfonic acid [New Experimental Chemistry Course, Vol. 14, "Synthesis of Organic Compounds" and reaction (m)” No. 1787~
17 Iso, Maruzen (197 & Wang)] In such a reaction in a solvent, for example, chlorobenzene is reacted with 3 molar ratio of chlorosulfonic acid in chloroform, and although there is no mention of by-products, , the yield of 4-chlorobenzenesulfonyl chloride is only 74.6% (Japanese Patent Publication No. 1973-
No. 19457). As a production method for improving the yield of 4-chlorobenzenesulfonyl chloride, a method in which sodium 4-chlorobenzenesulfonate is reacted with chlorosulfonic acid is known.

The aforementioned AM. In the paper by Grigorovskly et al.
This method has produced the desired product with a yield of 80%. Moreover, carrying out this method in an organic solvent is also a no-go. That is, there is a method for producing 4-chlorobenzenesulfonyl chloride with a high yield of 89% by suspending dried sodium 4-chlorobenzenesulfonate in chloroform and reacting it with chlorosulfonic acid (2 molar ratio). It has been proposed [M. K mountain ka. J. Am. Ch
em. SM, 72, 1215 (1950)]. However, although this method uses only a small amount of chlorosulfonic acid and has a high yield, it is not economical because the raw material, sodium 4-chlorobenzenesulfonate, must be isolated and used in an anhydrous state. , it is hard to say that it is an industrially advantageous method. In view of these technical standards, it is possible to reduce the amount of chlorosulfonic acid used in the reaction between chlorobenzene and chlorosulfonic acid, suppress formation of formation organisms, and produce anhydrous 4-chlorobenzenesulfonyl chloride in high yield. This is a topic that is also demanded by industry.

The present inventors completed the present invention as a result of intensive studies aimed at industrially advantageously producing anhydrous 4-chlorobenzenesulfonyl chloride.

That is, in the first invention, chlorobenzene and chlorosulfonic acid are reacted, the resulting reaction mixture is concentrated with water in the presence of an aliphatic halogenated hydrocarbon solvent, and then water is removed from the separated organic solvent layer. This is a method for producing anhydrous 4-chlorobenzenesulfonyl chloride, characterized by distilling it off together with a solvent. In addition, the second invention involves reacting chlorobenzene and chlorosulfonic acid in an aliphatic halogenated hydrocarbon solvent in the presence of an alkali metal salt and/or ammonium salt of a key acid, and washing the resulting reaction mixture with water. This is a method for producing 4-chlorobenzenesulfonyl chloride, which is characterized by draining and then removing water from the separated organic solvent layer together with the solvent.

According to the method of the present invention, 4-chlorobenzenesulfonyl chloride has the property of being easily hydrolyzed into 4-chlorobenzenesulfonic acid when heated with water. An aliphatic halogenated hydrocarbon is added to the reaction mixture (in some cases, it may be used as a reaction solvent in advance), and the sulfuric acid and unreacted chlorosulfonic acid produced in Tomiyama are removed by washing with water, and the separated organic When water contained in the solvent layer is distilled off together with the solvent by azeotropic distillation, 4-chlorobenzenesulfonyl chloride is not hydrolyzed to 4-chlorobenzenesulfonic acid at all and can be easily produced in an anhydrous state.

This is a surprising fact that could not have been expected in view of conventional known techniques and the unstable property of 4-chlorobenzenesulfonyl chloride in water. Further, in the method of producing 4-chlorobenzenesulfonyl chloride by reacting an aliphatic halogenated hydrocarbon as a solvent and in the presence of an alkali metal salt and/or ammonium salt of a key acid, the solvent and the mineral acid The effects of salt are as follows.

For example, when chlorobenzene is reacted with 3 molar ratio of chlorosulfonic acid at 55 to 60°C, 4-chlorobenzenesulfonyl chloride is obtained with a yield of 70%,
4,4'-dichlorodiphenyl sulfone is produced in a yield of 9%. Furthermore, when the above reaction is carried out in a 1,2-dichloroethane solvent, the yield of the target product is 69%, and the corresponding sulfone is produced with a yield of 10%. This result shows that there is no effect of the solvent on the yield of the target product and the formation of by-products. Next, by using cross-sulfonic acid in a 3 molar ratio to chlorobenzene, adding 0.3 molar ratio of sodium chloride, and reacting at the above excess, the desired product can be obtained in a yield of 75%. However, the number of sulfones produced is decreasing. The effect of adding this sodium chloride is
Although the yield of the target product is only slightly improved, it is a significant fact that the production of sulfone in the created product is reduced.
On the other hand, in the case of the method of the present invention, i.e., using chlorosulfonic acid in a molar ratio of 3 to chlorobenzene, 1.2
When 0.3 molar ratio of sodium chloride is added to -dichloroethane and the reaction is carried out at 55 to 60 qo, the yield of the target product is significantly improved to 90%, and the yield of the created product is 25%. In this case, in addition to sodium chloride, stannic acids, such as hydrochloric acid, hydrobromic acid, hydrobrodic acid, sulfuric acid, sulfurous acid, nitric acid,
IJ tium, sodium, potassium alkali metal salts and/or ammonium salts such as phosphoric acid are effective and exhibit similar effects. In the first invention, the reaction between chlorobenzene and chlorosulfonic acid is carried out without a solvent or in the presence of an aliphatic halogenated hydrocarbon solvent.

When the reaction is carried out without a solvent, the aliphatic halogenated hydrocarbon is added to the reaction mixture and then subjected to a water washing step. If the reaction is carried out using the abovementioned solvent, the reaction mixture is subjected to a water washing step, either as such or with additional said solvent. In a second invention, the reaction mixture is subjected to a water washing step, either neat) or with an additional aliphatic halogenated hydrocarbon solvent.

In the first invention and the second invention, the molar ratio of chlorobenzene and chlorosulfonic acid used is preferably 2.5 to 4.0 mol, particularly 3.0 to 3.0 mol, of the latter to 1 mol of the former. 5 mol is preferred.

The aliphatic halogenated hydrocarbon used in the methods of both inventions is preferably a lower aliphatic halogenated hydrocarbon having 1 or 2 carbon atoms, in which some or all of the hydrogen atoms have been replaced with halogen. Examples of such aliphatic halogenated hydrocarbons are dichloromethane, chloroform, carbon tetrachloride,
1,1-dichloroethane, 1,2-dichloroethane, 1
・1・1-Trichrome. Ethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1
-2,2-tetrachloroethane, 1,2-dichloroethylene, trichlorethylene, tetrachloroethylene, bentachloroethane, hexachloroethane, and those in which part or all of the chlorine in these has been replaced with other halogens. The amount of the solvent used is not particularly limited, but it is usually used in an amount of 0.5 to 5 times the weight of chlorobenzene. The solvent used in the method of the second invention includes the same aliphatic halogenated hydrocarbons as in the first invention. The amount of the solvent to be used is not particularly limited, but it is usually used in an amount of 0.5 to 50 times the weight of chlorobenzene.

Preferably 1.0 to 3. It is the weight times the amount of As the alkali metal salt of stannic acid, halides, sulfates, sulfites, nitrates or phosphates of lithium, sodium or potassium are used. Ammonium salts of acetic acid include ammonium chloride, ammonium bromide, ammonium iodide, ammonium sulfate, ammonium sulfite, ammonium nitrate and ammonium phosphate. Two or more types of these alkali metal salts or ammonium salts of key acids may be mixed as necessary. The amount of alkali metal salt or ammonium salt of Sun acid to be used is 0.01 to 5 molar ratio to chlorobenzene, preferably 0.0
The molar ratio is 5 to 2. Although there is no particular problem in using it in a molar ratio of 5 or more, a sufficient effect can be obtained with a molar ratio of 5 or less.

In the processes of both inventions, the reaction temperature generally ranges from 0 to 100 pm, preferably from 10 to 90°C.

When carrying out the method of the present invention, in the first invention, it is sufficient that chlorobenzene and chlorosulfonic acid can react together, and in the second invention, although there is no particular limitation, generally chlorosulfonic acid and an alkali IJ metal salt are used. and/or dropping chlorobenzene into the mixture of ammonium salt and organic solvent.

In some cases, chlorosulfonic acid may be added dropwise to the mixture of chlorobenzene, alkali metal salt and/or ammonium salt, and organic solvent. After the dropwise addition is completed, the mixture is stirred at a predetermined temperature and reaction time to obtain a reaction mixture containing the desired 4-chlorobenzenesulfonyl chloride. This reaction mixture is usually cooled to room temperature and then the aliphatic halogenated hydrocarbon is added, or when previously used as a solvent with the above solvent, without or with the addition of additional solvent; Graves included in the reaction mixture.

After washing with enough water to remove the generated sulfuric acid and unreacted chlorosulfonic acid, usually, but not limited to, washing with water in an amount of 5 to 6 times the weight of the chlorosulfonic acid used, Separate the organic solvent layer. Anhydrous 4-chlorobenzenesulfonyl chloride is obtained by distilling off water contained in this separated solution together with the solvent while heating under normal pressure. The present invention will be further explained in detail by showing examples of the present invention below.

Example 1 112.5 mm (1.0 mol) of chlorobenzene was added dropwise into 349 mm (3.0 mol) of chlorosulfonic acid over 3 hours while maintaining the temperature at 50-60°C.

After further stirring at the same temperature for 5 hours, the mixture was cooled to room temperature.
Add 250 g of 1,2-dichloroethane to this, and then add 1 g of water.
Wash with water and separate the organic layer. Further, the same operation was carried out using the same water, and the solvent of the separated solution was removed by heating to obtain crystals of 4-chlorobenzenesulfonyl chloride. The results are shown in Table-1. Example 2 349 moles (3.0 moles) of chlorosulfonic acid were dissolved in 250 moles of 1,2-dichloroethane, and 112.5 moles (1.0 mole) of chlorobenzene was added dropwise over 3 hours while maintaining the temperature at 55 to 60°C. did.

After stirring for an additional 5 hours, the mixture was cooled to room temperature, washed with 1 tablespoon of water, and the organic layer was separated. Furthermore, after carrying out the same operation using the same water, the solvent of the separated solution is
The mixture was heated and removed to obtain crystals of 4-chlorobenzenesulfonyl chloride. The results are shown in Table-1.

Example 3 349 moles (3.0 moles) of chlorosulfonic acid and 17.5 moles (0.3 moles) of sodium chloride were suspended in 250 moles of 1,2-dichloroethane and maintained at a temperature of 55 to 60 °C. While doing so, 112.5 moles (1.0 mol) of chlorobenzene was added dropwise over 3 hours.

After further stirring at the same temperature for 5 hours, the mixture was cooled to room temperature, washed with 1 drop of water, and the organic layer was separated. Further, the same operation was carried out using the same water, and the solvent of the separated solution was distilled off under heating to obtain crystals of 4-k00benzenesulfonyl chloride. The results are shown in Table 1. Example 4
~15 Reaction was carried out in the same manner as in Example 3, except that the amount of chlorosulfonic acid used, the type and amount of alkali metal salt or ammonium salt, the type and amount of solvent used, and the reaction temperature were changed as shown in Table 1. and obtained the desired object.

Claims (1)

[Claims] 1. Reacting chlorobenzene and chlorosulfonic acid,
An anhydrous 4-method, characterized in that the reaction mixture obtained is washed with water in the presence of an aliphatic halogenated hydrocarbon solvent, and then the water is distilled off from the separated organic solvent layer together with said solvent.
Method for producing chlorobenzenesulfonyl chloride. 2. Adding chlorobenzene and chlorosulfonic acid to an alkali metal salt of a mineral acid and/or an alkali metal salt of a mineral acid in an aliphatic halogenated hydrocarbon solvent.
Alternatively, a method for producing 4-chlorobenzenesulfonyl chloride, which comprises carrying out the reaction in the presence of an ammonium salt, washing the resulting reaction mixture with water, and then distilling off the water together with the solvent from the separated organic solvent layer.